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  • Inorganic Chemistry  (83,665)
  • Electron Microscopy
  • Insulin
  • 1
    Electronic Resource
    Electronic Resource
    Short-term treatment with GLP-1 increases pulsatile insulin secretion in Type II diabetes with no effect on orderliness (2000)
    Springer
    Diabetologia 43 (2000), S. 583-588 
    Details
    ISSN: 1432-0428
    Keywords: Keywords GLP-1 ; Insulin ; pulsatility ; insulin secretion ; time series ; Type II diabetes ; human.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Aims/hypothesis. The enteric incretin hormone, glucagon-like peptide-1 (GLP-1), is a potent insulin secretagogue in healthy humans and patients with Type II (non-insulin-dependent) diabetes mellitus. In this study we assessed the impact of short-term GLP-1 infusion on pulsatile insulin secretion in Type II diabetic patients. Methods. Type II diabetic patients (n = 8) were studied in a randomised cross-over design. Plasma insulin concentration time series were obtained during basal conditions and during infusion with saline or GLP-1 (1.2 pmol/l · kg–1· min–1) on 2 separate days. Plasma glucose was clamped at the initial concentration by a variable glucose infusion. Serum insulin concentration time series were evaluated by deconvolution analysis, autocorrelation analysis, spectral analysis and approximate entropy. Results. Serum insulin concentrations increased by approximately 100 % during GLP-1 infusion. Pulsatile insulin secretion was increased as measured by secretory burst mass (19.3 ± 3.8 vs 53.0 ± 10.7 pmol/l/pulse, p = 0.02) and secretory burst amplitude (7.7 ± 1.5 vs 21.1 ± 4.3 pmol/l/min, p = 0.02). A similar increase in basal insulin secretion was observed (3.6 ± 0.9 vs 10.2 ± 2.2 pmol/l/min, p = 0.004) with no changes in the fraction of insulin delivered in pulses (0.50 ± 0.06 vs 0.49 ± 0.02, p = 0.84). Regularity of secretion was unchanged as measured by spectral analysis (normalised spectral power: 5.9 ± 0.6 vs 6.3 ± 0.8, p = 0.86), autocorrelation analysis (autocorrelation coefficient: 0.19 ± 0.04 vs 0.18 ± 0.05, p = 0.66) and the approximate entropy statistic (1.48 ± 0.02 vs 1.51 ± 0.02, p = 0.86). Conclusion/interpretation. Short-term stimulation with GLP-1 jointly increases pulsatile and basal insulin secretion, maintaining but not improving system regularity in Type II diabetic patients. [Diabetologia (2000) 43: 583–588]
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s001250051347
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  • 2
    Electronic Resource
    Electronic Resource
    Pharmacodynamics and pharmacokinetics of intravenous glibenclamide in Caucasian and Chinese patients with type-2 diabetes (2000)
    Springer
    European journal of clinical pharmacology 55 (2000), S. 721-727 
    Details
    ISSN: 1432-1041
    Keywords: Key words Glibenclamide ; Insulin ; Proinsulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: We analysed the kinetics and effects of glibenclamide (Gb) on glucose, insulin and proinsulin secretion in two ethnic groups (10 in each) of type-2 diabetic patients, one of Caucasian, the other of Chinese origin. Background: Diabetes mellitus type 2 is a global disease affecting all ethnic groups. There are ethnic differences in both the prevalence and metabolic characteristics of the disease. Important interethnic pharmacodynamic and pharmacokinetic differences have been reported for several drugs. With few exceptions, detailed studies on sulphonylurea are lacking. Material and methods: The patients were studied on two occasions when either no Gb (control) or 1.25 mg Gb was administered i.v., immediately before the administration of a 75-g oral glucose tolerance test. Concentrations of insulin and proinsulin were determined by means of radioimmunoassay without cross-reactivities. Gb concentration was determined using high-performance liquid chromatography. Pharmacodynamic results were calculated using net areas under the curves, with basal values set as zero. A P value less than 0.05 was considered significant. Results: When glucose was administered orally without Gb, Chinese patients had higher plasma glucose increases at 10 min (7.6 mmol/l × min vs 2.6 mmol/l × min) and higher increases of plasma insulin levels than Caucasians at both 10 min (198 pmol/l × min vs 54 pmol/l × min) and 30 min (2286 pmol/l × min vs 1198 pmol/l × min). When Gb was administered, the plasma glucose increases were reduced, and the increases of serum insulin and proinsulin levels were greater in both ethnic groups. Compared with the basal values (−1 min), proinsulin/insulin ratios (RPI) were lowest at 10–30 min, followed by an increase. Chinese patients had higher increases of serum insulin levels at 10 min (1109 pmol/l × min vs 550 pmol/l × min) and a lower RPI at 30 min (6.0% vs 7.6%) and 240 min (15.0% vs 21.0%) relative to Caucasians. Serum Gb data were best fitted to a biexponential i.v. model. There were no interethnic differences in any of the pharmacokinetic parameters. Conclusion: In summary, following oral glucose administration without Gb, Chinese type-2 diabetic patients had higher plasma insulin levels but also higher plasma glucose levels during the first 10 min, which might reflect reduced insulin sensitivity or more rapid glucose absorption. Gb augmented glucose-induced release of both insulin and proinsulin in both ethnic groups; the effect on insulin secretion was more pronounced. In conclusion, minor pharmacodynamic but no pharmacokinetic differences were found between the two groups. It seems appropriate to employ the same dosage principles when using Gb in Caucasians and Chinese.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s002280050004
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  • 3
    Electronic Resource
    Electronic Resource
    Growth, puberty and hypothalamic-pituitary function in children with suprasellar arachnoid cyst (2000)
    Springer
    European journal of pediatrics 159 (2000), S. 348-355 
    Details
    ISSN: 1432-1076
    Keywords: Key words Arachnoid cyst ; Growth ; Growth hormone deficiency ; Growth hormone treatment ; Insulin ; Leptin ; Puberty ; Precocious puberty
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract A suprasellar arachnoid cyst may cause disorders of growth, puberty and hypothalamic-pituitary function, due to the proximity of the cyst to the hypothalamic-pituitary area. A total of 30 patients (17 boys) with cyst diagnosed at 4.3 ± 1 years were routinely evaluated at 5.4 ± 1 years; 24 of them had one or multiple cyst derivations. Some 23 cases had an abnormal height, weight or puberty: short (〈−2SD, 5 cases) or tall (〉2SD, 10 cases) stature, overweight (body mass index, BMI, 〉2SD, 6 cases), central precocious puberty (10 cases) and/or no progression of pubertal development (3 cases). The growth hormone (GH) peaks after pharmacological stimulation test were low (〈10 μg/l) in 16 patients, confirmed by a second evaluation in 8/11 of them. The plasma free thyroxine was low in five patients, prolactin was high in two and the cortisol and concomitant plasma and urinary osmolalities were normal. BMI was correlated negatively with the GH peaks (r=−0.37, P 〈 0.01) and positively with the plasma leptin concentrations (r=0.55, P 〈 0.01). The plasma fasting insulin concentrations were also correlated negatively with the GH peaks (r=−0.55, P 〈 0.02) and positively with the plasma insulin-like growth factor I concentrations (r=0.64, P 〈 0.002). The adult height (12 cases) was at 4SD in 1 and 〈−2SD in 4 patients, two of whom had precocious puberty untreated with gonadotropin releasing hormone (GnRH) analogue, and two had untreated GH deficiency. The adult height of those treated was normal. One girl had primary amenorrhoea and two boys had low plasma testosterone, despite a normal gonadotropin response to a GnRH test. Conclusion Suprasellar arachnoid cysts may cause deficiencies of growth hormone and thyrotropin, stimulation of the hypothalamic-pituitary-gonadal axis, tall stature and/or overweight. These last two disorders may be due to hyperinsulinism, itself due to suprasellar arachnoid cyst.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004310051285
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  • 4
    Electronic Resource
    Electronic Resource
    IGF and Insulin Action in the Mammary Gland: Lessons from Transgenic and Knockout Models (2000)
    Springer
    Journal of mammary gland biology and neoplasia 5 (2000), S. 19-30 
    Details
    ISSN: 1573-7039
    Keywords: Insulin ; transgenic ; knockout ; mammary ; IGF
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Transgenic and knockout mice have become valuable experimental systems with which tostudy specific molecular events within the mammary gland of an intact animal. These modelshave provided a wealth of information about the effects of a number of oncogenes and growthfactors. This review focuses on results obtained from the application of transgenic and knockoutmodels to determine the roles of insulin and insulin-like growth factors (IGF)3 in the regulationof mammary gland development, lactation and tumorigenesis. Transgenic models whichoverexpress IGF-I or -II display specific alterations in mammary gland development and an increasedincidence of mammary tumors. Analysis of mammary gland development in knockout micewhich are deficient in IGF-I or the IGF-I receptor supports the conclusion that the IGF systemis important for normal mammary gland development. This review discusses these observationsin detail and attempts to fit them into a larger picture of IGF and insulin action in themammary gland.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1009559014703
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  • 5
    Electronic Resource
    Electronic Resource
    Nitric Oxide, Superoxide, and Peroxynitrite Effects on the Insulin Secretion and Viability of βTC3 Cells (2000)
    Springer
    Annals of biomedical engineering 28 (2000), S. 102-109 
    Details
    ISSN: 1573-9686
    Keywords: Nitric oxide ; Superoxide ; Pancreatic cells ; Insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Technology
    Notes: Abstract The onset of insulin-dependent diabetes mellitus (IDDM) is often associated with the infiltration of pancreatic cells by macrophages. Upon activation, macrophages release nitric oxide (NO) and superoxide (O 2 - ). These species or their reactive intermediates can be cytoxic, mutagenic, or carcinogenic. Previous studies have reported both positive and negative effects of extracellularly generated NO on insulin secretion and viability of pancreatic cells. Inherent problems of several previous studies assessing the effects of NO on insulin secretion include unsteady state NO concentration exposures and the generation of other potentially damaging species. In this study, these problems were eliminated by using a modified experimental system in which NO delivery was achieved via diffusion across a gas-permeable tube and O 2 - delivery was maintained using an enzymatic reaction. The delivery rates were constant, leading to steady state concentrations of NO and O 2 - in the experimental system. Based on reaction kinetics, a model was developed to predict NO, O 2 - and peroxynitrite ONOO- concentrations during the experiment. This study showed that NO, O 2 - and ONOO- at predicted concentrations as high as 2.8 μM, 0.25 μM, and 0.1 nM, respectively, do not affect the insulin secretion rates of βTC3 pancreatic cells over short times. © 2000 Biomedical Engineering Society. PAC00: 8717-d
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1114/1.258
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  • 6
    Electronic Resource
    Electronic Resource
    Bayesian Identification of a Population Compartmental Model of C-Peptide Kinetics (2000)
    Springer
    Annals of biomedical engineering 28 (2000), S. 812-823 
    Details
    ISSN: 1573-9686
    Keywords: C-peptide ; Population model ; Compartmental model ; Bayes estimation ; Markov chain Monte Carlo ; Insulin ; System identification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Technology
    Notes: Abstract When models are used to measure or predict physiological variables and parameters in a given individual, the experiments needed are often complex and costly. A valuable solution for improving their cost effectiveness is represented by population models. A widely used population model in insulin secretion studies is the one proposed by Van Cauter et al. (Diabetes 41:368–377, 1992), which determines the parameters of the two compartment model of C-peptide kinetics in a given individual from the knowledge of his/her age, sex, body surface area, and health condition (i.e., normal, obese, diabetic). This population model was identified from the data of a large training set (more than 200 subjects) via a deterministic approach. This approach, while sound in terms of providing a point estimate of C-peptide kinetic parameters in a given individual, does not provide a measure of their precision. In this paper, by employing the same training set of Van Cauter et al., we show that the identification of the population model into a Bayesian framework (by using Markov chain Monte Carlo) allows, at the individual level, the estimation of point values of the C-peptide kinetic parameters together with their precision. A successful application of the methodology is illustrated in the estimation of C-peptide kinetic parameters of seven subjects (not belonging to the training set used for the identification of the population model) for which reference values were available thanks to an independent identification experiment. © 2000 Biomedical Engineering Society. PAC00: 8715Aa, 0250Ga, 8714-g
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1114/1.1289459
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  • 7
    Electronic Resource
    Electronic Resource
    Early Development of the Secretory Cavity of Peltate Glands in Humulus lupulus L. (Cannabaceae) (2000)
    Springer
    Molecules and cells 10 (2000), S. 487-492 
    Details
    ISSN: 0219-1032
    Keywords: Development ; Electron Microscopy ; Humulus ; Peltate Gland ; Secretion ; Secretory Cavity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Early development of the secretory cavity of chemically fixed peltate glands in Humulus lupulus L. showed secretions with different densities, light, gray and dark, in the cytoplasm of disc cells and in the periplasmic space adjacent to the developing secretory cavity. Secretions were detected in the disc cell wall and subsequently in the developing secretory cavity under the subcuticular wall of the sheath. Light and gray secretions in the cavity possessed a membrane-like surface feature. Secretions were in contact with the irregular inner surface of the cuticle. Secretions contributed to the thickening of the cuticle, whereas the membrane-like surface feature contributed to a network of Cannabis striae distributed throughout the cuticle. This study supports an early development and organization of the secretory cavity in H. lupulus, parallel to those in Cannabis, and may represent common features for lipophilic glands in angiosperms.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s10059-000-0487-5
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  • 8
    Electronic Resource
    Electronic Resource
    Muscle glycogen resynthesis rate in humans after supplementation of drinks containing carbohydrates with low and high molecular masses (2000)
    Springer
    European journal of applied physiology 81 (2000), S. 346-351 
    Details
    ISSN: 1439-6327
    Keywords: Key words Carbohydrate ; Osmolality ; Glycogen ; Insulin ; Glucose
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The rate of muscle glycogen synthesis during 2 and 4 h of recovery after depletion by exercise was studied using two energy equivalent carbohydrate drinks, one containing a polyglucoside with a mean molecular mass of 500 000–700 000 (C drink), and one containing monomers and oligomers of glucose with a mean molecular mass of approximately 500 (G drink). The osmolality was 84 and 350 mosmol · l−1, respectively. A group of 13 healthy well-trained men ingested the drinks after glycogen depleting exercise, one drink at each test occasion. The total amount of carbohydrates consumed was 300 g (4.2 g · kg−1) body mass given as 75 g in 500 ml water immediately after exercise and again 30, 60 ad 90-min post exercise. Blood glucose and insulin concentrations were recorded at rest and every 30 min throughout the 4-h recovery period. Muscle biopsies were obtained at the end of exercise and after 2 and 4 h of recovery. Mean muscle glycogen contents after exercise were 52.9 (SD 27.4) mmol glycosyl units · kg−1 (dry mass) in the C group and 58.3 (SD 35.4) mmol glycosyl units · kg−1 (dry mass) in the G group. Mean glycogen synthesis rate was significantly higher during the initial 2 h for the C drink compared to the G drink: 50.2 (SD 13.7) mmol · kg−1 (dry mass) · h−1 in the C group and 29.9 (SD 12.5) mmol · kg−1 (dry mass) · h−1 in the G group. During the last 2 h the mean synthesis rate was 18.8 (SD 33.3) and 23.3 (SD 22.4) mmol · kg−1 (dry mass) · h−1 in the C and G group, respectively (n.s.). Mean blood glucose and insulin concentrations did not differ between the two drinks. Our data indicted that the osmolality of the carbohydrate drink may influence the rate of resynthesis of glycogen in muscle after its depletion by exercise.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004210050053
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  • 9
    Electronic Resource
    Electronic Resource
    Insulin alters cardiac muscle creatine kinase activity (2000)
    Springer
    Heart and vessels 15 (2000), S. 23-29 
    Details
    ISSN: 1615-2573
    Keywords: Key words Creatine kinase isoenzyme ; Insulin ; Atenolol ; Diabetes mellitus ; Myocardium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The expression of mRNAs of creatine kinase (CK)-B and CK-M has been show to be affected by insulin, and myocardial CK-MB activity is suppressed in insulin-deficient rats. We investigated the dose-related effect of insulin on CK-MB activity in cardiac and skeletal muscles. Male Wistar rats were divided into three groups: (1) control group, (2) diabetic group, injected with 65 mg/kg streptozotocin for 4 weeks, and (3) atenolol group, administered 30 mg/kg per day atenolol. Each group was further divided into three subgroups and administered either saline, or 20 (Ins 20) or 30 (Ins 30) U/kg per day insulin. After 3 weeks, the isoenzyme activity of CK and lactate dehydrogenase (LDH) in the left ventricle of the heart (LV) and the major pectoral muscle (PM) was measured. Serum insulin increased and plasma glucose decreased in Ins 20 and Ins 30, dose-dependently, in all three groups. Both CK-MB and -BB activity in LV increased dose-dependently with insulin treatment in the control, diabetes, and atenolol groups, although these changes did not occur in skeletal muscles. CK-MB in LV correlated with the serum insulin levels in all rats, while no correlation was found in the skeletal muscles. These findings suggest that insulin possibly regulates the distribution of CK isoenzymes in rat heart muscle, and that the effect of insulin is not due to the sympathetic drive induced by hypoglycemia.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s003800070044
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  • 10
    Electronic Resource
    Electronic Resource
    The autumnal fattening of the long-distance migratory garden warbler (Sylvia borin) is stimulated by intermittent fasting (2000)
    Springer
    Journal of comparative physiology 170 (2000), S. 627-631 
    Details
    ISSN: 1432-136X
    Keywords: Key words Fattening ; Food availability ; Insulin ; Glucagon ; Corticosterone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract To investigate the proximate influence of a changing food availability on the seasonal fattening of migratory birds, garden warblers (Sylvia borin) following postnuptial moult were food restricted once a week. Body mass, food intake, plasma hormone and metabolite levels were measured and compared to birds which always had ad libitum food access. The food-restricted birds increased their body mass significantly earlier than the controls. The accelerated fattening was initially not accompanied by hyperphagia and may be due to either an increased food utilisation efficiency or a reduced metabolic rate. An increase of basal glucagon and corticosterone and a decrease of insulin levels prior to fattening were not significant, however, they resulted in a significant decrease of the insulin:glucagon ratio. This ratio was also lower in food-restricted birds than in control birds and may account for the difference in the fattening progress. We conclude that seasonal fattening may be stimulated by a catabolic impulse which could be imposed in free-living birds by a decrease of food availability and/or by an increase of energy expenditure. A negative energy balance is hypothesised to be a common proximate factor affecting migratory as well as winter fattening.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s003600000143
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  • 11
    Electronic Resource
    Electronic Resource
    Nutrient-dependent distribution of insulin and glucokinase immunoreactivities in rat pancreatic beta cells (1999)
    Springer
    Virchows Archiv 434 (1999), S. 75-82 
    Details
    ISSN: 1432-2307
    Keywords: Key words Rat ; Pancreatic beta cell ; Insulin ; GLUT2 glucose transporter ; Glucokinase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Functional heterogeneity among pancreatic beta cells is a characteristic feature of the islets of Langerhans. Under physiological conditions, beta cells in the pancreas of fed rats exhibited heterogeneous immunohistochemical staining for insulin and glucokinase. Intracellular beta cell glucokinase staining was either faint or dense. In the pericapillary space beta cell glucokinase immunoreactivity had a polar orientation, with the highest density in cytoplasmic regions close to the blood vessels. Starvation resulted in a loss of heterogeneity with homogeneous insulin staining in all beta cells of the islets, and this was accompanied by a loss of heterogeneous glucokinase staining. The intracellular polarity of glucokinase staining in contact to blood vessels also disappeared after starvation. Refeeding resulted in the reappearance of intercellular heterogeneity. In dependence on the functional demand, the endocrine pancreas recruited insulin from beta cells according to a well-defined hierarchy, with an initial preferential mobilization of medullary beta cells. In the course of this process intracellular polarity of glucokinase staining reappeared in areas of the beta cell with functional contact to the GLUT2 glucose transporter in the plasma membrane. This can be regarded as the morphological correlate of an activation of the glucose signal recognition apparatus. Interestingly, the study also provides evidence that the changes in glucokinase distribution apparently preceded those in insulin distribution, which is in keeping with the central role of glucokinase as the glucose sensor of the pancreatic beta cell.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004280050308
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  • 12
    Electronic Resource
    Electronic Resource
    Effects of combination of insulin and acarbose compared with insulin and gliclazide in type 2 diabetic patients (1999)
    Springer
    Acta diabetologica 36 (1999), S. 93-97 
    Details
    ISSN: 1432-5233
    Keywords: Key words Type 2 diabetes mellitus ; Insulin ; Acarbose ; Gliclazide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract In this prospective study we aimed to compare insulin plus acarbose with insulin plus gliclazide with respect to their effect on insulin requirement, lipid profiles and body mass index (BMI) while achieving good glycemic control. Forty patients with type 2 diabetes mellitus who were on conventional insulin therapy (subcutaneous insulin therapy consisting of regular and NPH insulin, two times a day) were included in the study. They were randomized to double blind treatment with insulin in combination with gliclazide or acarbose for 6 months. For both groups, acceptable glycemic control was achieved at the end of study period. The mean HbA1c levels decreased from 8.32±0.26 to 7.13±0.18% in acarbose group and 8.6±0.15 to 7.48±0.21% in the gliclazide group. The difference between groups was not significant (P 0.29). In the acarbose group, total cholesterol and LDL concentration decreased significantly while other parameters did not change. In the gliclazide group, HDL levels decreased significantly from 46.6±2.48 mg/dl to 41.3±2.09 mg/dl (P 0.001) BMI increased significantly from 27.60±1.21 kg/m2 to 28.69±1.26 kg/m2. (P 0.003) Total daily insulin dose was not changed in the acarbose group significantly, but increased from 42.6±2.73 to 49.27±3.58 U/day, which was significant in gliclazide group of (P 0.016). In the acarbose group, there were no significant differences between responders and nonresponders with respect to fasting and stimulated C-peptide, HbA1c levels and baseline BMI values. But in the gliclazide group, baseline BMI values were significantly higher in the nonresponding group compared to responders (P 0.02). In conclusion, combination of insulin with acarbose can be a good alternative for type 2 diabetic patients on insulin therapy; seems more beneficial than combination with gliclazide; may have advantage of achieving good glycemic control without increasing insulin dose and BMI; also may have the advantage of providing a decrease in LDL level, which are all important to prevent atherosclerosis.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s005920050151
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  • 13
    Electronic Resource
    Electronic Resource
    Increased glucagon-stimulated insulin secretion of cryopreserved rat islets transplanted into nude mice (1999)
    Springer
    Journal of molecular medicine 77 (1999), S. 107-110 
    Details
    ISSN: 1432-1440
    Keywords: Key words Pancreatic islet transplantation ; Cryopreservation ; Conservation ; Insulin ; Nude mice
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Cryopreservation is the only available technique for long-term storage of pancreatic islets. The freezing/thawing protocol may cause considerable loss of viable islet tissue and impair its function in vivo. The aim of this study was to investigate glucose and insulin levels after transplantation of fresh and cryo/thawed rat islets. Rat pancreatic islets were isolated following intraductal collagenase injection and Ficoll gradient purification. After isolation, islets were cultured for 24 h and then either transplanted or frozen after stepwise addition of DMSO according to Rajotte et al. and stored in liquid nitrogen. After rapid thawing islets were stepwise transferred into RPMI medium and cultured for another 24 h. The recipients were athymic mice with streptozotocine-induced diabetes. Two hundred fresh (n=13) or cryo/thawed (n=15) islets were transplanted beneath the renal capsule. Glucose levels were measured for 14 days and blood samples for insulin determination were obtained 15 min after i.p. glucagon (10 mg/kg) administration on day 14. Glucose levels were normalized (〈9 mmol/l) in all recipients within 3 days since transplantation. On day 14, mean fasting values±SE in fresh and cryo/thawed islet groups were 4.0±0.6 and 4.4±0.4 mmol/l, respectively (P〉0.05). Fasting insulin levels were higher in the cryo/thaw than in the fresh islet group (1.67±0.33 vs 0.57±0.13 ng/ml; P〈0.01). Post-glucagon levels did not differ significantly (1.45±0.24 vs 0.86±0.24 ng/ml; P=0.06). While glucagon significantly increased insulin levels (P〈0.01) in the fresh islet group, no change in insulin levels was observed (P〉0.05) in the cryo/thaw group. Immunohistochemical staining demonstrated fragmentation of viable islet tissue which was more apparent in the cryo/thaw group. We conclude that in a short-term study cryo/thawed rat islets produce higher insulin levels than fresh islets transplanted into nude mice. This may be due to better islet survival or loss of feed-back regulation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s001090050313
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  • 14
    Electronic Resource
    Electronic Resource
    Gene transfer into insect brain and cell-specific expression of bombyxin gene (1999)
    Springer
    Development genes and evolution 209 (1999), S. 447-450 
    Details
    ISSN: 1432-041X
    Keywords: Key words Bombyxin ; Insulin ; Bombyx mori ; Electroporation ; Cell-specific expression
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  A transgene reporter consisting of the bombyxin gene promoter and the green fluorescent protein coding region was introduced into intact brains of the silkworm Bombyx mori by in vitro electroporation. After in vitro culture of the brains, the fluorescence derived from the introduced reporter gene was observed in all cases in eight neurosecretory cells that had previously been identified as bombyxin-producing cells (BPCs). Although the fluorescence was not always observed in all cells, it was specific to BPCs, indicating that the reporter was under the control of the bombyxin gene promoter in a BPC-specific manner. Electroporatical introduction of a reporter gene was therefore found to be a suitable method for analyzing cell-specific expression in intact tissues and to be substitute for germ-line transmission of reporters in the transgenic system. Application of this technique enables us to analyze the cell-specific expression of transgene reporters within a few days and treat more than several dozens of the reporters within 1 month, which is difficult to do with the transgenic system.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004270050277
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  • 15
    Electronic Resource
    Electronic Resource
    Insulin modulation of ATP-sensitive K+ channel of rat skeletal muscle is impaired in the hypokalaemic state (1999)
    Springer
    Pflügers Archiv 437 (1999), S. 235-240 
    Details
    ISSN: 1432-2013
    Keywords: Key words Hypokalaemic periodic paralysis ; ATP-sensitive K+ channels ; Insulin ; Skeletal muscle ; Patch clamp
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  In the present work, we examined the effects of in vivo administration of insulin to rats made hypokalaemic by feeding a K+-free diet. The i.p. injection of insulin in the hypokalaemic rats provoked muscle paralysis within 3–5 h. Consistent with this observation, the skeletal muscle fibres of the paralysed rats were depolarized. In contrast, in the normokalaemic animals, insulin neither provoked paralysis nor produced significant fibre hyperpolarization. In the hypokalaemic rats, insulin almost completely abolished the sarcolemma adenosine triphosphate (ATP)-sensitive K+ currents without altering the sensitivity of the channels to ATP or glibenclamide. In contrast, in the normokalaemic rats, insulin enhanced ATP-sensitive K+ currents that became also resistant to ATP and glibenclamide. Our experiments indicate that the modulation of the sarcolemma ATP-sensitive K+ channels by insulin is impaired in the hypokalaemic state. This phenomenon appears to be related to the fibre depolarization and paralysis observed in the same animals.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004240050774
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  • 16
    Electronic Resource
    Electronic Resource
    Interleukin-1β-induced nitric oxide synthesis in aortic rings from normal and hyperinsulinaemic rats: effect of physical exercise (1999)
    Springer
    Naunyn-Schmiedeberg's archives of pharmacology 360 (1999), S. 63-68 
    Details
    ISSN: 1432-1912
    Keywords: Key words Arterial smooth muscle ; Glucose ; Inducible NO synthesis ; Insulin ; Lean and obese Zucker rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Insulin has been suggested to prevent the induction of nitric oxide synthase (NOS) in vitro in arterial smooth muscle, but whether such a mechanism is operative in vivo is not known. Therefore, we evaluated the sensitivity of smooth muscle NOS to induction by interleukin-1β (IL-1β) in aortic rings of lean and obese Zucker rats, a model of experimental hyperinsulinaemia. In order to modulate the insulin and glucose balance of the rats, a 22-week-long treadmill exercise was included in the study. The training attenuated weight gain and reduced blood glucose in the obese and lean rats, whereas the abnormally high plasma insulin of the obese rats remained unaffected. A 6-h incubation of aortic rings with IL-1β (10 ng/ml) increased cyclic GMP in smooth muscle by approximately threefold in all groups, and this effect was prevented by methylene blue. The contractile sensitivity of endothelium-denuded aortic rings to phenylephrine was reduced by incubation with IL-1β (1 ng/ml and 10 ng/ml) in the exercised obese and lean rats, whereas no significant change was observed in the sedentary groups. The aortic maximal contractile force induced by phenylephrine was reduced in sedentary and exercised obese rats by incubation with IL-1β, while no change was detected in the lean rats. The aortic relaxation to exogenous L-arginine was augmented by IL-1β in all groups, while the relaxation sensitivity to L-arginine after induction by IL-1β was enhanced by exercise in the obese but not in the lean rats. Finally, the relaxation to nitroprusside was not significantly affected by IL-1β in any of the study groups. In conclusion, since maximal contractile force generation to phenylephrine was reduced by IL-1β in the obese but not in the lean rats, the sensitivity of NOS to induction by IL-1β was higher in arterial smooth muscle of the obese than the lean Zucker rats. Thus, this model of hyperinsulinaemia was not associated with reduced sensitivity of smooth muscle NOS to induction by IL-1β. Regular exercise did not change plasma insulin concentrations, but it enhanced the action of insulin in both strains as reflected by reduced blood glucose, and increased the sensitivity of smooth muscle NOS to induction by IL-1β.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s002109900036
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  • 17
    Electronic Resource
    Electronic Resource
    Forskolin increases apical sodium conductance in cultured toad kidney cells (A6) by stimulating membrane insertion (1999)
    Springer
    Pflügers Archiv 438 (1999), S. 195-204 
    Details
    ISSN: 1432-2013
    Keywords: Key words A6 cells ; Capacitance ; Hormones ; Insulin ; Membrane area ; Membrane traffic ; Renal epithelia ; Water permeability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The role of membrane traffic in the stimulation of apical Na+ permeability caused by increases in cytoplasmic cyclic AMP was assessed by measuring the effects of forskolin on transepithelial capacitance (C T), transepithelial conductance (G T), and short-circuit current (I sc) in A6 cultured toad kidney cells. Apical water permeability was probed by recording cell volume changes after reducing the osmolality of the apical bath. We found that forskolin does not increase the osmotic water permeability of the apical membrane of A6 cells, and thus does not stimulate the insertion of water channels. Comparison of the effects of forskolin and insulin on Na+ transport demonstrated that both agents produce reversible increases in C T, G T and I sc. G T and C T increased proportionally during the rising phase of the insulin response. However, a non-linear relationship between both parameters was recorded when forskolin was given in NaCl Ringer’s solution. The relationship between C T and G T became linear after the effects of forskolin on Cl– conductances were eliminated by substituting Cl– by an impermeant anion. In contrast, in Cl–-containing Na+-free solutions, the non-linearity became more pronounced. Successive additions of insulin and forskolin caused additive increases in C T. Because increases in C T and Na+ transport occurred in the absence of stimulation of water permeability and increases of C T and G T were directly proportional when Na+ was the major permeating ion across the apical membrane, we suggest that the increase in apical Na+ permeability in the presence of either forskolin or insulin is due to the insertion of channels residing in intracellular pools. In contrast, the increased Cl– permeability caused by forskolin may be related to the activation of channels already present in the membrane.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004240050898
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  • 18
    Electronic Resource
    Electronic Resource
    Metabolic and ultrastructural effects of cyclosporin A on pancreatic islets (1999)
    Springer
    Transplant international 12 (1999), S. 208-212 
    Details
    ISSN: 1432-2277
    Keywords: Key words Cyclosporin A ; Langerhans ; Insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We investigated the effect of different doses of cyclosporin A (CyA) on glucose and insulin levels, as well as its residual effects on pancreatic islets ultrastructure after discontinuation of the drug. We studied four groups of Wistar rats. One control- (n = 5) and three experimental groups, n = 10 each, were treated with different doses of CyA IM for 14 days: group I, 5 mg/Kg; group II, 15 mg/Kg; and group III, 25 mg/Kg. Five animals of each group were sacrificed after 14 days, and the remaining five after 21 days to assess residual CyA effects. On the day of sacrifice, the rats underwent maltose absorption test, and glucose and insulin levels were measured. Pancreatic biopsies were obtained on day 21 to evaluate islets ultrastructure by electron microscopy. As a result, statistically significant, dose dependent (P 〈 0.05) increases in glucose and insulin levels were observed in CyA-treated groups. Groups II and III showed insulin levels significantly higher after fasting (P 〈 0.05) on day 14 comparing to the controls, while in groups I and II values returned to normal after CyA discontinuation. Group III showed persistently increased insulin levels on day 21. Pancreatic ultrastructural changes were observed only in group III. We can conclude that CyA effects on glucose and insulin levels were temporary and reversible at low doses. Ultrastuctural changes in the pancreatic islets may occur with high doses of CyA.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s001470050212
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  • 19
    Electronic Resource
    Electronic Resource
    Insulin-induzierte Hypoglycaemia factitia aus diätetischen Gründen (1999)
    Springer
    Rechtsmedizin 9 (1999), S. 190-192 
    Details
    ISSN: 1434-5196
    Keywords: Key words Hypoglycaemia factitia ; Insulin ; Diet ; Lethal outcome ; Schlüsselwörter Hypoglykaemia factitia ; Insulin ; Diät ; Tödlicher Verlauf
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Law
    Description / Table of Contents: Zusammenfassung Wir berichten über den Fall einer 28jährigen, nicht insulinpflichtigen nicht-Diabetikerin, in deren Anamnese eine hypoglykaemische Episode vor dem Todeseintritt bekannt wurde. Autoptisch wurde eine (heimliche) Applikation von Insulin durch letal hohe Insulinspiegel im zentralen und peripheren Blut mit Hypoglykaemie diagnostiziert. Nach der Anamnese, den Ergebnissen des Ermittlungsverfahrens und der Autopsie konnte die Applikation von Insulin aus suizidaler und homizidaler Absicht oder im Rahmen eines Münchhausen-Syndroms ausgeschlossen werden. Vielmehr handelte es sich in der Gesamtschau um eine Hypoglykaemia factitia aus diätetischen Gründen.
    Notes: Abstract The medical history of a 28-year-old non-insulin-dependent and non-diabetic patient with a hypoglycaemic episode before death is reported. At autopsy, an (surreptious) insulin administration was documented by lethally high serum insulin in central and peripheral blood during hypoglycaemia, According to the anamnesis, the judical inquiry and the autopsy findings, a suicidal intent, murder by insulin or Munchhausen-syndrome could be excluded. We therefore diagnosed a hypoglycaemia factitia caused by the diet.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s001940050107
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  • 20
    Electronic Resource
    Electronic Resource
    Effect of moderate physical activity on plasma leptin concentration in humans (1999)
    Springer
    European journal of applied physiology 79 (1999), S. 331-335 
    Details
    ISSN: 1439-6327
    Keywords: Key words Leptin ; Exercise Energy balance ; Insulin ; Glucocorticoids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract In subjects who maintain a constant body mass, the increased energy expenditure induced by exercise must be compensated by a similar increase in energy intake. Since leptin has been shown to decrease food intake in animals, it can be expected that physical exercise would increase energy intake by lowering plasma leptin concentrations. This effect may be secondary either to exercise-induced negative energy balance or to other effects of exercise. To delineate the effects of moderate physical activity on plasma leptin concentrations, 11 healthy lean subjects (4 men, 7 women) were studied on three occasions over 3 days; in study 1 they consumed an isoenergetic diet (1.3 times resting energy expenditure) over 3 days with no physical activity; in study 2 the subjects received the same diet as in study 1, but they exercised twice daily during the 3 days (cycling at 60 W for 30 min); in study 3 the subjects exercised twice daily during the 3 days, and their energy intake was increased by 18% to cover the extra energy expenditure induced by the physical activity. Fasting plasma leptin concentration (measured on the morning of day 4) was unaltered by exercise [8.64 (SEM 2.22) 7.17 (SEM 1.66), 7.33 (SEM 1.72) 1μg · l−1 in studies 1, 2 and 3, respectively]. It was concluded that a moderate physical activity performed over a 3-day period does not alter plasma leptin concentrations, even when energy balance is slightly negative. This argues against a direct effect of physical exercise on plasma leptin concentrations, when body composition is unaltered.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004210050516
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  • 21
    Electronic Resource
    Electronic Resource
    Genome-wide scanning for type 2 diabetes susceptibility in Canadian Oji-Cree, using 190 microsatellite markers (1999)
    Springer
    Journal of human genetics 44 (1999), S. 10-14 
    Details
    ISSN: 1435-232X
    Keywords: Key words Complex disease ; Carbohydrate ; Insulin ; Aboriginal populations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract We undertook a genome-wide scan using 190 markers with an average separation of 20 cM in 49 Canadian Oji-Cree sib pairs affected with type 2 diabetes. Four of these markers, one each on chromosomes 6, 8, 16, and 22, showed both suggestive linkage and suggestive association with type 2 diabetes in the Oji-Cree. None of these markers corresponded to any chromosomal region or marker that has so far been linked with type 2 diabetes in other populations. Thus, there might be several genetic loci that confer susceptibility to type 2 diabetes in this study sample. We are following up on these preliminary leads by increasing the density of the markers within these linked and associated regions, and also by increasing the number of study subjects. Also, we found instances in which there were wide disparities between the Oji-Cree and reference Caucasians with respect to marker heterozygosity. This suggests that a particular set of markers for genome-wide scanning will have different informativeness in different ethnic groups. Thus, different marker sets will likely be required for different ethnic groups in order to maximize their information content for linkage calculations.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s100380050097
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  • 22
    Electronic Resource
    Electronic Resource
    The effect of euglucaemic hyperinsulinaemia on forearm blood flow and glucose uptake in the human forearm (1998)
    Springer
    Acta diabetologica 35 (1998), S. 203-206 
    Details
    ISSN: 1432-5233
    Keywords: Key words Glucose ; Insulin ; Hyperinsulinaemia ; Blood flow
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Insulin-mediated stimulation of blood flow to skeletal muscle has been proposed to be of major importance for insulin-mediated glucose uptake. The aim of this study was to investigate the relative importance of blood flow and glucose extraction as determinants of insulin-mediated glucose uptake in the human forearm. Forearm blood flow (FBF), glucose extraction and oxygen consumption were evaluated for 100 min during the euglycaemic hyperinsulinaemic clamp (92 mU/l) in nine healthy subjects. FBF was measured by venous occlusion plethysmography. Forearm glucose uptake increased sevenfold during the hyperinsulinaemia (P〈0.001). Forearm glucose extraction showed a minor increase during the first 10 min of hyperinsulinaemia, but the most marked increase took place between 10 and 20 min (+170%). Thereafter, only a minor further increase was seen. During the first 10 min of hyperinsulinaemia FBF was unchanged. Thereafter, FBF increased steadily to a plateau reached after 60 min (+50%, P〈0.001). A close relationship between whole body glucose uptake and FBF was seen at the end of the clamp (r = 0.75, P〈0.02), but at this time the relationship between whole body glucose uptake and forearm glucose extraction was not significant. The modest increase in O2 consumption seen at the beginning of the clamp (+19%) was not related to FBF during the early phase of the clamp. In conclusion, the early course of insulin-mediated glucose uptake in the human forearm was mainly due to an increase in glucose extraction. However, with time the insulin-mediated increase in blood flow increased in importance and after 100 min of hyperinsulinaemia FBF was the major determinant of glucose uptake.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s005920050132
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  • 23
    Electronic Resource
    Electronic Resource
    Functioning human insulinomas (1998)
    Springer
    Virchows Archiv 433 (1998), S. 495-504 
    Details
    ISSN: 1432-2307
    Keywords: Key words Insulinomas ; Prohormone convertases ; Carboxypeptidase H ; Insulin ; Proinsulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Sixty-seven insulinomas were investigated by immunohistochemistry using site-directed antibodies against insulin, proinsulin, chromogranin A, HISL-19, and four proteins directly or indirectly involved in the proteolytic processing of proinsulin: the prohormone convertases PC2 and PC3, carboxypeptidase H (CPH) and 7B2. Results were expressed in a six-grade score according to the frequency of immunoreactive tumour cells. Insulin was expressed by all tumours, appearing in either a diffuse or a polarized pattern and being detected in more than 30% of tumour cells in all cases but three. Proinsulin was also expressed in all tumours, with more than 50% of tumour cells immunoreactive in all cases but 5. It was consistently localized in the Golgi apparatus. In about half the cases, moreover, it also showed diffuse cytoplasmic staining, usually with a very sparse distribution. Trabecular and solid insulinomas did not present specific, homogeneous patterns of insulin immunostaining. However, insulin immunoreactivity was much more abundant in trabecular than in solid neoplasms, being present in virtually all tumour cells (score 6) in 50% and 8% of cases, respectively. Virtually all insulinomas expressed PC2, PC3, CPH and 7B2, usually in 30–100% of tumour cells, with a frequency significantly related to that of insulin. However, detection of PC2 and 7B2 was slightly less frequent than that of PC3 and CPH. In consecutive sections these proteins were found to be mostly co-localized with insulin and chromogranin A but not with proinsulin. They were heavily expressed in all 10 tumours with more than 10% of cells showing cytoplasmic proinsulin immunoreactivity, indicating that the leakage of proinsulin from the Golgi compartment is not associated with faulty expression of converting enzymes and possibly reflects a saturated processing capacity. HISL-19 immunoreactivity was found in both Golgi apparatus and insulin stores, indicating that the relevant antigen is different from all other proteins investigated. These results do not support a defect in expression or localization of proinsulin-processing enzymes in most insulinomas.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004280050280
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  • 24
    Electronic Resource
    Electronic Resource
    Neuropathy in diabetic BB/Wor rats treated with insulin implants (1998)
    Springer
    Acta neuropathologica 96 (1998), S. 144-150 
    Details
    ISSN: 1432-0533
    Keywords: Key words Neuropathy ; Hypoglycaemia ; Hyperglycaemia ; Insulin ; BB/Wor rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract To elucidate the pathophysiology of diabetic neuropathy many workers have examined nerve specimens from diabetic rats. While most workers found that animals with high blood glucose levels develop neuropathy, some researchers report that the peripheral nerves are normal in hyperglycaemic rats. Hypoglycaemia may also cause neuropathy. Some workers suggest that neuropathy is linked to fluctuations of the blood glucose level. In the present study we examine plantar nerves of diabetic BB/ Wor rats maintained on an eu-/hyperglycaemic or an eu-/ hypoglycaemic regime with insulin implants. Treatment with implants worked well. Light microscopic examination of nerve fibres in non-diabetic control rats and in eu-/ hyperglycaemic diabetic rats showed a normal picture. Preparations from eu-/hypoglycemic rats showed irregular myelin sheaths and signs of Wallerian degeneration. The lengths and diameters of the largest internodes were significantly subnormal. We conclude, that periodic moderate hypoglycaemia, but not periodic moderate hyperglycaemia, elicits neuropathy in diabetic BB/Wor rats treated with insulin implants.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004010050874
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  • 25
    Electronic Resource
    Electronic Resource
    Hypoglycaemic neuropathy in BB/Wor rats treated with insulin implants: electron microscopic observations (1998)
    Springer
    Acta neuropathologica 96 (1998), S. 151-156 
    Details
    ISSN: 1432-0533
    Keywords: Key words Neuropathy ; Hypoglycemia ; Insulin ; implant ; Rat ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Insulin-dependent diabetes mellitus is a chronic metabolic disease that causes long-term secondary complications such as neuropathy. The occurrence of diabetic neuropathy has generally been thought of as being associated with hyperglycaemia. However, in a previous light microscopic examination of plantar nerves in diabetic BB/Wor rats treated with insulin implants we found that eu-/hyperglycaemic rats present a normal picture, whereas eu-/hypoglycaemic rats show severe changes. The aim of the present work is to supplement our previous light microscopic report with electron microsocpic data from the lateral plantar nerve of normal, eu-/hyperglycaemic and eu-/hypoglycaemic BB/Wor rats. Under the electron microscope lateral plantar nerves collected from eu-/hyperglycaemic rats presented a qualitatively normal picture. In addition, the fibre numbers and the size distribution of the myelinated fibres were normal. In contrast, specimens from eu-/hypoglycaemic BB/Wor rats showed severe qualitative changes, interpreted as signs of axonal de- and regeneration. The total number of axons was somewhat subnormal and the sizes of the myelinated fibres were strongly shifted towards smaller diameters. These data confirm our previous light microscopic observations. We conclude that eu-/hypoglycaemic BB/Wor rats treated with insulin implants, but not similarly treated eu-/hyperglycaemic animals, develop a neuropathy in their plantar nerves.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004010050875
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  • 26
    Electronic Resource
    Electronic Resource
    A novel member of the bombyxin gene family: structure and expression of bombyxin G1 gene, an insulin-related peptide gene of the silkmoth Bombyx mori (1998)
    Springer
    Development genes and evolution 208 (1998), S. 407-410 
    Details
    ISSN: 1432-041X
    Keywords: Key words Bombyxin ; Insulin ; Bombyx mori ; Multigene family ; Brain neurosecretory cell
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Bombyxin G1 gene, a novel insulin-related peptide gene of the silkmoth Bombyx mori, has been identified. The G1 gene encodes a precursor peptide which shows 41–56% and 28% sequence identities with preprobombyxins previously characterized and human preproinsulin, respectively. The G1 gene forms a pair with bombyxin C2 gene with opposite transcriptional orientation in a bombyxin gene cluster. The bombyxin G1 mRNA in Bombyx brain was shown to locate in four pairs of medial neurosecretory cells.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004270050197
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  • 27
    Electronic Resource
    Electronic Resource
    Cyclosporin A induces apoptosis in rat hepatocytes in culture (1998)
    Springer
    Archives of toxicology 72 (1998), S. 559-565 
    Details
    ISSN: 1432-0738
    Keywords: Key words Proliferation ; Epidermal growth factor (EGF) ; Insulin ; Hepatocyte ; Cyclosporin A
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Cyclosporin A (CsA) at concentrations up to 1 μM induced apoptosis in a dose-dependent manner in cultured rat hepatocytes for 48 h in the presence of insulin and epidermal growth factor (EGF). The effect of CsA was evidenced by the DNA fragmentation pattern constituted by fragments of multiples of 180–200 base pairs, which is a characteristic of programmed cell death. The metabolic activity did not change significantly in the presence of 0.1 μM CsA and diminished to 49% of control in the presence of 1 μM CsA. Changes in the metabolic activity were correlated with a decrease in both [methyl-3H]thymidine uptake and DNA content, which reflects a decrease in the cell number. The treatment of cells with CsA (1 μM) decreased the metabolic activity/DNA content ratio by 24% with respect to dimethyl sulphoxide (DMSO) control, which also suggests, under these conditions, that the necrosis achieved is at most only 24%. In addition, the changes observed (apoptotic process, arrest of the cell cycle and apparition of a necrotic process) were correlated with an increase in the high-affinity guanosine triphosphatase (GTPase) enzymes.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s002040050543
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  • 28
    Electronic Resource
    Electronic Resource
    Slowly deteriorating insulin secretion and C-peptide production characterizes diabetes mellitus in infantile cystinosis (1998)
    Springer
    European journal of pediatrics 157 (1998), S. 738-742 
    Details
    ISSN: 1432-1076
    Keywords: Key words Diabetes mellitus ; Infantile cystinosis ; Insulin ; C-peptide ; Chronic renal failure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Infantile cystinosis, a rare lysosomal storage disease of cystine, leads to Fanconi syndrome and end-stage renal failure. After renal transplantation, no recurrence of the disease occurs in the graft, but other organ involvement becomes evident later in life. Diabetes mellitus has been associated with cystinosis, but the mechanisms of impaired glucose tolerance have not yet been characterized. Here, we studied glucose tolerance, glucose constant decay (k-values), insulin and C-peptide by intravenous glucose tolerance test (IVGTT) in eight patients with infantile cystinosis (three with impaired GFR (CRF) and five after kidney transplantation (KTX)). For comparison, 15 age-matched children with CRF and 15 age-matched KTX patients were analysed. Both early and second insulin secretion phases were diminished in patients with infantile cystinosis, whereas in CRF, k-values were no different from control patients. After renal transplantation, k-values were significantly lower in cystinotic patients with a markedly reduced early insulin secretion phase. There was a significant negative correlation between k-values and age in patients with cystinosis. Repetitive IVGTTs in these patients demonstrated progressive but rather slow loss of first phase insulin secretion and C-peptide production, suggesting a slowly reducing secretion potential of the beta cell due to cystine storage. Conclusion Unlike type I diabetes mellitus, glucose intolerance in patients with infantile cystinosis is characterized by a slow, progressive loss of insulin secretion and C-peptide production. For these patients, the data indicate a 50% risk of developing glucose intolerance by the age of 18 years. We recommend to perform intravenous glucose tolerance tests at 5-year intervals.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004310050926
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  • 29
    Electronic Resource
    Electronic Resource
    Expression of type III hyperlipoproteinemia in patients homozygous for apolipoprotein E-2 is modulated by lipoprotein lipase and postprandial hyperinsulinemia (1998)
    Springer
    Journal of molecular medicine 76 (1998), S. 355-364 
    Details
    ISSN: 1432-1440
    Keywords: Key words Postprandial hyperlipoproteinemia ; Lipoprotein lipase ; Insulin ; Apolipoprotein E ; Hyperlipoproteinemia type III
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Type III hyperlipoproteinemia (HLP) is a multifactorial disorder associated with homozygosity for the apolipoprotein (apo) E-2 allele. Factors which may promote the development of HLP include lipoprotein lipase (LPL) and hyperinsulinemia. These factors were investigated in eight patients with type III HLP and in nine normolipidemic controls. In vitro the interaction of apoE with LPL was analyzed in cell binding assays. All type III HLP patients showed delayed triglyceride (TG) clearance and remnant lipoprotein accumulation in an oral fat tolerance test. Normolipidemic apoE-2/2 controls revealed normal TG clearance comparable to apoE3/3 controls. HLP patients showed lower LPL activity and mass than controls. Analysis of the LPL gene revealed an Asn 291→Ser mutation in three patients and a –93 T-G substitution combined with an Asp 9→Asn mutation in one control subject. In addition to LPL abnormalities, postprandial hyperinsulinemia was observed in five out of eight patients. In vitro LPL compensated the defective function of apoE-2 in mediating remnant lipoprotein binding to cells. In summary, seven out of eight patients with type III HLP showed LPL abnormalities and/or postprandial hyperinsulinemia. Together with the in vitro data these findings support a coordinate effect of apoE and LPL for the manifestation of type III HLP. Hyperinsulinemia appears to be an additional factor important for disease expression.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s001090050227
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  • 30
    Electronic Resource
    Electronic Resource
    Cellular regulation of islet hormone secretion by the incretin hormone glucagon-like peptide 1 (1998)
    Springer
    Pflügers Archiv 435 (1998), S. 583-594 
    Details
    ISSN: 1432-2013
    Keywords: Key words GLP-1 ; cAMP ; Insulin ; Calcium ; NIDDM ; Glucagon ; Islet ; GIP
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Glucagon-like peptide 1 is a gastrointestinally derived hormone with profound effects on nutrient-induced pancreatic hormone release. GLP-1 modulates insulin, glucagon and somatostatin secretion by binding to guanine nucleotide binding protein-coupled receptors resulting in the activation of adenylate cyclase and generation of cyclic adenosine monophosphate (cAMP). In the B-cell, cAMP, via activation of protein kinase A, interacts with a plethora of signal transduction processes including ion channel activity, intracellular Ca2+ handling and exocytosis of the insulin-containing granules. The stimulatory action of GLP-1 on insulin secretion, contrary to that of the currently used hypoglycaemic sulphonylureas, is glucose dependent and requires the presence of normal or elevated concentrations of the sugar. For this reason, GLP-1 attracts much interest as a possible novel principle for the treatment of human type-2 diabetes. Here we review the actions of GLP-1 on islet cell function and attempt to integrate current knowledge into a working model for the control of pancreatic hormone secretion.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004240050558
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  • 31
    Electronic Resource
    Electronic Resource
    Insulin dominantly suppresses hepatitis B virus gene expression in cultured human hepatoma cells (1997)
    Springer
    Journal of biomedical science 4 (1997), S. 295-299 
    Details
    ISSN: 1423-0127
    Keywords: Hepatoma ; Hepatitis B surface antigen ; Insulin ; Glucocorticoid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract We have shown previously that insulin suppresses the expression of hepatitis B surface antigen (HBsAg) gene from an endogenous integrated viral genome in cultured human hepatoma Hep3B cells. In this study, we demonstrated that insulin suppresses the viral mRNA transcribed from transiently transfected tandem repeat hepatitis B virus (HBV) dimer DNA or DNA fragment that contains only the major HBsAg gene. Insulin treatment also resulted in a decrease in HBV viral particles produced by the HBV-DNA-transfected cells in a dose-dependent manner. Furthermore, when insulin was simultaneously added with glucocorticoid, which stimulates HBV gene expression, the stimulatory effect of glucocorticoid was completely abolished. Our results suggest that insulin has a dominant negative effect on the HBV gene expression in cultured human liver cells.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02258353
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  • 32
    Electronic Resource
    Electronic Resource
    Insulin effects on ouabain binding in A6 renal cells (1997)
    Springer
    Pflügers Archiv 434 (1997), S. 11-18 
    Details
    ISSN: 1432-2013
    Keywords: Key words A6 epithelia ; Ouabain binding ; Insulin ; Cycloheximide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The effects of insulin on the Na+-K+-ATPase pump of the basolateral membrane of tight epithelia were evaluated by measuring transepithelial transport and [3H]ouabain binding in cultured A6 kidney cells. [3H]Ouabain binding in epithelia incubated in either K+-containing or K+-free solutions was measured. Insulin induced increases in transepithelial sodium transport, as measured by the short-circuit current (I sc), and in the initial rate of [3H]ouabain binding determined when the preparation was bathed in K+-containing solutions. However, when initial [3H]ouabain binding in tissues incubated in K+-free solutions was measured the stimulation of the initial rate of [3H]ouabain binding caused by insulin was markedly reduced. Incubating the apical side of the epithelium with either amiloride or Na+-free solutions also reduced or abolished the increase in the initial rate of [3H]ouabain binding caused by insulin. Equilibrium binding measurements showed that insulin did not increase the maximum number of [3H]ouabain-binding sites in tissues incubated with either normal K+ or K+-free solutions. These results indicate that the increase in the initial rate of [3H]ouabain binding under transporting conditions is due to an effect on the binding kinetics of ouabain, probably related to an increased rate of Na+ entry, rather than to an increase in the number of Na+-K+-ATPases in the basolateral membrane. Cycloheximide inhibited both the increase in I sc and the increase in the initial rate of [3H]ouabain binding caused by insulin in epithelia incubated in K+-containing solutions. However, cycloheximide was without effect on the initial rate of [3H]ouabain binding in insulin-treated tissues incubated in K+-free solution. This finding suggests that the cycloheximide-sensitive step of the action of insulin is related to Na+ delivery to the pump.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004240050357
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  • 33
    Electronic Resource
    Electronic Resource
    Multisite regulation of insulin secretion by cAMP-increasing agonists: evidence that glucagon-like peptide 1 and glucagon act via distinct receptors (1997)
    Springer
    Pflügers Archiv 434 (1997), S. 515-524 
    Details
    ISSN: 1432-2013
    Keywords: Key words GLP-1 ; Exocytosis ; B-cell ; Glucagon ; Insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The mechanisms by which glucagon-like peptide 1(7–36)amide (GLP-1[7–36]amide) potentiates insulin secretion were investigated by measurements of whole-cell K+ and Ca2+ currents, membrane potential, the cytoplasmic Ca2+ concentration ([Ca2+]i) and exocytosis in mouse pancreatic B-cells. GLP-1(7–36)amide (10 nM) stimulated glucose-induced (10 mM) electrical activity in intact pancreatic islets. The effect was manifested as a 34% increase in the duration of the bursts of action potentials and a corresponding 28% shortening of the silent intervals. GLP-1(7–36)amide had no effect on the electrical activity at subthreshold glucose con- centrations (≤6.5 mM). In cultured B-cells, GLP-1(7–36)amide produced a decrease of the whole-cell ATP-sensitive K+ (KATP) conductance remaining at 5 mM glucose by ≈30%. This effect was associated with membrane depolarization and the initiation of electrical activity. GLP-1(7–36)amide produced a protein-kinase-A- (PKA-) and glucose-dependent fourfold potentiation of Ca2+-induced exocytosis whilst only increasing the Ca2+ current marginally. The stimulatory action of GLP-1(7–36)amide on exocytosis was mimicked by the pancreatic hormone glucagon and exendin-4, a GLP-1 receptor agonist. Whereas the stimulatory action of GLP-1(7–36)amide could be antagonized by exendin-(9–39), this peptide did not interfere with the ability of glucagon to stimulate exocytosis. We suggest that GLP-1(7–36)amide and glucagon stimulate insulin secretion by binding to distinct receptors. The GLP-1(7–36)amide-induced stimulation of electrical activity and Ca2+ influx can account for (maximally) a doubling of insulin secretion. The remainder of its stimulatory action results from a cAMP/PKA-dependent potentiation of Ca2+-dependent exocytosis exerted at a stage distal to the elevation of [Ca2+]i.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004240050431
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  • 34
    Electronic Resource
    Electronic Resource
    The β cell transcription factors and development of the pancreas (1997)
    Springer
    Journal of molecular medicine 75 (1997), S. 327-340 
    Details
    ISSN: 1432-1440
    Keywords: Key words Pancreas ; Islet ; β Cell ; Insulin ; Transcription ; PDX-1 ; Development
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The pancreatic β cell is the major source of circulating insulin in adult mammals. In the multistep process of insulin synthesis it is initiation of transcription that restricts insulin synthesis to the β cell since all subsequent steps can be performed by other cell types. Many of the transcription factors that bind to the insulin promoter and activate insulin gene transcription have been isolated. Some of these factors are restricted in their expression pattern, but so far no truly β cell-specific transcriptional activator has been found. Since different transcription factors synergize to activate insulin gene transcription, cell-specific transcription of insulin is probably realized through the interactions of a unique set of regulatory proteins in the β cell. The same transcription factors that regulate insulin gene transcription in the adult β cell are involved in determining cell differentiation during pancreatic development. The endocrine and exocrine pancreas form from the gut endoderm as a dorsal and a ventral bud which later fuse to build a single organ. The homeodomain protein PDX-1, an insulin gene transcription factor, is uniformly expressed in the early pancreatic bud, and null mutation of PDX-1 in mice results in a failure of the pancreatic bud to grow and differentiate. Other transcription factors, such as the helix-loop-helix protein Beta-2 and the homeodomain protein Nkx 6.1, show a restricted pattern of expression during embryogenesis and in the mature islet. Those proteins may serve a dual role for the organism: during embryogenesis they may determine islet cell differentiation and in the adult they may ensure tissue-specific expression of the islet cell hormones. A better understanding of the factors involved in insulin gene transcription and islet cell differentiation will ultimately provide the basis for novel therapy of diabetes.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s001090050118
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  • 35
    Electronic Resource
    Electronic Resource
    Effects of reduced electrochemical Na+ gradient on contractility in skeletal muscle: role of the Na+-K+ pump (1997)
    Springer
    Pflügers Archiv 434 (1997), S. 457-465 
    Details
    ISSN: 1432-2013
    Keywords: Key words Na+-K+ pump ; Membrane potential ; Muscle fatigue ; Catecholamines ; Insulin ; Soleus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Continued excitation of skeletal muscle may induce a combination of a low extracellular Na+ concentration ([Na+]o) and a high extracellular K+ concentration ([K+]o) in the T-tubular lumen, which may contribute to fatigue. Here, we examine the role of the Na+-K+ pump in the maintenance of contractility in isolated rat soleus muscles when the Na+, K+ gradients have been altered. When [Na+]o is lowered to 25 mM by substituting Na+ with choline, tetanic force is decreased to 30% of the control level after 60 min. Subsequent stimulation of the Na+-K+ pump with insulin or catecholamines induces a decrease in [Na+]i and hyperpolarization. This is associated with a force recovery to 80–90% of the control level which can be abolished by ouabain. This force recovery depends on hyperpolarization and is correlated to the decrease in [Na+]i (r = 0.93; P〈0.001). The inhibitory effect of a low [Na+]o on force development is considerably potentiated by increasing [K+]o. Again, stimulation of the Na+-K+ pump leads to rapid force recovery. The Na+-K+ pump has a large potential for rapid compensation of the excitation-induced rundown of Na+, K+ gradients and contributes, via its electrogenic effect, to the membrane potential. We conclude that these actions of the Na+-K+ pump are essential for the maintenance of excitability and contractile force.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004240050421
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  • 36
    Electronic Resource
    Electronic Resource
    Impacts of components of the metabolic syndrome on health status and survival in an aged population (1997)
    Springer
    European journal of epidemiology 13 (1997), S. 429-434 
    Details
    ISSN: 1573-7284
    Keywords: Elderly ; Health-status ; Insulin ; Lipids ; Metabolic-syndrome ; Survival
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The clinical significances of different components of the multiple metabolic syndrome were studied in a five-year follow-up study of random persons (n = 1,199) of four birth cohorts at ages 65, 75, 80, and 85 years. The subjects were examined clinically and their serum lipids, blood glucose, plasma insulin, blood pressure, and health score were determined. The health score was measured using a visual analogue scale. All subjects were followed for 5 years. Health score, diastolic blood pressure and body mass index declined over age, but serum triglycerides, and blood glucose were similar, whilst serum high density lipoprotein (HDL)-cholesterol increased. Among women fasting plasma insulin was lowest in the age group of 65 years. The associations of components of the multiple metabolic syndrome varied by age. In the age groups of 65 and 75 years high body mass index, plasma insulin, glucose, triglycerides and low HDL-cholesterol were associated with impaired health. In the age group of 85 years high blood pressure, total cholesterol, and HDL-cholesterol were associated with good health. The baseline health score was consistently lower in the decedents than survivors of all age groups, but components of the metabolic syndrome were generally not associated with impaired survival.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1007325609315
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  • 37
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    Electronic Resource
    Morphologische Wirkung von Adrenalin und Insulin auf Knochenkapillaren nach Rezeptorenblockade (1997)
    Springer
    Langenbeck's archives of surgery 382 (1997), S. 164-166 
    Details
    ISSN: 1435-2451
    Keywords: Key words Cortical bone ; Capillaries ; TEM ; Receptor blockade ; Epinephrine ; Insulin ; Schlüsselwörter Knochenkapillaren ; TEM ; Rezeptorenblockade ; Adrenalin ; Insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Bei 3mal sechs Mäusen wurden die α- und β-Rezeptoren mit Phentolamin und Propranolol blockiert. Den 3 Gruppen wurden Kochsalz, Adrenalin und Insulin injiziert. Kortikale Knochenkapillaren aus der Tibiadiaphyse wurden für die TEM aufgearbeitet. Ihre Lumen- und Endothelflächen wurden als Estimator angegeben und gruppenweise verglichen. Signifikante Änderungen wurden nur im Endothel nach Insulin gesehen. Das spricht für spezifische Insulinrezeptoren in der terminalen Strombahn von Knochen und bestätigt frühere Beobachtungen von Adrenalinwirkungen.
    Notes: Abstract In three groups of six mice each, the α- and β-receptors were blocked by phentolamine and propranolol. The mice in the three groups then received an intravenous bolus injection of saline solution, epinephrine, and insulin, respectively. Cortical bone capillaries from the tibia diaphysis were submitted to transmission electron microscopy (TEM). The lumen and endothelium were measured and the results compared. Significant changes were only noted in the endothelium after the administration of insulin. These findings suggest that there are also insulin receptors in bone. Furthermore, they support previous findings in similar studies with epinephrine.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/PL00008036
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  • 38
    Electronic Resource
    Electronic Resource
    Urinary phosphate excretion in the pathophysiology of idiopathic recurrent calcium urolithiasis: Hormonal interactions and lipid metabolism (1997)
    Springer
    Urological research 25 (1997), S. 417-426 
    Details
    ISSN: 1434-0879
    Keywords: Phosphaturia ; Glucose ; Insulin ; lipids ; Idiopathic recurrent calcium urolithiasis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Previous work in younger males with recurrent idiopathic calcium urolithiasis (RCU) demonstrated inappropriately high postprandial phosphaturia, hyperinsulinemia and insulin resistance, but normal glycemia. To investigate further whether these abnormalities occur also in RCU patients with a mean age corresponding to the life period with peak formation of calcium-containing stones, two trials were carried out in 155 males of comparable age and body mass index. All participants underwent a standardized laboratory examination, including collection of urine and blood before and following a test meal rich in carbohydrate and calcium but low in phosphorus. In trial 1, comprising control subjects (n = 12, mean age 42 years) and RCU patients (n = 24, mean age 41 years), phosphate (Pi) excretion and fractional Pi excretion in postprandial urine of controls did not change compared with the values in fasting urine, but were significantly increased in RCU, despite the fact that there was almost equal suppression of serum parathyroid hormone (PTH) and increase in serum calcitonin. Postprandially, RCU patients were hyperinsulinemic but still normoglycemic versus controls. In trial 2, carried out in unclassified (in terms of calciuria) RCU patients (n = 119, mean age 40 years) only, the post-load Pi-uria was similar in magnitude to Pi-uria of RCU patients in trial l; increased postprandial Pi-uria was a phenomenon also of normocalciuria but was slightly more pronounced in hypercalciuria, while changes in calcium phosphate (brushite) and calcium oxalate supersaturation of urine were unrelated to calciuria. In RCU patients, but not controls, there was a tendency toward higher urinary glucose in post-load as compared with fasting urine. When urinary Pi and fractional Pi excretion in trial 2 were considered as dependent variables in multivariate regression analysis, they appeared unrelated to age, but positively associated with postprandial glycemia as the best predictor, followed by insulinemia, insulin resistance, to a lesser degree fasting serum PTH and the metabolic activity of stone disease, negatively associated with blood total lipids and very low density lipoprotein (VLDL) cholesterol. It was concluded that RCU males (1) show low Piuria during fasting but impaired renal Pi conservation in response to a mixed meal, a situation carrying the risk of Pi deficiency over the long term; (2) represent a population developing hyperei-uria despite suppressed PTH; (3) exhibit insulin resistance but are still able to maintain normoglycemia at the expense of hyperinsulinemia. It is suggested that calcium-containing renal stones are related to impaired Pi and glucose translocation across cell membranes, and that the role of lipids in this setting deserves further investigation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01268860
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  • 39
    Electronic Resource
    Electronic Resource
    Beta-endorphin infusion alters pancreatic hormone and glucose levels during exercise in rats (1997)
    Springer
    European journal of applied physiology 76 (1997), S. 203-208 
    Details
    ISSN: 1439-6327
    Keywords: Key words Naloxone ; Insulin ; Glucagon ; C-peptide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract β-Endorphin (BE) infusion at rest can influence insulin and glucagon levels and thus may affect glucose availability during exercise. To clarify the effect of BE on levels of insulin, glucagon and glucose during exercise, 72 untrained male Sprague-Dawley rats were infused i.v. with either: (1) BE (bolus 0.05 mg · kg−1 +0.05 mg · kg−1 · h−1, n = 24); (2) naloxone (N, bolus 0.8 mg · kg−1 + 0.4 mg · kg−1, n = 24); or (3) volume-matched saline (S, n = 24). Six rats from each group were killed after 0, 60, 90 or 120 min of running at 22 m · min−1, at 0% gradient. BE infusion resulted in higher plasma glucose levels at 60 min [5.93 (0.32) mM] and 90 min [4.16 (0.29) mM] of exercise compared to S [4.62 (0.27) and 3.41 (0.26 mM] and N [4.97 (0.38) and 3.44 (0.25) mM]. Insulin levels decreased to a greater extent with BE [21.5 (0.9) and 18.3 (0.6) uIU · ml−1] at 60 and 90 min compared to S [24.5 (0.5) and 20.6 (0.6) uIU · ml−1] and N [24.5 (0.4) and 21.6 (0.7) uIU · ml−1] groups. Plasma C-peptide declined to a greater extent at 60 and 90 min of exercise with BE infusion compared to both S and N. BE infusion increased glucagon at all times during exercise compared to S and N. These data suggest that BE infusion during exercise influences plasma glucose by augmenting glucagon levels and attenuating insulin release.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004210050237
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  • 40
    Electronic Resource
    Electronic Resource
    Metabolic and hormonal responses during repeated bouts of brief and intense exercise: effects of pre-exercise glucose ingestion (1997)
    Springer
    European journal of applied physiology 76 (1997), S. 197-202 
    Details
    ISSN: 1439-6327
    Keywords: Key words Glucose ; Insulin ; Epinephrine ; Lactate ; Force-velocity test
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We investigated metabolic and hormonal responses during repeated bouts of brief and intense exercise (a force-velocity test; Fv test) and examined the effect of glucose ingestion on these responses and on exercise performance. The test was performed twice by seven subjects [27 (2) years] according to a double-blind randomized crossover protocol. During the experimental trial (GLU), the subjects ingested 500 ml of glucose polymer solution containing 25 g glucose 15 min before starting the exercise. During the control trial (CON), the subjects received an equal volume of sweet placebo (aspartame). Exercise performance was assessed by calculating peak anaerobic power ( W˙ an,peak). Venous plasma lactate concentration increased significantly during the Fv test (P 〈 0.001), but no difference was found between CON and GLU. Blood glucose first decreased significantly from the beginning of exercise up to the 6-kg load (P 〈 0.001) and then increased significantly at W˙ an,peak and for up to 10 min during the recovery period (P 〈 0.001) in both CON and GLU. Insulin concentrations decreased significantly in both groups, but were higher at W˙ an,peak in GLU compared with CON (P 〈 0.05). Glucagon and epinephrine did not change significantly in either group, but epinephrine was significantly lower in GLU after glucose ingestion (P 〈 0.05) and at W˙ an,peak (P 〈 0.05). W˙ an,peak was not significantly different between CON and GLU. In conclusion, blood glucose and insulin concentrations decreased during repeated bouts of brief and intense exercise, while blood lactate concentration increased markedly without any significant change in glucagon and epinephrine concentrations. Glucose ingestion altered metabolic and hormonal responses during the Fv test, but the performance as measured by W˙ an,peak was not changed.
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    URL: http://dx.doi.org/10.1007/s004210050236
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  • 41
    Electronic Resource
    Electronic Resource
    The effect of zinc(II) and some chromium complexes on the constant current chronopotentiometry of insulin (1997)
    Weinheim : Wiley-Blackwell
    Electroanalysis 9 (1997), S. 554-559 
    Details
    ISSN: 1040-0397
    Keywords: Insulin ; Zinc ; Chromium ; Chronopotentiometry ; Disulfide ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The constant current chronopotentiometry (CCCP) of zinc-free insulin was examined and the effect of additions of zinc(II) or either of two chromium complexes to the zinc-free zinc was studied. The zinc free insulin gave a constant current chronopotentiometric (CCCP) response which indicated that the freeze drying process, which was part of its preparation, may have denatured the insulin. The addition of zinc(II) appeared to reverse this since the response following zinc additions was similar to that of native insulin. Of the two chromium complexes investigated for their influence on insulin electrochemistry tripicolinato chromium(III) had no effect on the CCCP response, trans-Diaquoethylenebis-(salicylideneiminato) chromium(III) had an indirect effect by appearing to restore the native conformation of the insulin following the apparent denaturation caused by the removal of zinc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/elan.1140090710
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  • 42
    Electronic Resource
    Electronic Resource
    Asymmetric Catalysis, 105Part 104: Ref.. Stereoselective Hydrogenation of Folic Acid with Immobilized Optically Active Rhodium(I)/Diphosphane Catalysts (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 55-62 
    Details
    ISSN: 0009-2940
    Keywords: Diastereoselective hydrogenation ; Folic acid ; Immobilized optically active rhodium(I)/diphosphane catalysts ; Leucovorin ; HPLC analysis of 5-formyltetrahydrofolic acid derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For the hydrogenation of the C=N bonds in the pyrazine ring of the vitamin folic acid (1) optically active rhodium(I)/diphosphane complexes immobilized on supports such as silica gel or Al2O3 were used. The reduction was carried out at 50 bar hydrogen pressure in an aqueous solution buffered to pH 7. Thus, 5,6,7,8-tetrahydrofolic acid (2) was obtained which contains a new asymmetric center at C-6 of the pterine system. Therefore, in combination with the (S) configuration of the natural L-glutamic acid part of the molecule two diastereomers with (6S,S) and (6R,S) configuration arise. The relatively unstable tetrahydrofolic acid (2) was converted into its 5-formyl derivative folinic acid (4) by treatment with methyl formate/formic acid in a 5:1 mixture of DMSO/pyridine. The Ca salt of folinic acid (4) is the widely used drug leucovorin. The diastereomers were separated by silica gel HPLC. To the column bovine serum albumine (BSA) is covalently bound. With optically active rhodium(I)/diphosphane catalysts, immobilized on silica gel supports, a diastereoselectivity of up to 90% could be achieved in the hydrogenation of folic acid (1).
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300109
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  • 43
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    Electronic Resource
    Conformational Mobility and Preferences of Allyl-Type Organometallic Intermediates: Dodec-2-enylpotassium (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 83-88 
    Details
    ISSN: 0009-2940
    Keywords: Torsional (Z/E) isomerization ; Selectivity, regio- and stereo- ; Allylsilanes ; Allylic oxidation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alk-2-enylpotassium compounds having the endo conformation are synthetically very valuable precursors of (Z)-olefinic derivatives substituted at the outward allylic position. They may be generated by „stereoconservative‘ metalation of the readily available (Z)-alk-2-enes by using the superbasic mixture of butyllithium and potassium tert-butoxide or by metalation under similar conditions of stereorandom mixtures of alk-2-enes or alk-1-enes followed by torsional isomerization of the concomitantly formed exo conformers to the thermodynamically more stable endo species. The principal factors that dictate the rate and the extent of the endo/exo equilibration are the substrate geometry, the solvent, the temperature, the reagent stoichiometry, and catalysis.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300113
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  • 44
    Electronic Resource
    Electronic Resource
    Organophosphorus Compounds, 114. Tetracyclic Phosphorus-Aluminium-Carbon Compounds - Synthesis by Cooligomerization of Kinetically Stabilized Phosphaalkynes with Trialkylaluminium CompoundsDedicated to Professor Michael Hanack on the occasion of his 65th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 255-259 
    Details
    ISSN: 0009-2940
    Keywords: Phosphaalkynes ; Triorganoaluminium compounds ; Cooligomerization ; Cage compounds ; Aluminium compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When the trialkylaluminium reagents 5 are allowed to react with phosphaalkynes 4 in n-pentane, a highly selective phosphaalkyne cyclotrimerization with incorporation of two organometallic units occurs (→ 6). The tetracyclooctane derivatives 6a-e represent the first examples of phosphorus-aluminium-carbon cage compounds. The polycyclic products 6 are able to function as ligands in transition-metal complexes (→ 7), which is illustrated by the reactions of 6b, c with nonacarbonyldiiron and pentacarbonyl(tetrahydrofuran)tungsten, respectively.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300219
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  • 45
    Electronic Resource
    Electronic Resource
    On the Ligating Properties of Sulfonate and Perchlorate Anions Towards Zinc (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 283-289 
    Details
    ISSN: 0009-2940
    Keywords: Zinc ; Sulfonate ligands ; Perchlorates ; Coordination modes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Attempts are reported to incorporate sulfonate and perchlorate anions as ligands in zinc complexes of tripodal ligands. Using tris(benzimidazolylmethyl)amine (BIMA) only the aqua complexes [ (BIMA)Zn-OH2](RSO3)(ClO4) and [(BIMA)Zn-OH2](RSO3)2(R=CH3, CF3, p-tolyl) were accessible. Using substituted pyrazolylborates (Tp*), the same three sulfonate anions were found to be ligands in the complexes Tp*Zn-OSO2R. Spectroscopic evidence for perchlorate coordination in Tp*ZnClO4 · 2 DMSO conflicts with crystallograpic evidence against it in Tp*ZnClO4 · pyridine. The crystal structures of [(BIMA)Zn-OH2](CH3SO3)2, TpCum,MeZn-OS02CH3, TPtBu,MeZn-OSO2C6H4-p-CH3, and [TpCum,MeZn · NC5H5]ClO4 were determined.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300223
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  • 46
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    Multiple Bonds Between Main-Group Elements and Transition Metals, CLXIV. Alkylrhenium(VI) Oxides-Synthesis and Characterization (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 295-298 
    Details
    ISSN: 0009-2940
    Keywords: Rhenium ; Oxides ; Alkyl ligands ; Dirhenium compounds ; Metal-metal interactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Most alkylrhenium(VII) oxides, e.g. ((cyclo)-C3H5)Re03 (2) are rather sensitive to temperature and moisture with the prominent exception of methyltrioxorhenium (1). The corresponding alkylrhenium(VI) oxides of formula [RR′(O)- Re(μ-O)]2 [R=R′=(cyclo)-C3H5 (3), iPr (4); R=CH3, R′=C2H5 (5), R=CH3, R′=iPr (6)] are much more stable in this regard. They can be handled in air at room temperature. They were synthesized from Re207 and dialkylzinc precursors, fully characterized and are available in much higher yields than their ReVII congeners. Mixed tetraalkyltetraoxodirhenium(VI) complexes (R # R′) synthesized from 1 and dialkylzinc compounds form as a mixture of cis/trans isomers. They are oily liquids at room temperature. The Re=O and Re-Re stretching force constants as a measure of the bond strengths, were determined from IR and Raman data.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19971300225
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    Heterobimetallic Complexes with a Propynylidene C3-Bridge: General Synthetic Routes to Bimetallic Ethynylcarbene Complexes (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 479-488 
    Details
    ISSN: 0009-2940
    Keywords: Heterobimetallic complexes ; Carbene complexes ; Alkynes ; Coupling reaction ; Bridging ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sequential reaction of the dimethylamino(trimethylsilylethylnyl)carbene complexes [(CO)5M'=C(NMe2)C≡CSiMe3] [M' = W (1a)] with KF/THFMeOH, nBuLi and transition metal halides, [XMLn], affords heterobimetallic propynyliden complexes of the type [(CO)5M'=C(N-Me2)C≡CMLn] [MLn = Ni(PPh3) Cp (4a, b). Ni(PMe2Ph)2- {Mes) (Mes=2,4,6-C6H2Me3) (5a), Rh(CO)(PPh3)2 (6a), Fe(CO)2Cp (7a,b)]. In contrast, reaction of 1a with MeLi · LiBr and [IFe(CO)2Cp] yields the novel N-metallated complex [(CO)5W=C{N(ME)Fe(CO)2Cp}C≡CSiMe3] (8a). The complexes [(CO)5M'=C(NMe2)C≡CMLn=Fe(CO)2Cp (7a, b), Ru(CO)2Cp (10a,b), Ru(CO)(PPh3)Cp (11a), Mn(CO)5 (12a), Re(CO)5 (13a)] are accessible by Pd-catalyzed coupling of the C-stannylated carbene complexes [(CO)5M'=C-(NMe2)C≡CSnBu3] (9a, b) with [XMLn]. The related monomethylaminocarbene complexes [(CO)5M'=C(NHMe)C≡ CSnBu3] (16a, b), obtained by stannylation of [(C))5M'=C(NHMe)C=CH] (15a, B) with Bu3SnNEt2, react with [IFe(CO)2Cp] to give the bimetallic complexes [(CO)5M'=C(NHMe)C≡CFe(CO)2Cp] (17a, b). The complexes 4a, 5a, 7a and 10a were characterized by X-ray structural analysis. The spectroscopic and structural data suggest that the two metal centers in 4-7, 10-13, and 17 interact only weakly.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300407
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  • 48
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    Diazosulfonate Substitutents: A Route to Transition-Metal Complexes with Switchable Water Solubility (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 515-520 
    Details
    ISSN: 0009-2940
    Keywords: Water-soluble ligands ; Diazo compounds ; Photolysis ; Cleavage reactions ; Zinc ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The single-crystal X-ray structure analysis of the diazosulfonate p-H2N-C6H4-N=N-SO3Na 3 features a Z configuration of the diazo moiety and a nitrogen-sulfur bond. Each sodium atom is coordinated by one diazosulfonate substitutent in a chelating manner. Upon reaction of 3 with excess salicylaldehyde, the highly water-soluble Schiff base ligand 6 is obtained in good yield. Treatment of ZnCl2 with 2 equiv. of 6 gives the zinc complex 7. In all cases, the solubilizing diazosulfonate groups can be cleaved off photolytically, which offers an opportunity to precipitate the molecules from their aqueous solutions.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300411
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  • 49
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    Organoamido- and Aryloxolanthanoids, 15Part 14: Ref. [1a].. Organometallic Compounds of the Lanthanoids, 116Part 115: Ref. [1b].. Syntheses of Low Coordination Number Divalent Lanthanoid Organoamide Complexes, and the X-ray Crystal Structures of Bis[(N-2,6-diisopropylphenyl)(N-trimethylsilyl)amido]bi(tetrahydrofuran)samarium(II)and -ytterbium(II) (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 409-415 
    Details
    ISSN: 0009-2940
    Keywords: Mercury ; Lanthanides ; Lanthanoid(II) complexes ; (N-2,6-Diisopropylphenyl)(N-trimethylsily)amide complexes ; Bis(trimethylsilyl)amide complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Mercury(II) amide complex Hg[N(SiMe3)(2,6-iPr2C6H3)]2 (1) was prepared by reaction of HgBr2 with Li[N(SiMe3) 2,6-iPr2C6H3)] in diethyl ether solvent. Redox transmetallation reactions of 1 with elemental samarium, europium or ytterbium in THF solvent (THF = tetrahydrofuran), generated the novel divalent complexes Ln[N(SiMe3)(2,6-iPr2C6H3]2(THF)2 with Ln = Sm (2), Eu (3) and Yb (4). 4 was also synthesized by reaction of elemental ytterbium, HgPh2 and HN(SiMe3)(2,6-Me3)2]2(THF)2 [Ln = Sm (5), Yb (6)] by reaction of the metals with HgPh2 and HN(SiMe3)2. Thermal desolvation of 4 under high vacuum gave Yb(N)(SiMe3)2,6-iPr2C6H3)]2 (THF) (7), whereas under identical conditions 6 yielded the solvent-free complex [Yb[N{SiMe3)2]2]2. (8). The new compounds 1-4 and 7 are hydrocarbon soluble and 171Yb-NMR spectra were recorded for 4, 6, 7 and 8. X-ray crystal structure determinations of 2 and 4 revealed four-coordinate, distorted tetrahedral metal environments augmented by weak Ln…ipso-C(aryl) interactions.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300316
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  • 50
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    Recent Developments in the Chemistry of Covalent Azides (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 443-452 
    Details
    ISSN: 0009-2940
    Keywords: Ab initio calculations ; Azides ; Density functional calculations ; Covalent azides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The experimental and theoretical chemistry of covalently bound azides is an area that has seen considerable renaissance over the past 10 years. This review is not exhaustive in scope but rather focuses on and highlights certain aspects in this field. In particular, the stability and dissociation of HN3 is discussed at a very high level of theory (CASSCF and MCSCF-CI) and compared and contrasted with experimental data and results from „medium“-level ab initio computations (MP2, B-LYP). From these results credence is given to those values calculated for larger systems and heavy elements for which very high level computations are not possible. The experimentally well-characterized covalent halogen azides (XN3, where X = F, Cl, Br, I) as well as the heavy-element group-15 compound Sb(N3)3 are discussed. The review also includes discussion of the bond properties of the highly unstable N-bound azides ON-N3 and (FSO2)2N-N3. In the final chapter attention is drawn to the recently predicted and eventually experimentally verified elusive species OCN-NCO, which is isoelectronic to the hitherto unknown diazide N6.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300403
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    Divalent Tin and Lead Compounds EX2 Acting as Bridging Ligands in [{(CO)5M}2EX2]2- (E = Sn, Pb; M = Cr, Mo, W): Preparation and PropertiesDedicated to Professor G. E. Herberich on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 687-699 
    Details
    ISSN: 0009-2940
    Keywords: Tin ; Lead ; 119Sn NMR ; Salt metathesis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of Na2[M2(CO) 10] (M = Cr, Mo, W) with SnHal2 (Hal = Cl, Br) is a well established procedure for the synthesis of anions of type A, [{(CO)5M)SnHal3]-. Conditions are described which, for the same type of procedure, result in the additional formation of dianions of type B, [{(CO)5M}2SnHal2]2-. Procedures for separating these two types of anions in the form of their stable [Ph4P]+ or [nBu4N]+ salts by appropriate salt metathesis are presented. The structures of theses species have been characterized by X-ray analysis of three salts containing type A anions and two salts containing type B anions. The reactivity of the type B salts containing the bulky cations [Ph4P]+ or [nBu4N]+, respectively, is remarkably low; the salts are, however, transformed into highly reactive sodium salts by further metathesis with Na[BPh4]. In such salts the halide substitutents are easily exchanged as shown by the synthesis of ]})CO(5Cr}2oxinato]- (4)- from [Na-(THF)x]2[{(CO)5Cr}2SnCl2] and sodium 8-oxoquinolate, Na[C9H6NO]. The structure of the anion, 4 is compared to the structure of [[(CO)5Cr)SnCl2· THF] and sodium 8-oxochinolate. The preparation of the dinuclear anions [{(CO)5Cr}2E(OOCCH3)2]2- (E = Sn, 2g; E = Pb, 3) is accomplished by the reaction of [Ph4P]2[Cr2(CO)10] with the corresponding acetates E(OOCCH3)2. While 2g and 3 are formal analogues of the type-B anions, their structures reveal an asymmetrical η2-coordination of the two acetato ligands, in each case ending up in a 4+2 coordination for the main group centres, instead of the four-coordination observed for [{(CO)5M}2SnHal2]2-, All compounds have been characterized by usual spetroscopic and analytical techniques. X-ray analyses have been performed for selected examples. 119Sn-NMR data are presented for all of the compounds which contain tin-centred ligands.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300604
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    Organophosphorus Compounds, 118Part 2: 117: Ref1. Reactions of 1-Chloro-1H-phosphirenes with Nucleophiles (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 711-723 
    Details
    ISSN: 0009-2940
    Keywords: Phosphorus heterocycles ; 1H-Phosphirenes ; Nucleophilic substitution reactions at 1H-phosphirenes ; Metal-complexation of functionalized 1H-phosphirenes ; Carbonyl complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The halogen atoms in the 1-chloro-1H-phosphirenes, 5a-c, are easily substituted on reaction with organolithium and Grignard reagents, 14a-p, with formation of the corresponding O-, N-, C-, Si-, and Ge-substituted 1H-phosphirenes, 15a-t. C1/H exchange reactions also occur on reaction with lithium metal hydrides (5a → 17). Furthermore, substitution reactions are also realized with the alkali metal borates, 18a-g (→19a-g); the same is true for reactions with trimethylsilyl cyanide and azide (→22a-d). Some of the substitution products have been characterized in the form of their metal complexes, 16, 23, 24, and 25.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19971300607
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    Synthesis of Germatranyl Derivatives of Esters of Carboxylic Acids via Organometallic (Si, Ge, Sn) Reagents (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 739-746 
    Details
    ISSN: 0009-2940
    Keywords: Germatranes ; Organotrihalogenogermanes ; Organometallic (Si, Ge, Sn) reagents ; Transmetallation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Trialkylstannyl esters of tris(2-hydroxyalkyl)amines, N(CH2CHROSnAlk3)3 (9-11 (R = H, Me; Alk = Et, Bu), react with X3GeC(R1)(R2)COOR3 (12-17) (X = Cl or Br; R1, R2=H, Me, Ph, SiMe3, COOEt; R3=Me, Et) to give esters of α-germatranylcarboxylic acids, N(CH2CHRO)3GeC(R1)(R2)-COOR3 (1-8), in high yields. The synthesis of esters 12-17 is reported. Esters of α-germatranyldiphenylacetic acid 24 and 25 can be obtained by treatment of diphenylketene with Et3SnOMe to give in situ Et3SnC(Ph2)COOMe (23), followed by reaction with GeCl4 to give in situ Cl3GeC(Ph2)COOMe (22 and further reactions with 9 or 11, respectively. Reduction of germatrane 6 with LiAlH4 in diethyl ether leads to cleavage of the germanium-carbon bond with subsequent formation of (2-hydroxyethyl)trimethylsilane. The crystal structures of 3, 6 and 7 are reported. 1-Acyloxygermatranes 26 and 27 are obtained by treatment of 1-methoxygermatrane (28) with diphenyl- and dichloroacetic acid, respectively.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300611
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  • 54
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    Base-Induced Synthesis of a Tetrastannatriazabicyclo[3.1.1]heptane from Tris)dimethylchlorostannyl)amineDedicated to Professor W. Sieber on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 765-769 
    Details
    ISSN: 0009-2940
    Keywords: Tin - Nitrogen cage compounds ; Sn—X—Sn intramolecular bridges ; Distannylamine pyridine adduct ; Tin ; Moessbauer spectroscopy ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tris(dimethylchlorostannyl)amine (2a) reacts with pyridine in a 3:4 molar ratio to produce the tin-nitrogen containing bicyclo[3.1.1]heptane (3) with elimination of the adduct Me2SnCl2·2 py. Treatment of the distannylamine 2,6-[Pr2H3N(SnMe2Cl)2 (4) with pyridine, however, leads to the formation of the 1:1 pyridine adduct 4 and this can be regarded as a model to explain the route to 3. The molecular structures of 3 and 5 were determined by multinuclear magnetic resonance spectroscopy in solution, as well as by X-ray structure analysis of their crystals. Typical structural features for both compounds are intramolecular Sn—X—Sn bridges. Support for the structures comes from MS fragmentation patterns, IR spectra, and the Mössbauer spectra.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300615
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    Thermal Reactions of 5-Alkylidene-4,5-dihydro-3H-1,2,4(λ3)-diazaphospholes (4-Phosphapyrazolines) - A Route to Various P—Heterocycles and to 2-PhosphabutadienesDedicated to Professor M. Hanack on the occasion of his 65th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 779-788 
    Details
    ISSN: 0009-2940
    Keywords: 1,2,4-Diazaphospholes ; Phosphiranes, alkylidene- ; 2-Phosphabutadienes ; Phosphorus heterocycles ; pyrazolines, thermolysis ; Rearrangements ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 5-alkylidene-4,5-dihydro-3H-1,2,4(λ3)-diazaphospholes (4-phosphapyrazolines) are thermally much more stable than related compounds without the exocyclic double bond. Thermolysis reactions typically occur in the range 110-150°C in toluene solution, and different, mostly competing, reaction pathways are observed. Thermal extrusion of nitrogen from 8a-g gives rise to β-phosphanaylsiloxyalkenes 10, benzo[c]-phosphole derivatives 11, 14 and 115, (β-siloxyalkylidene)-Phosphiranes 12, and dihydro-1,3-oxaphospholes 13. The thermolysis of 5-alkylidene-4,5-dihydro-4-trimethylsilyl-3-trimethylsilyloxy-3H-1,2,4-dizaphospholes 17 afforded three products, including the highly substituted and stable 2-phosphabutadienes 18 formed by nitrogen extrusion and rearrangement. Finally, the 4-chloro-3-trimethylsilyloxy-substituted heterocycle 21 was transformed at 170°C into 4H-1,2,4-diazaphosphole 23. The structures of 13c and 18a were determined by single-crystal X-ray diffraction.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300617
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  • 56
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    N-Alkylation of Ammine - Undecahydro-Closo-dodecaborate(1-)Dedicate to Prof. Dr. Walter Siebert on the occasion of hbis 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 795-799 
    Details
    ISSN: 0009-2940
    Keywords: Boron ; Alkylations ; N ligands ; Dodecaborate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of the ammine-undecahydro-closo-dodecaborate(1-) anion with alkyl halides have been studied in detail. The degree of alkylation of the nitrogen was found to be dependent upon the steric demands of the alkyl groups. The derivatives were characterized by NMR and infrared spectroscopy. Four compounds were crystallized for single crystal X-ray diffraction studies. The tetrahedral coordination of the nitrogen atom of the bis-alkylated derivatives was found to deviate towards planarity with increasing steric hindrance of the substitutents. - The syntheses, crystal structures, and spectral properties of four N-alkyl derivatives of [H3N—B12H11]-, ammine - undecahydro-closo-dodecaborate(1-) (3), are reported. Alkylation of 3 with ethyl iodide was achieved in dimethyl sulfoxide using potassium hydroxide as base. This led to orthorhombic crystals of [N(nC4H94][(CH3CH2)3N—B12H11] (4). The reaction of 3 with benzyl chloride resulted in the bisbenzylated product, isolated as triclinic crystals of [PPN][(C6H5CH2)2 NH—B12H11] (5). The alkylation of 3 with 2-bromopropane gave a mixture of the mono- and bisalkylated products. The monoalkylated derivative [PPN][(CH3)2CH)NH2-12H11] (6, crystallized in the triclinic space group p1) and the bisalkylated product [PPN]{[(CH3)2NH—B12H11) (7, monoclinic, P21./c) were separated on the basis of their different water solubilities. The solid-state structures of the compounds 4-7 revealed a slight distortion of the B12 icosahedron. The length of the B(1)-N(1) bond was found to be dependent on the steric requirements of the attached amine, e.g. primary amine 〈 secondary amine 〈 tertiary amine. This is demonstrated by the variation in the B—N bond length; from 157.8(2) pm for 6, 158.5(5) pjm for 5, 160.0(3) pm for 7, to 163.7(6) pm for 4.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300619
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    Unusual Ring-Closure Reactions During the Oxidation of 1,1′-Bi(3-methylphosphol-2-ene) with Hexafluoroacetone  -  Formation of a Tricyclic Fluorine-Containing PhosphoraneDedicated to Professor Rudolf Taube on the occasion of hbis 65th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 819-822 
    Details
    ISSN: 0009-2940
    Keywords: Hexafluoroacetone ; Phosphorus, pentacoordinated ; Diphosphane diselenide ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reduction of the isoprene - PCl3 adduct 1 with magnesium powder, or with Si2Cl6, furnished P-chloro-3-methyl-phosphol-2-ene, 2, in satisfactory yield. Further reduction of 2 with Si2Cl6 gave the new trichlorosilyl-3-methylphosphol-2-ene, 3. The reaction of 2 with magnesium powder, with 3, or with 1/2 equivalent of Si2Cl6 provided the new γ3P-γP-diphosphane 1,1′-bi(3-methylphosphol-2-ene) 4. Reduction of 4 with Si2Cl6 led to 3. Oxidation of 4 with selenium gave the 1,2-diphosphane diselenide, 5. The oxidation of 4 with hexafluoroacetone led to a mixture of products, from which a novel tricyclic phosphorane 6 was separated. the structure of 196 was determined by X-ray diffraction; the coordination geometry at phosphorus in distorted trigonal bipyramidal, with a very long equatorial P - C(CF3)2 bond of 193.2(2) pm.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300623
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    Organophosphorus Compounds, 119Part 118: Ref.. The Phosphaalkyne Cyclotetramer System  -  Syntheses, Valence Isomerizations, and Reactions (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 823-834 
    Details
    ISSN: 0009-2940
    Keywords: Phosphaalkynes ; Phosphaalkyne cyclotetramers ; Cage compounds ; Valence isomerization ; Cyclotetramerization ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In contrast to their all-carbon analogues, phosphaalkyne cyclooligomers only became accessible a few years ago. A milestone in the chemistry of cyclotetramers was the synthesis and structural characterization of the tetraphosphacubane 5, obtained as a thermolysis product of tert-butylphosphaacetylene (1). Since then, the construction of eleven cyclotetramers has been achieved, covering seven different frameworks (A-G). As a consequence of the use of kinetically stabilized phosphaalkynes as starting materials, all known cyclotetramers bear sterically demanding substituents (tert-butyl, tert-pentyl, 1-adamantyl). Cyclotetramerizations are not only achieved by thermolysis of 1, but also by alternative and selective routes such as transition-metal-mediated, Lewis acid- and base-induced processes, as well as by cycloadditions to phosphaalkyne cyclotrimers. Interestingly, these tetramers can be interconverted by various valence isomerizations. The results of thermal and photochemically-induced rearrangements are in good agreement with MO calculations carried out for the parent compounds. Phosphaalkyne cyclotetramers exhibit a highly interesting reactivity and other peculiar features. One outstanding example is the tetraphosphacubane 5, which shows unusual structural and spectroscopic properties as a result of its unique bonding arrangement.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300703
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    2-Phosphanylphosphinines as Bridging Ligands for Dinuclear Transition Metal Carbonyls (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 843-849 
    Details
    ISSN: 0009-2940
    Keywords: P ligands ; Phosphorus heterocycles ; 2-Phosphanylphosphinines ; Dinuclear complexes ; Metal carbonyls ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 2-phosphanyl-4,5-dimethylphosphinines 1-5 are powerful bridging ligands able to stabilize metal-metal single and triple bonds between low-valent transition metal centres. Their reaction with Mn2(CO)10 in refluxing xylene yields the corresponding Mn2(CO)8 complexes 6 and 7. Reaction with [Fe2Cp2(CO)4] under UV irradiation similarly yields the Fe-Fe-bridged Fe2Cp2(CO)2 complexes 8 and 9. An additional observation is that the 2-phosphininyl-3,4-dimethylphosphaferrocene 10 is formed upon reaction of the 2-phospholylphosphinine 5 with [Fe2Cp2(CO)4] at high temperature under CO pressure. A clean addition occurs at the Mo≡Mo triple bond of [Mo2Cp2(CO)4] to give the Mo-Mo single-bonded complexes 11-15. The thermolysis of these complexes succeeds when the phosphanyl group is a phosphonite P(OEt)2 (13) or P(OAr)2 (14), affording cleanly the Mo2Cp2(CO)4 triple-bonded complexes 16 and 17, respectively. The metal-metal triple bonds of these complexes readily add two molecules of CO to reform 13 and 14, or one molecule of tBu-N≡C to give 18 and 19. The X-ray crystal structure analysis of the MO2C2(CO)4 complex 13a, with the 2-P(OEt)2- phosphinine, shows a gauche orientation of the two Cp rings and very short P-Mo bonds of 2.3565(4) and 2.406(2) Å to the phosphinine and P(OEt)2 groups, respectively.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300706
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    On the Polymorphism of White PhosphorusDedicated to Professor Gottfried Huttner on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1235-1240 
    Details
    ISSN: 0009-2940
    Keywords: Phosphorus ; Phase transitions ; Molecular crystal ; Crystal growth ; Low-temperature crystal structure ; Librational motion ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: White phosphorus occurs in three modifications. The α form, which exists at roomtemperature, transforms reversibly to the β form at -77°C. The α · β transformation may be strongly delayed. Quenching the α form to -185°C followed by slow warming results in an exothermic reactions with formation of the γ form which transforms into the β form at -120°C in an endothermic reaction. A transition β · γ is not observed. The γ form is characterized by its powder diagram. The structure of the β form is redetermined from a single crystal at -185°C (P., α = 547.88(5), b = 1078.62(11), c = 1096.16(11)pm, α= 94.285(8), β = 99.695(7), γ = 100.680(7)., V = 623.79(10) · 106 pm3, Z = 6 formula units per cell). The P4 molecules exhibit pronounced librational motion in spite of the low temperature of investigation. The arrangement of the centers of the tetrahedra corresponds to the atom positions in the γ-plutonium structure, which is discussed in relation to the bcc structure.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300911
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    Chiral Polysiloxane-Fixed Metal 1,3-Diketonates (Chirasil-Metals) as Catalytic Lewis Acids for a Hetero Diels-Alder Reaction -Inversion of Enantioselectivity Upon Catalyst -Polymer Binding (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 879-885 
    Details
    ISSN: 0009-2940
    Keywords: Asymmetric catalysis ; Cycloadditions ; Lewis acids ; Polymers ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A dimethylpolysiloxane chain is covalently bound to the monomeric Lewis acid catalyst (1R)-(+)-oxovanadium(1V) bis[3- heptafluorobutanoylcamphorate] [(+)-5a] at the C-10 position of the camphor moiety yielding the novel chiral polymeric (1S)-( +)-oxovanadium(1V) bis[3-heptafluorobutanoylcamphorate] -dimethylpolysiloxane [( +)-6a][1]. The Lewis acid promoted hetero Diels-Alder reaction of trans-l-methoxy-3-(trimethylsilyloxy)- 1,3-butadiene (1) and benzaldehyde (2) is studied in the presence of the enantiomerically pure monomeric (5a, 5b) and polymeric (6a, 6b) catalysts. The monomeric and polymeric catalysts of identical chirality[1] invoke opposite enantioselectivities toward the formation of 2-phenyl- 2,3-dihydro-4H-pyrone (4). This remarkable result is corroborated by numerous control experiments. Thus, it is demonstrated that the environment of the active site of the catalyst is changed when the complex is fixed to a polymeric chain. In contrast to 5 and 6, the monomeric 12 and polymeric 13 europium(III) tris[3-heptafluorobutanoylcamphorates] of identical chirality invoke the same enantioselectivity toward the formation of 4. The concept of polymer attachment is utilized to recover the catalyst from the reaction mixture by precipitation and to recycle it for subsequent catalytic runs.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300711
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    Cp3Zr(acetonitrile)+: Structure of an Electron-Rich Organometallic d0-Cation (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 899-902 
    Details
    ISSN: 0009-2940
    Keywords: Cp3Zr complexes ; Cationic organometallic Lewis acid ; d0-Configured metal complex ; Acetonitrile ; crystal structure analysis of Zirconium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The organometallic salt [Cp3Zr(N≡C-CH3)]+ [CH3B-(C6F5)3]- (3a) has been prepared by treatment of Cp3ZrCH3 with B(C6F5)3 followed by the addition of acetonitrile. X-ray crystal structure analysis of 3a shows that its cation consists of three uniformly coordinated η5-cyclopentadienyl ligands about the zirconium atom. The acetonitrile ligand is end-on coordinated. In the linear [Zr] -N≡C-CH3 unit the C≡N triple bond [N-C2 1.126(5) Å] is slightly shorter than in the free acetonitrile molecule [dC≡N = 1.141(2) Å], the structure of which was determined as a reference by X-ray diffraction of a crystal obtained by IR-laser-induced zone melting on the diffractometer.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300714
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  • 63
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    Benzophenoneimine Complexes of Copper(1)Dedicated to Professor J. Strähle on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 947-950 
    Details
    ISSN: 0009-2940
    Keywords: Copper ; N ligands ; Copper(I) complexes ; (Imine)copper(I) complexes ; Ketimines ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of [(MeCN)4Cu]BF4 with two or three equivalents of benzophenoneimine lead to the formation of [(Ph2C=NH)2]BF4 (1) and [ (Ph2C=NH)3Cu]BF4 (2), respectively. A further equivalent of the ligand does not coordinate to the cation of complex 2. The crystal structures of both compounds were determined. 1 shows a linearly two-coordinated copper(I) center with a Cu-N distance of 1.877(2) Å. In compound 2 a distorted trigonal planar coordination of copper is observed with N-Cu-N angles of 114.5(2), 112.9(2) and 132.4(2)°, corresponding to two nearly equal Cu-N distances [Cu-N2 1.947(5) and Cu-N3 1.934(5) Å] dnd a significantly longer third one (Cu-N1 2.011(5) Å]. A comparison of these data with recently determined structures of bis(benzophenoneimine)silver(I) and -gold(I) complexes shows that the covalent radii of the monovalent coinage metals decrease in the order Ag(I) 〉 Au(I) 〉 Cu(I).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300721
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    Organoantimony Oxides: Preparation and Crystal Structures of [(2-PhOC6H4)O (C6H4)2Sb]2O2 and (o-Tol2Sb)4O6Dedicated to Prof. Dr. Gottfried Huttner on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 959-961 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Air oxidation of (Oxydi-2,1-phenylene)(2-phenoxyphenyl)stibane (1) gives the phenoxystibane oxide [(2-PhOC6H4)O(C6H4)2Sb]2O2 (2). Single crystals of (o-Tol2Sb)4- O4(O2)2 (3) were obtained by air oxidation of o-TolSb-(SiMe3)2. Crystal structures of 2 and 3 are reported.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300724
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    Zinc Pyrazolylborate Complexes with Phenoxide and Alkoxide LigandsDedicated to Professor Wolfgang Beck on the occasion of his 65th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 975-980 
    Details
    ISSN: 0009-2940
    Keywords: Zinc complexes ; Phenoxide complexes ; Alkoxide complexes ; Terminal alkoxide ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The zinc hydroxide complexes Tp*Zn-OH of highly substituted pyrazolylborate ligands react with phenols, and alcohols, of sufficient acidity, in a condensation reaction with release of H2O. Starting with phenols the following were attached:phenolate, p-nitropehnolate, o-vanillinate, o-hydroxymethylphenolate, o,o-bis(hydroxymethyl) -p-methylphenolate. Whilst aliphatic alcohols and benzyl alcohol did not react, their derivatives, with highly electronegative substituents could be incorporated. Thus, the arylmethoxides OCH2C6F5 and OCH2C6H4NO2-p, as well as the alkoxides OCH2CF3 and OCH2CCl3, were attached. 2-Mercaptoethanol was bound via its thiolate function. The crystal structures of TpCum,Me ZN-OC6H4NO2-p,TpCum,Me ZN-OCH2-C6F5, TpCum,Me ZN-OCH2CF3, TpCum,Me ZN-OCH2CCl3 and TpCum,MeZn-SCH2CH2OH were determined.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300727
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    Pseudoelement Compounds, XPart IX: Ref. Synthesis and Crystal Structure of New Complexes of the Type trans-[Pt(H)X(PPh3)2 with Cyanamide and Cyanomethanide LigandsDedicated to Professor S. Engels on the occasion of his 65th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1007-1012 
    Details
    ISSN: 0009-2940
    Keywords: Platinum ; Nitrocyanamide ; Nitrosodicyanomethanide ; 1,1,3, 3-Tetracyano-2-azapropenide ; 1,1,2,3,3-Pentacyanopropenide ; Hydrido complexes ; Coordination modes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new coordination compounds trans-[Pt(H)X(PPh3)2] with NCN- and C(CN)2-functionalized anions (X- = [N(O)C(CN)2]-, [NO2NCN]-, [N{C(CN)2}2]-, [NCC{C-(CN)2}2]-, have been characterized by 1H-, 31P-, 13C-NMR, and IR spectroscopy and elemental analyses the crystal structures of trans-[Pt(H)N(O)C(CN)2(PPh3)2], trans- [Pt(H)N{C(CN)2}2(PPh3)2], and trans-[Pt(H)NCC{C(CN)2}2-(PPh3)2) have been determined by X-ray diffraction. Remarkably, [N(O)C(CN)2]- is coordinated through the central nitrogen atom, while [N{C(CN)2}2]- and [NCC(C(CN)2]2]- are bonded through terminal nitrogen atoms of a C(CN)2 unit.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300730
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    New Coupling Reactions and Phosphorylations Using Organozinc Reagents (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1021-1027 
    Details
    ISSN: 0009-2940
    Keywords: Zinc ; Chirality ; Cross-coupling ; Phosphorylations ; Catalysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This Microreview on the chemistry of organozinc reagents starts by briefly showing the methods of preparation of organozinc compounds and then discusses the considerable synthetic utility of zinc organometallics for the formation of new carbon-carbon bonds in the presence of transition-metal catalysts. Finally, the use of organozinc chemistry for the preparation of polyfunctional and chiral phosphanes is described.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300802
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    Synthesis and Structures of Bis(tetramethylipiperidino)aluminum Halides-X-ray Crystal Structures of tmp2AlX (X = Cl, Br, I) and [tmp2A1(μ-F)l2 (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1047-1052 
    Details
    ISSN: 0009-2940
    Keywords: Bis(tetramethylipiperidino)aluminum halides ; Alkoxy((tetramethylpiperidino)aluminum halides ; 27Al-NMR spectra ; Aluminum ; Amides ; Synthetic methods ; Bridging ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Lithio-2,2,6,6-tetramethylpiperidine [Li(tmp)] reacts with AlX3 (X = Cl, Br) in diethyl ether/ n-hexane solution to generate the products of substitution and ether cleavage, [tmpAl(X)(μ-OEt)], (la, X = Cl; 1b, X = Br). However, when the reaction is allowed to proceed in n-hexane alone, an almost quantitative yield of compounds tmp2AlX (2a, X = Cl; 2b, X = Br; 2c, X = I) is obtained. According to 27AI-NMR spectroscopy, mass spectroscopy, cryoscopy, and X-ray crystal structure determinations, these compounds are monomeric in the solid state, in solution, and in the gas phase. 2b reacts with AgBF4 yielding the fluoride-bridged dimer (tmp2AlF), 2d, as shown by X-ray crystal structure determination.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300805
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  • 69
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    Structure and Reactivity of Sodium Phenoxide - Following the Course of the Kolbe-Schmitt Reaction (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1461-1465 
    Details
    ISSN: 0009-2940
    Keywords: Kolbe-Schmitt reaction ; Solid-state structures ; Sodium phenoxide ; Solvent Complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solvent-free sodium phenoxide (NaOPh) crystallises as a polymer and forms a polymeric chain in the [0 0 1] direction. The low coordination of the sodium atoms, as evident in the crystal structure, is confirmed by the easy coordination of oxoligands (α-donors). Hence, the four-membered ring chain of the solvent-free sodium phenoxide is separated by oxoligands, and forms partial structures as the polymer fragments. Thus, NaOPh crystallises in THF with the formation of an Na6O6 core, consisting of two face-fused heterocubes, and in N, N, N′, N′-tetramethyl urea (TMU) with the formation of a Na4O4 heterocubane. The solvent-free NaOPh-CO2 complex obtained from the addition of CO2 to a solution of sodium phenoxide is, when exposed to a temperature of 80°C, subject to an irreversible phase transition, as demonstrated by FT-IR and DTA studies. The complex formed at 80°C is, apparently, another intermediate of the Kolbe-Schmitt reaction.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971301017
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    1,8-Bis(phosphanyl)naphthalenes: 1,8-Bis[(diethylamino)phosphanyl]-naphthalene, 1,8-Bis(dichlorophosphany)naphthalene, and 1, 3-Dichloro-2,-3-dihydro-1,3-dioxo-2-oxa-1,3-diphosphaphenaleneDedicated to Professor Huns Burger on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1485-1489 
    Details
    ISSN: 0009-2940
    Keywords: Naphthalenes ; Phosphanes ; Phosphorus heterocycles ; Protecting groups ; Strained molecules ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1.8-dilithionaphthalene 1 reacted with bis(dimethylamino)-chlorophosphane to form 1,8-bis[(diethylamino)phosphanyl]-naphthalene 2, whose structure was confirmed by X-ray crystal structure analysis; there are two independent molecules, in which the P(NEt2)2 groups adopt an eclipsed conformation. Reaction of 2 with gaseous HCl gave in low yield 1,8-bis-(dichlorophosphanyl)naphthalene 3, which was characterized by 1H- and 31P-NMR spectroscopy, mass spectrometry and elemental analysis. Attempted recrystallization of 3 led to oxidative hydrolysis which furnished 4, an anhydride of a bis(chlorophosphonic acid), whose structure was elucidated by X-ray crystal structure analysis. The geometry of 4 reveals a relief of strain from the bis (aminophosphane) 2; the naphthalene groups are less distorted and the P atoms are displaced less far from the naphthalene best plane.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301021
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    Coordination Compounds of Coinage Metals with Vinylidenebis(diphenyl-phosphane) and Its Disulfide and Their Reactivity towards NucleophilesDedicated to Professor P. Royo on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1513-1517 
    Details
    ISSN: 0009-2940
    Keywords: Gold ; Silver ; Diphosphane ; Diphosphane Disulfide ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinylidenebis(diphenylphosphane) reacts with gold(I) or gold(III) compounds to give dinuclear {[{Au(C6F5)]2[(PPh2)2C=CH2{] or [Au{PPh2C(=CH2)Ph2P)]2(ClO4)2] or mononuclear complexes ([Au(C6F5)3(PPh2C(=CH2)Ph2P)]}, respectively. The latter reacts with gold(I) or silver(I) compounds to afford dinuclear [[Au(C6F5)3[PPh2C(=CH2)Ph2P}AuX], X=Cl or C6F5) or trinuclear species {[{Au(C6F5)3{PPh2C(=CH2)Ph2P{]2M]ClO4, M=Au or Ag}. No addition of nucleophiles to the C=C double bond is observed in these complexes, which contain the diphosphane acting as bridging or monodentate ligand. (SPPh2)2C=CH2 reacts with AgClO4 to give [Ag{SPPh2C(=CH2)Ph2PS}]2-(ClO4)2or[Ag[PPh2C(=CH2)Ph2P]2]ClO4. The crystal structure of [Au(C6F5)3{PPh2C(=CH2)Ph2P}Au(C6F5)] has been established by X-ray crystallography, and confirms the expected square planar and linear geometry for the Au111 and Au1 centres, respectively.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301026
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    Diastereoselective Synthesis and Molecular Structure of a Bicyclic and a Cage Phosphane (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1547-1550 
    Details
    ISSN: 0009-2940
    Keywords: Phosphane ; 1,3α., 5,7β-Tetrakis(trifluoromethyl)-6,-9-dioxa-2-phosphabicyclo[3.3.1]nonane-3β, 7α-diol ; 1,7-Trifluoromethyl-3,5-methyl1-2,4.8-trioxa-6-phosphaadamantane ; Phosphorus heterocycles ; Ketones ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A two-step formal insertion of 1,1,1,5,5,5-hexafluoro- (2a) and 1,111-trifluoropentane-2,4-dione (2b) into the P-H bonds of phosphane gave the primary a-hydroxyphosphanes 3 and 4, precursors for the resulting secondary phosphanes, 6,9-dioxa-2-phosphabicyclo[3.3.l]nonane (6a) and 2,4,8-trioxa-6-phosphaadamantane (7), both formed diastereospecifically. The molecular structures of 6a and 7 were established by single-crystal X-ray structure analysis which revealed two independent molecules for 6a in the unit cell possessing a chair-boat conformation with a C-P-C angle of 95.4(2)°, and a characteristic heteroadamantane geometry for 7, with the corresponding angle being smaller by 4.9°.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301031
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    Reactions of Complex Ligands, LXXVII. Axial-Chiral Metal Carbenes: Synthesis and Structure of 1,1-Binaphthyl-Derived Carbonyl-Carbene Complexes of Chromium (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1605-1609 
    Details
    ISSN: 0009-2940
    Keywords: Axial-chiral complexes ; Biaryls ; Carbene complexes ; Circular dichroism ; Chromium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Axial-chiral mono- and biscarbene complexes of chromium containing the 1,1-binaphthyl skeleton have been obtained in both racemic and enantiopure forms in a one-pot reaction starting from lithiated 2,2-dimethoxy-1,1-binaphthyl (1) and hexacarbonyl chromium via the Fischer route. An X-ray structure analysis of the biscarbene complex 2 reveals that the biscarbene functionalization significantly increases the dihedral angle defined by the biaryl planes. The enantiopure complexes have been characterized by CD spectroscopy.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301108
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    Evidence for Internal Ion Pair Formation upon Insertion of Reactive Alkene in the Zirconium-Carbon Bond of the cp2Zr(μ-C4h6)b(c6f5)3 Metallocene-Boron-Betaine Ziegler Catalyst System (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1261-1267 
    Details
    ISSN: 0009-2940
    Keywords: Single-component metallocene catalyst ; Olefin insertion ; Organometallic ions pairs ; (Alkene)metallocene complex ; Metallocene betaines ; C-C coupling ; Zirconium ; Homogeneous catalysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of the (butadiene)ML2 complexes 1 [ML2 = Cp2Zr (a), Cp2Hf (b), and (.-C5H4CH3)2Zr (c)] with B(C6F5)3 gives the 1:1 addition products (CH2CHCHCH2-B(C6F5_3)ML2 (3a-c). At -40°C the betaine complex 3a inserts one equivalent of methylenecyclopropane to give the regioisomeric insertion products 5a and 6a in a 60:40 ratio. These products exhibit the cyclopropylidene moiety in the α- and β-positions, respectively, relative to zirconium. The corresponding hafnocene complexes 5b and 6b are obtained in a 70:30 ratio starting from 3b. The reaction of 3(a-c) with allene gives a single insertion product (7a-c) in each case where the exo-methylene group is in the α-position to the metal center ([2,1]-insertion). The complexes 5-7 are chiral. They all exhibit a pronounced ·-interaction of the internal -C4H=C5H- double bond of the s̰-ligand chain with the metal center in addition to a metallocene/-C6H2-[B] ion pair interaction. The relative contributions of the cationic metallocene end of the dipolar complexes 5-7 are quite dependent on the steric and electronic properties of the respective metallocene units involved. This is revealed by a comparison to typical 13C-NMR parameters of the complexes 5-7 with a pair of suitable model complexes, namely the ethylene insertion product 4 into the betaine system 3a and its THF adduct 4.THF.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19971300914
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    Tripod Ligands Containing a Mixed P/N/S Doner Set: Synthesis and Coordination Chemistry (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1279-1294 
    Details
    ISSN: 0009-2940
    Keywords: Tripodal ligands ; Aminolytic cleavage of oxetanes ; Tripod molybdenum compounds ; Mixed donor set ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of neopentane-based tripod ligands CH3C(CH2X)(CH2Y)(CH2Z( 3 (X = NR2, NHR; Y = PR2; Z = PR2, SR, S-) in a convergent manner is described. The procedure is based on the aminolytic cleavage of functionalized oxetanes CH3C(CH2OCH2)CH2R 1 by primary or secondary amines, leading to functionalized amino alcohols CH3C(CH2NHR)(CH2OH)(CH2R) or CH3C(CH2NR2)-(CH2OH)(CH2R) 2. The appropriate activation of the R (e.g. OR) and OH groups present in 2 allows for substitution vs. SR or PR2 donor functions. Depending on the nature of the groups present in each reaction step, various protection and groups present in each reaction step, various protection and deprotection steps have to be taken in the course of this type of preparation of the tripod ligands 3. By reaction with (CH3CN)3Mo(CO)3, ligands 3 form Mo(CO)4 derivatives 4 or Mo(CO)3 derivatives 5, depending on the reaction conditions. In compounds 4, the ligands are coordinated in a bidentate mode with the soft donor atoms (P, S) coordinated and the hard donor function playing the role of the dangling arm. In the trihapto bonding mode present in 5, all three donor functions, two soft (P, S) and one hard (NHR′, NR′2), are coordinated. The two types of coordination compounds may be interconverted: 4e (X = NMe2′ Y = PPh2, Z = SiPr) with a non-coordinating CH2NMe2 group is transformed into 5c upon photolytic decarbonylation. Under 1 bar CO at 20°C, 5c reverts to 4e. X-ray structure analysis of a series of compounds of types 4 and 5 reveals characteristics of the relevant conformational patterns. All compounds have been fully characterized by the standard analytical techniques (NMR, MS), as well as elemental analysis.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300917
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    Neutral Gold(I) Complexes with Mixed Phosphorus LigandsDedicated to Professor Wolfgang Beck on the occasion of his 65th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1333-1338 
    Details
    ISSN: 0009-2940
    Keywords: Gold ; Gold(I) complexes ; Phosphinite complexes ; Phosphite complexes ; Configuration determination ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of compounds (R3P) AuMe with diphenylphosphinous acid Ph2P(O)H affords methane and neutral complexes of the type (R3P(O)Ph2 (1a: R = Me; 1b: R = Ph, lc: R = o-Tol). 1a, b are obtained in high yield, but the yield of lc is lower owing to a side-reaction which leads to a different product: Ph2P(OH)-Au-P(O)Ph2 (2). The crystal structure of 1a was determined by a single-crystal X-ray diffraction study. The compounds is a monomer with a linear P-Au-P′ axis and the phosphane and phosphinite ligands in a staggered conformation. In solution (CHCl3, CH2Cl 2/) compounds 1a-c undergo a ligand redistribution, establishing equilibria that involve ionic isomers of the type [R3P)2Au]+ [Au-(P(O)Ph2)2]-, which are readily identified through their NMR data. The analogous reaction of (R3P)b AuMe with dimethylphosphite (MeO)2P(O)H gives methane and the corresponding dimethylphosphites of the type (R3P)AuP(O)(OMe)2 (3a: R = Me; 3b: R = Ph; 3c: R= o-Tol). The crystal structure of 3b has also been determined. It features a linear structure with an eclipsed conformation of the ligands. In polar solvents (CHCl3, methanol) there is again an eqilibrium between neutral and ionic isomers, the latter comprising bis(phosphane)gold cations [(R3P)2Au]+ and {Au[P(O)-(OMe)2]2)- anions, as confirmed by NMR spectroscopy and mass spectrometry.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300925
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  • 77
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    Regioselective Complexation of New Multiple Piperazine/Pyridine Ligands: Differentiation by 113Cd-NMR Spectroscopy (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1353-1359 
    Details
    ISSN: 0009-2940
    Keywords: 113Cd NMR ; Multidentate ligand ; Multinuclear metal complex ; Piperazine ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Eleven novel piperazine containing open-chain ligands L1-L11 were designed to offer symmetrical and asymmetrical complexation sites for metal ions and were synthesized by repetitive synthetic method. The divergent use of aromatic bishalomethyl and mono-N-alkylated piperazine compounds as spaces led toa series of long (up to M. W. = 836) oligomeric multidentate N-ligands. Due to the lack of solid state methods for structure analysis, an NMR technique using 113 Cd nucleus as a probe in solution state was utilised. 113 Cd chemical shifts were observed to be dependend on the coordination site and similar coordination sites in different ligands gave characteristically similar 113 Cd chemical shifts. As a result 113 Cd-NMR spectroscopy proved to be an excellent tool to distinguish between the structures of the different complexation sites on a nearly quantitative level.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300929
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  • 78
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    Design of Self-Adapting N-Heteroaromatic Substituted Claw Ligands as E-/M+(E = P-Block Element, M = Main-Group Metal) Charge Spacers (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1365-1374 
    Details
    ISSN: 0009-2940
    Keywords: N ligands ; Chelates ; Coordination modes ; Ligand effects ; Structure-activity relationships ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monoanionic bi- and tridentate ligand systems emulating the structural features of the well-known poly(pyrazolyl)borates are created by bridging heteroaromatic rings with formally negatively charged p-block elements. Their properties and versatility are exemplified by their complexes with main group metals. Due to their N(σ)-donating and π-interacting ability, as well as the flexibility of the substituent bonding, these ligand systems have the potential to adapt both geometrically and electronically to the coordination requirements of the complexed metal. Within these complexes, the heteroaromatic substituents operate as charge spacers between the formally anionic center and the metal cation without encapsulating either site. This provides possible applications in the creation of reactive soft/hard bimetallic reagents, the realization of multinuclear arrays, and the design of preorganized CVD precursors, particularly en route to III/V-semiconducting thin films.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301004
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  • 79
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    Cyclic and Bicyclic Poly(phosphane)borane Cations (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1411-1416 
    Details
    ISSN: 0009-2940
    Keywords: Phosphane-boranes ; Boranes ; Phosphanes ; Umpolung, attempted ; Bond polarity ; Configuration determination ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of (Me2S)BH2Br and (Me2S)BHBr2 with equimolar quantities of 1,2-bis(diphenylphosphanyl)ethene (1) or -benzene (2) lead to cyclic, cationic bis(phosphane)boranes [4[(1)BH2]+ Br-; 6: [(2)BH2]+ Br; 7: [(2)BHBr]+ Br-]. The Br counterions can be exchanged in metathesis reactions (e.g. with AgBF4 to afford 4a). The tritertiary phosphane bis[2-(diphenylphosphanyl)phenyl]phenyl-phosphane (3), reacts with (Me2S)BHBr2 to give bicyclic dicationic tris(phosphane)borane 8, [(3)BH]2+ Br-, which can be converted into the bis(hexafluorophosphate) 8a using NH4PF6. All compounds have been characterized by analytical and NMR-spectroscopic data. The crystal and molecular structures of 5 - 7 have been determined by single-crystal X-ray diffraction. The five-membered rings C2P2B have an envelope conformation and show no sign of electron delocalization. Attempts to deprotonate the B—H functions in 5 - 8 have not been successful. Clearly, the two (5 - 7) or three phosphonium centers (8) adjacent to the boron atom are not sufficient to induce an “umpolung” of the B—H group
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301009
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  • 80
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    Reactivity of the Heavier Group-13 Monochlorides [{CH(SiMe3)2}2AlCl], InCl, TlCl, and of the Elements Ga and Hg Towards the Unsupported Ni-Ni Bond of [{(η5-Cp)Ni(PEt3)}2]  -  A Straightforward Synthetic Approach to the Synthesis of Mixed Main-Group/Transition-Metal Clusters Containing Unsupported Metal-Metal BondsDedicated to Prof. Dr. G Hutter on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1433-1440 
    Details
    ISSN: 0009-2940
    Keywords: Metal - metal bonds ; Insertion reactions ; Group-13 monochlorides ; Main-group elements ; Nickel ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dinuclear compound [{(η5 - Cp)Ni(PEt3)}2] (1) containing an unbridged Ni-Ni bond reacts with the heavier group 13 monochlorides [{CH(SiMe3)2)2}AlIIICl], InCl, and TlCl by scission of the metal-metal bond. In the case of InCl and TlCl the chloro-bridged dimmers [{(η5-Cp)Ni(PEt3)2ECl2Ecl}2] (E = In 2, Tl 5) were formed. The Tl compound 5 is unstable and decomposes via disproportionation a and formation of the halogen-free Tl [III] compound [{(η5-Cp)Ni(PEt3)}3Tl] (6). 2 can be dehalogenated with activated magnesium to yield the halogen-free In [III] compund [{(η5-Cp}Ni(PEt3)}3In] (4). The Ga analogue of 4 and 6 [{(η5-Cp)Ni(PEt3)}3Ga] (7) is accessible by a conproportionation of 1 with Ga metal in refluxing THF. In contrast to InCl and TlCl the aluminium (III) monochloride [{CH(SiMe3)2}2AlCl] reacts with 1 by a ligand redistribution reaction and formation of the salt [{(η5-Cp)Ni(PEt3)2]+-[{CH(SiMe3)2]2AlCl]2-. (8). Elemental Hg or Mg amalgam show the same activity as elemental Ga towards 1 and insert into the Ni—Ni bond by forming the linear Hg-bridged complex [(n3-Cp)Ni(PEt3)]2Hg] (9). The molecular structures of 2, 4, 8, and 9 were determined by X-ray crystallography. The In atom in 4 has a distorted trigonal-planar configuration with the central In atom being surrounded by three [(n5-Cp)Ni(PEt3)] fragments. 4 represents the first Ni-In cluster containing exclusively unsupported In - Ni bonds, as well as the first carbonyl-free Ni - In cluster. On the basis of spectroscopic data the same structure is assigned to the Ga and Tl analogues of 4. The Ni—Hg—Ni arrangement in 9 is exactly linear, as determined by X-ray crystallography.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301013
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  • 81
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    Hydrocarbon-Bridged Complexes, XL. Polyene-Bridged Iridium(III), Palladium(II), and Platinum(II) Complexes of Schiff Bases from α,ω-Polyene Dialdehydes and α-Amino Acids or o-AminophenolDedicated to Professor Dieter Seebach on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1467-1473 
    Details
    ISSN: 0009-2940
    Keywords: Schiff bases ; Polyene dialdehydes ; α-Amino acids ; Pantamethylcyclopentadienyl complexes ; P ligands ; Iridium ; Palladium ; Platinum ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Schiff bases 1—11 were synthesized from α-amino acids or o-aminophenol and crocetindialdehyde, 2,7-dimethyloctatrienedial, terephthalaldehyde, or β,β′ -p-phenylendiacroleine. The reactions of these Schiff bases with chloro-bridged complexes [(R3P)(Cl)M(η-Cl)]2 (M = Pd, Pt) and [(C5Me5)(Cl)Ir(°Cl)]2 gave the dinuclear complexes 12-31.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301018
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  • 82
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    Enantioselective Catalysis. New Chiral Expanded Phosphanes Derived from Substituted Deltacyclenes (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1495-1498 
    Details
    ISSN: 0009-2940
    Keywords: Deltacyclenes ; Deltacyclanes ; P-H addition reactions ; Chiral phosphanes ; Enantioselective catalysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The suitability of enantiomerically pure deltacyclenes as building blocks in the synthesis of expanded phosphanes was examined. Different substituted deltacyclenes were irradiated with diphenylphosphane and three bisphosphanyl derivatives. With these P—H addition reactions, new chiral deltacyclane-derived phosphorus ligands were synthesized. They were tested in the Rh-catalyzed asymmetric hydrogenation of (Z)-(ã)-N-acetamidocinnamic acid and in the Pd-catalyzed asymmetric allylation of 1,5-dimethylbarbituric acid.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301023
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  • 83
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    Masthead (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300101
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    Photochemical reactions of transition metal organyl complexes with olefins, 17Part 16: Ref.. Light-Induced [6+2] Cycloadditions of Dienes to Tricarbonyl(η6-1,3,5,7-cyclooctatetraene)chromium(0) (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 9-12 
    Details
    ISSN: 0009-2940
    Keywords: Chromium ; Chromium(0) complexes ; Cyclooctatetraene complexes ; Photochemistry ; Cycloadditions ; Photochemical [6+2] cycloadditions ; Dienes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tricarbonyl(η6-1,3,5,7-cyclooctatetraene)chromium (1) yields upon UV irradiation in ether at 233 K with 2,3-dimethyl-1,3-butadiene (2) or 2-methyl-1,3-butadiene (3) by [6+2] cycloadditions the correspondingly substituted tricarbonyl(η6-bicyclo[4.2.2]deca-2,4,7-triene)chromium complexes 4, 5a and 5b. With ammonium cerium(IV) nitrate the organic ligand of complex 4, 9-isopropenyl-9-methyl-bicyclo[4.2.2]-deca-2,4,7-triene (6) is liberated. The complexes 4, 5a and 5b were characterised by IR and NMR spectroscopy, the ligand 6 by NMR spectroscopy.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300103
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    A Structural Study of Selenobenzamides: Crystal Structures and Dynamic 13C NMR (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 49-54 
    Details
    ISSN: 0009-2940
    Keywords: 4-(p-Bromoselenobenzoyl)morpholine ; 4-[(p-(Dimethylamino)selenobenzoyl]morpholine ; Hindered rotation ; Hammett treatment ; Selenoamides ; Amides ; Selenium compounds ; Structure elucidation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solid-state structures of (p-bromoselenobenzoyl)morpholine (2a) and [p-(dimethylamino)selenobenzoyl]morpholine (2b) were determined by X-ray diffraction. Both molecules show a flat selenoamide group. The larger contribution of resonance stabilization by the aromatic ring carrying the p-dimethylamino substituent is reflected by the smaller interplanar angle Θ between the aromatic ring and the selenoamide group [53.3(1)° vs. 81.1(1)°] and by the shorter length of the C=Se bond [1.824(5) Å vs. 1.840(3) Å]. The Gibbs free energy of activation of C-N bond rotation (ΔG≠rot) of five p-substituted (selenobenzoyl)morpholines was determined by dynamic 13C NMR. The activation barriers were found to range from 61.6 kJ/mol (X = NNMe2) to 75.1 kJ/mol (X = H). The ΔG≠rot values of the corresponding (thiobenzoyl)morpholines were found to be from 3.2 kJ/mol (X = NMe2) to 5.0 kJ/mol (X = H) lower. In both cases, ΔG≠rot showed an excellent linear Hammett correlation with s̰+p.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300108
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  • 86
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    Synthesis and Characterization of Substituted Benzyl Zinc Derivatives - Molecular Structures of (tmeda) Li-CH (GeMe3)Ph, (tmeda)Zn(CH2Ph)2, (tmeda)Zn[CH(SiMe3)Ph]2, and (tmeda)Zn[CH(SiMe3)Ph]N(H)Si(SiMe3)3Dedicated to Professor Manfred Weidenbruch on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1499-1505 
    Details
    ISSN: 0009-2940
    Keywords: Lithium ; Zine ; Dibenzylzinc ; Tmeda complexes ; Heteroleptic alkylzinc amide ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of lithium phenyl(trimethylsilyl)methanide with phenyl(trimethylsilyl)methylzinc chloride-tmeda in the presence of tmeda yields the addition product, a bis(tmeda)-lithium dialkylchlorozincate. The elimination of lithium chloride leads to the formation of a tmeda adduct of bis[phenyl-(trimethylsilyl)methyl]zinc. The metathesis reaction of phenyl(trimethylsilyl)methylzinc chloride-tmeda with lithium tris(trimethylsilyl)silylamide allows the isolation of the corresponding heteroleptic tmeda complex of an alkylzinc amide. The metalation of phenyl(trimethylstannyl)methane with butyllithium yields the transmetalation product benzyllithium. From the metathesis reaction of this lithium base with anhydrous zinc(II) chloride in the presence of tmeda, the tmeda adduct of dibenzylzinc crystallizes. The molecular structures of (tmeda)Li—CH(GeMe3)Ph, (tmeda)Zn(CH2Ph)2, (tmeda)Zn[CH(SiMe3)Ph]2, and (tmeda)Zn[CH(SiMe3)-Ph[N(H)Si(SiMe3)3 are reported. Whereas lithium bonds in an η3-fashion, the zinc atom forms a σ(Zn—C) bond. The extremely wide Zn—N—Si angle in (tmeda)Zn[CH(SiMe3)-Ph[N(H)Si(SiMe3)3 of 157° is remarkable.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971301024
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    Unusual Dinuclear Hydridorhodium(III) Complexes Containing Bulky Phosphanyl(stibanyl)methanes as Chelating LigandsDedicated to Professor Luigi Venanzi on the occasion of his 70th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1529-1531 
    Details
    ISSN: 0009-2940
    Keywords: Rhodium ; Chelate complexes ; Hydrido complexes ; Bridging ligands ; P Ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mononuclear starting materials [Rh(η4-C8H12)(k2-P,Sb-iPr2PCH2SbR2)]PF6 (la, b) react with CF3CO2H in the presence of H2 to give the dinuclear hydridorhodium(II1) complexes [{RhH(k2-P,Sb-iPr2PCH2SbR2)]PF6 (2a, b) in almost quantitative yield. The X-ray crystal structural analysis of 2b (R = tBu) reveals a distorted octahedral geometry around the two metal centers with the two phosphanyl(stibanyl)methanes in a chelating and the two trifluoracetate ligands in a bridging coordination mode.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301028
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  • 88
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    X-ray and Solution Structure of Inosine 5' -Monophosphate Coordinated to (Ethylenediamine)palladium(II).  - the Importance of Intramolecular Hydrogen Bonding (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1551-1555 
    Details
    ISSN: 0009-2940
    Keywords: Antitumor agents ; Nucleotides ; Palladium ; Hydrogen bonds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The compound [Pd(en)(5′-IMP-N7)2].11 H2O, where 5′-IMP = inosine 5′-monophosphate, crystallizes in the tetragonal space group P4322 with the unit cell parameters: a = b = 12.060(5) and c = 28.510(5) Å, V = 4147(3) Å3, Z = 4. A head-to-tail orientation with A configuration is observed for the nucleotides which are coordinated through the N(7) positions such that d[Pd-N(7)] = 2.053(8) Å. The sugar moieties exhibit anti orientations toward the purine bases while their pukkers adopt C(3)′-endo conformation. The overall conformation about the phosphate backbone is gauche+. Intramolecular hydrogen bonding is observed between the phosphates and the NH groups of the en ligand with a donor-acceptor distance of 2.88 Å. The coordination mode of the solid-state structure is shown to be identical to that observed by 1H-NMR spectroscopy in solution under slightly acidic conditions, where the N (l) positions of the nucleotides are protonated. The results are discussed in reference to closely related systems reported in the literature with emphasis on the importance of hydrogen bonding in such complexes.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301032
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  • 89
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    Synthetic and Structural Studies of 1-Sila-2,5-diaryltetrazenes (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1579-1583 
    Details
    ISSN: 0009-2940
    Keywords: Silatetrazenes ; Nitrogen-silicon ring systems ; Bissilylamines ; Silicon-29 solid state NMR ; Aryl azides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between aryl azides and lithiated aryl amines leads to tetrazenes 3 and 9 which contain a chain of four nitrogen atoms. Reaction with different halosilanes gives the cyclic silatetrazenes 10, 12, and 15 where substitutents on the silicon vary form alkyl to hydrogen and chlorine atoms. The structures of 10, 12, and 15 in the solid state are reported. Variation of the solvent and the Lewis acidity of the halosilane influence the ratio of silatetrazene to side products, bissilyated amines. These effects are studied for different halosilanes.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19971301105
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  • 90
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    Bildung und Charakterisierung des Dinatrium-tetraphosphendiids (tBu3Si)NaP-P=P-PNa(SitBu3) und seines Dimeren (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 135-140 
    Details
    ISSN: 0009-2940
    Keywords: Synthesis ; Phosphorus ; Supersilyloligophosphides ; Crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of P4 in THF or DME with 2 R*Na (R* = SitBu3) at -78°C leads quantitatively to deep red THF or DME adducts of R*NaP-P=P-PNaR* (3). According to 31P NMR, the P4 skeleton 3 is cis-configurated. On the other hand, reaction of P4 in TBME with 2 R*Na at -78°C leads quantitatively to (R*NaP)4 (4), a [2+2] cycloadduct of 3, the Na4P8 skeleton of which according to X-ray structure analysis forms a double cube with four P atoms in the second layer and two P and two Na atoms in alternating positions in the first and in the third layer (the Na atoms are coordinated with donors). By resolving the THF adduct 3 in TBME (the TBME adduct of 4 in THF) the compound 4 (the compound 3) is rapidly formed under reversal of the P-P=P-P configuration by way of [2+2] cycloaddition (by way of [2+2] cycloreversion). 3 and 4 are sensitive to oxidation and to protolysis. With TCNE, 3 is oxidized to R*2P4 (bicyclic P4 skeleton), with CF3SO3H, 3 may be transformed into R*3P5Na2 X 4 THF or in (R*P3)3 and R*PH2.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300123
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  • 91
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    Cyclopentadienyl Ring Metathesis with Organocalcium and Organopotassium Compounds (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 155-159 
    Details
    ISSN: 0009-2940
    Keywords: Cyclopentadienes ; Metathesis ; Potassium ; Calcium ; Main-group elements ; Sandwich complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclopentadienyl ring metathesis occurs between [Ca(C5Me5)2] and [Ln(C5H5)3] complexes in toluene to generate the mixed ring compounds [Ln(C5Me5)2(C2H5)] (Ln=1-La, 1-Nd). 1-Nd has been characterized with X-ray diffraction as a sterically crowded monomer. Only one ring is exchanged between [Ca(C5Me5)2(thf)x] and [La(C5H5)3(thf)x] in toluene to yield [La(C5Me5)C5H5)2 (thf)] (2). In reaction with [M(C5H5)2] (M=Sn, Pb, Mn), [Ca(C5M5)2(thf)x] yields the corresponding [M(C5Me5)2] complexes. K[C5Me5] reacts with [La(C5H5)3(thf)], [Sn(C5H5)2] and [Pb[C5H5)2] in toluene to yield the ring-exchanged products 2, [Sn(C5Me5)2], and [Pb(C5Me5)2], respectively.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300204
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    Sterically Shielded Titanocene Enolates - Synthesis, Structure and Their Exceptional Stability towards Hydrolysis (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 195-199 
    Details
    ISSN: 0009-2940
    Keywords: Titanium ; Enolates ; Kinetics ; Enols ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of various sterically congested sodium enolates, generated by quantitative deprotonation of stable enols (of diphenylacetaldehyde in the case of 5), with dichlorotitanocene afforded a series of novel titanium enolates 1-5. The crystal structure of 1 could be determined. Due to the considerable steric shielding of the β,β-diaryl moiety, all the titanium enolates exhibit an oustanding stability towards hydrolysis, which increases with the higher steric demand of the substitutents at the C-C double bond. The kinetics of the hydrolysis, which is pseudo-first-order in THF/water (1 : 1) and acetonitrile/water (1 : 1), was investigated by UV spectroscopy. The pseudo-first-order rate constants measured in these solvent mixtures are in the range 6.4 · 10-4 s-1 〈 k1 〈 1.1 · 10-3 s-1. For comparison, the hydrolysis of 6, which should exhibit the usual sensitivity of titanium enolates towards hydrolysis, is about 1000 times faster.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300209
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  • 93
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    (Triphenylphosphane)gold(I) Scrambling in a Hexanuclear Complex of Phenylene-1,2-bis(phosphane) (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 217-219 
    Details
    ISSN: 0009-2940
    Keywords: Gold compounds ; (Phosphane)gold(I) complexes ; Clusters ; P Ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phenylene-1,2-bis(phosphane) reacts with two mole-equivalents of tris[(triphenylphosphane)gold(I)]oxonium tetrafluoroborate in dichloromethane at -78°C to give high yields of a hexanuclear complex {C6H4]P(AuPPh3)3]2}2+ · 2 BF-4 (1). The variable-temperature 31P{1H}-NMR spectra of the product in CD2Cl2 at - 80°C are compatible with a static structure featuring three Ph3PAu units associated with each of the two C6H4P2 phosphide functions, as derived from a clear doublet/quartet pattern. At 50°C in CDCl3, however, there is rapid intramolecular scrambling of these Ph3PAu units, which gives rise to a triplet/septet pattern with the J(P,P) value reduced to exactly one half of the value at the low temperature limit.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300212
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  • 94
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    Synthesis and Properties of New Mixed-Halide Derivatives of Iron-Sulfide Dimers-Crystal Structure of (Et4N)2[Fe2S2Cl2Br2] (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 235-239 
    Details
    ISSN: 0009-2940
    Keywords: Iron-sulfur cluster ; Mixed halide ligands ; Magnetic properties ; Clusters ; Iron compounds ; Sulfur compounds ; Halogen compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterization of the new mixed-halide clusters (Et4N)2[Fe2S2Cl4-nBrn] (n=2, 3), together with an improved synthesis of (Et4N)2[Fe2S2Br4] and the crystal and molecular structure of (Et4N)2[F2S2Cl2Br2], are reported here. The structure consists of [Fe2S2Cl2Br2] dianions, with a pseudo-tetrahedral symmetry around each iron atom. A disorder problem precludes precise identification of the locations of the chloride and bromide ligands. A syn (or anti) conformation is however considered to be most likely, for steric hindrance reasons and on the basis of Mössbauer data. The Mössbauer, magnetic susceptibility, cyclic voltammetry and UV/Vis properties of the new clusters remain similar to those of the parent single-type halide clusters. These new clusters are interesting precursors for complexes with mixed thiolate and non-thiolate coordination at the iron sites.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300216
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  • 95
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    Synthesis, Structure, and Reactivity of Tetrakis(O,O-phosphorus)-Bridged Calix[4]resorcinols and Their Derivatives (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1715-1720 
    Details
    ISSN: 0009-2940
    Keywords: Calix[4]resorcinols ; Dioxaphosphocins ; Supramolecular chemistry ; Solid-state NMR spectroscopy ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterisation of the reactive tetrakis (O,O-phosphorus)-Bridged calix[4]resorcinols 3 and 4 is described. Because of its poor solubility in common organic solvents, a solid-state NMR investigation of 3 (1H, 13C, 31P) was conducted. Reaction of 3 with MeMgl, Me3 SiMNe2, and HNMe2 furnished the η3γ3P-substituted cavitands 5 and 6. Oxidative addition reactions of 6 with the (H2N)2C(=O)/H2O2 (1:1) adduct, tetrachloro-o-benzoquinone (TOB), and hexafluoroacetone (HFA) led to the η4γ5P derivative 7, and to the η5γ5P derivatives 8 and 9. An X-ray crystal-structure determination of the tetrakis(O,O-phosphorus)-bridged calix[4]resorcinol 4 has been conduced. The framework displays the cone conformation; the chlorine atoms are directed inwards.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301124
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  • 96
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    Tetra(amino)methanes: Implications of Their Structure and Reactivity Pattern for Hypothetical Carbon Nitride FrameworksDedicated to Professor George A. Olah. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1739-1744 
    Details
    ISSN: 0009-2940
    Keywords: Carbon nitride ; Tetra(amino)methanes ; Guanidinium salts ; Amination ; Conformation analysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Because of their possible role as model compounds for the structural units of carbon nitride C3N4, the preparation, structural chemistry, and some representative reactions of tetra(amino)methanes have been (re)investigated. In the crystal, C(NMe2)4 (1) has a molecular geometry close to D2a symmetry as proposed by theoretical calculations using state-of-the-art density functional methods. The coordination of the central carbon atom is distorted tetrahedral and the configuration of the nitrogen atoms is strongly pyramidal, as opposed to almost planar in the tetra(amino)silanes. Tetra(pyrrolidinyl)methane has a similar core structure, with all heterocyclic substituents in an envelop conformation flexible in solution. Tetra(piperidinyl)methane is more rigid in solution, owing to a more congested structure, with much higher inversion barriers for the six-membered rings. Hydrolysis of 1 leads to MezNH and hexamethylguanidinium hydroxide, and treatment of 1 with HAuCl4(aq) affords crystalline [C(NMe2)3]4 AuCl4- the structure of which has also been determined. Compound 1 is a strong nucleophile and can be used as an aminating agent, converting e.g. halosilanes into dimethylaminosilanes, with the guanidinium cation as the leaving group. The experimental results are discussed in the light of recent predictions regarding bulk carbon nitrides.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301206
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  • 97
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    Halogenation of 1-Ethoxy-1-oxophosphindolin-3-one, a Potential Phosphaindigo Precursor (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1765-1770 
    Details
    ISSN: 0009-2940
    Keywords: Phosphinic acid ; Phosphaindole bromination and chlorination ; Layer structure ; Hydrogen bonds ; Bromine-bromine interaction ; Phosphorus heterocycles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bromination of 1-ethoxy-1-oxophosphindolin-3-one (1) with two equivalents oi bromine occurs with elimination of hydrogen bromide and ethyl bromide, providing 2,2-di- bromo-1-hydroxy-1-oxophosphindolin-3-one (4) in high yield. In the presence of triethylamine this process leads to 2,2-dibromo-1-ethoxy-1-Oxophosphindolin-3-one (3) instead. Triethylamine deprotonates 4, providing the solid triethylammonium salt 5. Silylation of 4 with chlorotrimethylsilane leads to the trimethylsilyl ester 6. Monobromination in a two-phase reaction allows the isolation of a mixture of isomers of 2-bromo-1-ethoxy-1-oxophosphindolin-3-one (2a, b). Chlorination with chlorine furnishes 2,2-dichloro-1-ethoxy-1-oxo-phosphindolin-3-one (7). The new compounds 2-7 were characterized analytically and spectroscopically (EI-MS, 1H, 13C and 31P NMR). The crystal structure of acid 4 was determined by X-ray diffraction. Solid 4 consists of aryl stacks connected by chains of P—OH…O==P hydrogen bonds and secondary Br…Br contacts.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301210
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  • 98
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    Kinetics and Mechanism of Substitution Reactions of cis-[PtMe2(dmso)2] with Pyridine (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1791-1799 
    Details
    ISSN: 0009-2940
    Keywords: Platinum substitution ; Metal-carbon bonds ; trans-Labilization ; Kinetics ; Activation parameters ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The substitution reactions of cis-[PtMe,(dmso),] with pyridine (py) to produce cis-[PtMe2py2] in toluene proceeds in two steps. In the absence of added dimethylsulfoxide (dmso), these steps can not be separated due to the rate constants being very similar. In the presence of added dmso, the rate of the first step, the formation of the monopyridine complex is retarded, which is indicative of a dissociative mechanism. A parallel associative reaction path with pyridine could also be observed. This pathway is independent of the concentration of added dmso. Above a 40-fold excess of dmso, the dissociative pathway is suppressed and only the associative reaction occurs. A plot of Kobs vs the pyridine concentration for this pathway is linear at low [py], but shows a saturation at high [py]. This suggests that the reaction occurs via the formation of a precursor-complex, for which the formation constant was found to be 0.32 · 0.03 M-1. The volume of activation at a high pyridine concentration is -11.4 · 0.8 cm3 mol-1, which indicates that the ligand interchange process is of the associative type. The second step, the formation of the bispyridine complex, can clearly be separated from the first reaction step. This step occurs via a dissociative mechanism, as demonstrated by the decrease in kobs with increasing pyridine concentration. The dissociation of dmso was characterized by a rate constant of (8.1 · 0.9).10-45-1 at 25°C, ·H = 116 ·9 kJ mol-1 and AS. = 86 · 29 JK-1 mol-1. At higher pyridine concentrations evidence for a parallel associative reaction was found, for which the rate constant is (1.3 · 0.2).10-3 M-1S-1 25°C. The results are discussed in reference to available literature data.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301214
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  • 99
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    Synthesis and Properties of Me2Ge-Bridged Arenes (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 421-424 
    Details
    ISSN: 0009-2940
    Keywords: Macrocycles ; Germanium ; UV/Vis spectroscopy ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Linear and cyclic oligomers of Me2Ge-bridged π-systems have been obtained by the reaction of carbo- and heterocyclic anions and dianions with Me2GeCl2. The spectroscopic properties of the new compounds are compared with analogous carbon- and Me2Si-bridged π-systems.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300318
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  • 100
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    P/O Ligand Systems: Synthesis, Reactivity, and Structure of Tertiary o-Phosphanylphenol Derivatives (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 431-431 
    Details
    ISSN: 0009-2940
    Keywords: o-Phosphanylphenols ; P,O hybrid ligands ; P asymmetry ; C,O-dilithium reagents ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300320
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