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  • 1995-1999  (1,834)
  • 1955-1959  (3,070)
  • 1840-1849
  • Inorganic Chemistry  (4,843)
  • gene transfer
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  • 1
    ISSN: 1573-9368
    Keywords: gene construct ; gene transfer ; heritability ; marker gene ; pigmentation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Transgenic mice provide a valuable tool in all fields of basic and applied biological and medical research. In this study, we describe the fate of integrated transgenes in the mammalian host genome over a large number of generations. The stability of the germ-line transmission of integrated tyrosinase transgene copies was monitored up to generation F20 in a large number of individuals from seven transgenic mouse lines. Phenotypic and molecular genetic analysis of the offspring both within the different lines and in cross-breeding experiments revealed the high stability of the transgene integration sites in mice. Only very few individuals were affected by a transgene copy loss. These results indicate that, once homozygous transgenic lines are established, breeding programs can be continued to a high number of generations without further stringent molecular genetic analysis.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1573-0778
    Keywords: culture ; dog ; Duchenne dystrophy ; gene transfer ; satellite cells
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract We have developed and characterized cultures of healthy and dystrophic canine myoblasts for the evaluation of various gene transfer protocols. The number of desmin-positive myoblasts was elevated (〉〉80%) in cultures of myoblasts obtained from different muscle territories, the diaphragm muscle giving rise to the purest cultures. Myoblasts from dogs turned out to be a very convenient source of well transfectable and transducible cells. Transfection with plasmid DNA allowed efficient transgene expression (50% of β-galactosidase positive cells and about 375 ng luciferase/mg protein after transfection with a calcium phosphate-precipitated plasmid). Infection with high concentrations of adenoviral and retroviral vectors allowed transgene (β-galactosidase or mini-dystrophin) detection in about 75 to 90% of the canine cells. Therefore, primary dog myoblast cultures represent a useful in vitro model for viral and non-viral gene delivery, as well as for functional evaluation and cell grafting with applications in genetic diseases, vaccination or production of circulating therapeutic proteins.
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  • 3
    ISSN: 1573-7373
    Keywords: adenovirus ; dominant negative ; fibroblast growth factor receptor ; gene transfer ; glioma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Basic fibroblast growth factor (FGF-2) and high affinity FGF receptor (FGFR) have been detected in the nucleus as well as the cytoplasm of many human gliomas, and are known to stimulate cellular proliferation and angiogenesis in the tumors. To investigate the effects of inactivation of FGFR on the growth of malignant gliomas, we constructed a replication-deficient recombinant adenovirus vector encoding a truncated form of chicken FGFR1 (AxCA Δ FR). AxCA Δ FR-infected cells were confirmed to express truncated FGFR protein by immunoblotting and FGF-2-dependent clonogenicity of NIH3T3 cells was suppressed by infection with this virus vector. Then human malignant glioma cell lines U-251MG and T98G, both of which have been reported to express FGF-2 and FGFR, were infected with AxCA Δ FR. These infected cells showed nuclear as well as cytoplasmic expression of a truncated FGFR protein. Proliferation rate and the ability to form colonies in soft agar of the cells infected with this virus vector were significantly suppressed compared with those of uninfected and lacZ-expressing adenovirus-infected cells. Moreover, intratumoral injection of AxCA Δ FR significantly suppressed the subcutaneous tumor growth of the glioma cells in nude mice. We concluded that inactivation of the cytoplasmic and nuclear FGFR using this truncated FGFR-expressing adenovirus vector can inhibit the growth of malignant gliomas both in vitro and in vivo.
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  • 4
    ISSN: 1573-4935
    Keywords: Oligonucleotides ; gene transfer ; routing ; membrane lectins ; glycoconjugates
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Nucleic acids (plasmids as well as oligonucleotides) used to specifically express or modulate the expression of a gene, must reach the cytosol and/or the nucleus. Several systems have been developed to increase their uptake and their efficiency. Glycosylated polylysines have been shown to specifically help nucleic acids to be taken up in cells expressing a given cell surface membrane lectin. However, it appeared that the efficiency of the imported nucleic acid was not directly related to the extent of the uptake. Indeed, some glycosylated polylysines bearing sugar moities which are poor ligands of the cell surface lectins of a given cell were found to be more efficient than those bearing better sugar ligands. The interpretation of this paradoxal result is discussed with regards to the nature of the compartment allowing the nucleic acid to cross the membrane and to be delivered in the cytosol on the one hand, and to the presence of intracellular lectins on the other hand.
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  • 5
    ISSN: 1573-5028
    Keywords: cytochrome c biogenesis ; gene transfer ; mitochondria ; pea ; ribosomal protein ; soybean
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The pea mitochondrial genome contains a truncated rps7 gene lacking ca. 40 codons at its 5′ terminus. This single-copy sequence is immediately downstream of and slightly overlapping an actively transcribed and edited reading frame of 744 bp (designated ccb248) homologous to the bacterial helC gene which encodes a subunit of the ABC-type heme transporter involved in cytochrome c biogenesis. This region of mitochondrial DNA appears recombinogenic, and the carboxy-termini of helC-type proteins are predicted to vary in sequence and length among plants. Sequences corresponding to the 5′ coding region of rps7 were not detected elsewhere in the pea mitochondrial genome using wheat rps7 probes, and only a very short internal rps7 segment was observed in soybean mitochondrial DNA. The presence of rps7-homologous sequences in the nuclear genomes of pea and soybean is consistent with the recent transfer of a functional mitochondrial rps7 gene to the nucleus in certain plant lineages.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Journal of assisted reproduction and genetics 16 (1999), S. 546-550 
    ISSN: 1573-7330
    Keywords: breast cancer ; mycoplasma ; Ureaplasma urealyticum ; foreign DNA ; gene transfer ; transgenic
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Purpose: Biological vectors for cell transfection are mainly viral in origin, with inherent shortcomings. Mycoplasmas are ubiquitous organisms that traverse cells easily. The objective was to determine if Ureaplasma urealyticum (T-mycoplasma) would vector exogenous BRCA1 DNA into blastocysts. Methods: Hatching mouse blastocysts (N = 70) were incubated in the presence of either viable or dead Ureaplasma urealyticum at 37°C for 1 hr. The blastocysts were exposed to human BRCA1 DNA lacking homology in the mouse genome for 2 hr, followed by DNase-I treatment and wash. Polymerase chain reaction and agarose gel electrophoresis analysis of amplified products were performed. Results: The BRCA1 gene was detected in the blastocysts only when viable Ureaplasma was present. PCR analyses of control Ureaplasma and untreated blastocysts were negative. Conclusion: Viable Ureaplasma organisms were shown to mediate the uptake of DNA fragments into blastocysts, resulting in transgenic mouse blastocysts with a normal human BRCA1 exon 11 gene.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Plant cell, tissue and organ culture 58 (1999), S. 171-176 
    ISSN: 1573-5044
    Keywords: Bacillus thuringiensis Brassicaceae ; gene transfer ; insect resistance ; plant regeneration ; Rorippa nasturtium-aquaticum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Adventitious shoot regeneration could be obtained from more than 80% of the calluses initiated from stem explants of watercress (Rorippa nasturtium-aquaticum) by using an induction medium and a shoot regeneration medium. The induction medium contained 1.15 μM 2,4-dichlorophenoxyacetic acid and 5 μM thidiazuron; the shoot regeneration medium was composed of 0.5 μM thidiazuron and 2.25 μM 6-benzylaminopurine. This regeneration procedure was incorporated into an Agrobacterium-mediated transformation procedure for gene transfer into watercress. Factors affecting transformation included preculture, selection agents, use of tobacco nurse cells, and the length of coculture. A transgenic line of watercress transformed with a wild-type Bacillus thuringiensis insecticidal gene, cry1Ia3, was not toxic to larvae of the diamondback moth (Plutella xylostella), presumably due to premature polyadenylation of the transcript encoded by this gene in the plant.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Cell biology and toxicology 15 (1999), S. 193-202 
    ISSN: 1573-6822
    Keywords: DNA ; gene transfer ; importin ; nuclear import ; nuclear localization signal
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract One of the major steps limiting nonviral gene transfer efficiency is the entry of plasmid DNA from the cytoplasm into the nucleus of the transfected cells. The nuclear localization signal (NLS) of the SV40 large T antigen is known to efficiently induce nuclear targeting of proteins. We have developed two chemical strategies for covalent coupling of NLS peptides to plasmid DNA. One method involves a site-specific labeling of plasmid DNA by formation of a triple helix with an oligonucleotide–NLS peptide conjugate. After such modification with one NLS peptide per plasmid molecule, plasmid DNA remained fully active in cationic lipid-mediated transfection. In the other method, we randomly coupled 5–115 p-azidotetrafluorobenzyllissamine–NLS peptide molecules per plasmid DNA by photoactivation. Oligonucleotide–NLS and plasmid–lissamine–NLS conjugates interacted specifically with the NLS-receptor importin α. Plasmid–lissamine–NLS conjugates were not detected in the nucleus, after cytoplasmic microinjection. Plasmids did not diffuse from the site of injection and plasmid–lissamine–NLS conjugates appeared to be progressively degraded in the cytoplasm. The process of plasmid DNA sequestration/degradation stressed in this study might be as important in limiting the efficiency of nonviral gene transfer as the generally recognized entry step of plasmid DNA from the cytoplasm into the nucleus
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 1573-904X
    Keywords: gene transfer ; cytotoxicity ; polyethylenimine ; polyfection
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. Low molecular weight branched polyethylenimine (LMW-PEI) was synthesized and studied as a DNA carrier for gene delivery with regard to physico-chemical properties, cytotoxicity, and transfection efficiency. Methods. The architecture of LMW-PEI, synthesized by acid catalyzed ring-opening polymerization of aziridine was characterized by size exclusion chromatography in combination with laser light scattering and 13C-NMR-spectroscopy. In vitro cytotoxic effects were quantified by LDH and MTT assay and visualized by transmission electron microscopy. The potential for transgene expression was monitored in ECV304 cells using luciferase driven by a SV40 promoter as reporter gene system. Results. LMW-PEI (Mw 11′900 D) with a low degree of branching was synthesized as a DNA carrier for gene delivery. In contrast to high molecular weight polyethylenimines (HMW-PEI; Mw l′616′OOO D), the polymer described here showed a different degree of branching and was less cytotoxic in a broad range of concentrations. As demonstrated by transmission electron microscopy the LMW-PEI formed only small aggregates which were efficiently taken up by different cells in the presence of serum, most likely by an endocytic pathway. LMW-PEI yielded transfection efficiencies measured via expression of the reporter gene luciferase which were up to two orders of magnitude higher than those obtained with HMW-PEI. The reporter gene expression was concentration dependent, but in contrast to lipofection independent of serum addition. Conclusions. The LMW-PEI described here is a new, highly efficient, and non-cytotoxic vector with a favorable efficiency/toxicity profile for gene therapeutic applications.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    World journal of microbiology and biotechnology 15 (1999), S. 1-6 
    ISSN: 1573-0972
    Keywords: Bacteria ; conjugation ; DNA ; evolution ; gene transfer ; transduction ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The transfer of genetic information by transformation, conjugation and transduction in bacteria occurs frequently in nature. These diverse gene transfer mechanisms in bacteria are the result of evolution and are not linked to reproduction as in eukaryotic organisms. In this review, gene transfer in bacteria will be considered from an evolutionary perspective.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 41 (1998), S. 1401-1409 
    ISSN: 1432-0428
    Keywords: Keywords Beta-cell lines ; conditional transformation ; gene transfer ; glucose-regulated promoters ; immunomodulation ; insulin biosynthesis ; insulin secretion ; islet regeneration ; proinsulin processing ; transplantation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The application of gene therapy to Type I (insulin-dependent) diabetes mellitus awaits improvements in gene transfer technologies and the development of better tools for accurate diagnosis of pre-diabetic people. Identification of the most promising candidate genes for gene transfer requires further elucidation of the molecular events involved in beta-cell autoimmune destruction, islet ontogeny and differentiation, and beta-cell function. This review outlines a number of possible targets for gene therapy in Type I diabetes, which could help prevent the autoimmune damage to islets, induce islet regeneration, and restore insulin production through engineering of self non-beta cells or beta-cell transplantation. It also evaluates their potential merits and drawbacks. [Diabetologia (1998) 41: 1401–1409]
    Type of Medium: Electronic Resource
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  • 12
    ISSN: 1432-0428
    Keywords: Keywords Lentiviral vector ; retrovirus ; human islet beta-cell ; gene transfer ; transplantation.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Pancreatic islet cells are terminally differentiated endocrine cells and are refractory to stable infection by retroviral vectors, which require the breakdown of the nuclear membrane during cell division in order to insert the transgene into the host cell genome. Thus, attempts to render beta-cell allografts less immunogenic have had to rely on stable transfection of surrogate cells. Similarly, this problem has precluded the development of conditionally immortalized human beta cells for clinical allotransplantation. In this report, we demonstrate that adult human islet beta cells can be transduced by a new three-plasmid integrating lentiviral vector with an efficiency of 62 ± 1.8 % at a multiplicity of infection (MOI) of 2.5 in vitro. This work makes genetic engineering of adult human pancreatic beta cells possible for the first time, allowing strategies to render beta-cell allografts non-immunogenic to be optimized and to creating conditionally immortalized human beta cells for clinical transplantation. [Diabetalogia (1998) 41: 736–739]
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  • 13
    ISSN: 1569-8041
    Keywords: cytotoxic T lymphocyte (CTL) ; dendritic cell ; Epstein-Barr virus (EBV) ; EBV-associated lymphoproliferative disease (EBV-LPD) ; gene-marking ; gene transfer ; Hodgkin's disease ; immunotherapy ; latent membrane protein 2 (LMP2)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Donor-derived Epstein-Barr virus (EBV)-specific cytotoxic T lymphocytes (CTL) are successful in the prevention and treatment of Epstein-Barr virus (EBV)-associated lymphoproliferative disease (LPD) in allogeneic bone marrow transplant (BMT) recipients [1, 2]. This finding prompted us to use a similar approach to the treatment of relapsed EBV-positive Hodgkin's disease [3]. Autologous EBV-specific CTL lines could be generated on the first or second attempt from 11 of 15 patients with Hodgkin's disease. Peripheral blood TCR ζ-chain levels were low, but increased in the activated CTL lines. Three patients have received gene-marked autologous CTL. The first two patients experienced alleviation of stage B symptoms and a drop in peripheral blood EBV load. However, this situation reversed between 6 and 12 weeks after infusion, when chemotherapy and radiation were reinstated. Both patients eventually progressed and died. The third patient had a pleural effusion, which increased after CTL infusion. Analysis of the pleural effusion revealed both tumor cells and levels of marker gene over 100 fold greater than in peripheral blood. The infused CTL line showed activity against LMP2. The patient initially improved and then remained stable for over eight months after CTL infusion, but now has progressive disease. We currently are evaluating methods for introducing the LMP2 gene into dendritic cells and using these to present LMP2 to autologous T cells. Using both retrovirus and herpesvirus vectors to express LMP2 in dendritic cells, LMP2-specific CTL were successfully generated from individuals who were EBV-seronegative or who were non-responsive to LMP2 when presented on autologous LCL. In future protocols, LMP2-specific CTL will be used for treatment.
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  • 14
    ISSN: 1573-4919
    Keywords: FGF-2 ; transcription ; gene transfer ; HSV-thymidine kinase promoter
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract We have cloned the rat fibroblast growth factor-2 (FGF-2) promoter region including 1058 base pairs (bp) of 5′-flanking DNA. Complete sequencing of this promoter region revealed a 74 bp domain between nucleotides -793 and -720 that was greater than 97% A/G-rich. A repeat of the sequence 5′-AGGGAGGG-3′ separated by 11 bp was located at the core of this domain. A 37 bp A/G-rich oligonucleotide containing these AGGG-repeat sequences was synthesised, and tested for function on a minimal herpes simplex virus thymidine kinase (TK) promoter, fused to the firefly luciferase gene (TKp.luc), in transiently transfected neonatal rat cardiac myocytes. Promoter activity was stimulated ~3 fold in the presence of AGGG-repeat sequences. This effect was neither tissue or species-specific since TK promoter activity was increased ~11 fold in both rat and human glial tumor cells. Four specific complexes (C14) were detected between neonatal rat heart nuclear proteins and the 37 bp A/G-rich oligonucleotide by gel mobility shift assay. Competition with excess unlabelled 37 bp A/G-rich oligonucleotide revealed that two complexes represented very high affinity/specificity interactions (C2 〉 C4) while C1 and C3 were of lower affinity. As a result, competition with up to a 25 fold molar excess of 37 bp A/G-rich oligonucleotide led to the loss of C2 and C4, and a corresponding and transient increase in the levels of C1 and C3, which themselves were reduced with more competitor oligonucleotide. The AGGG-repeat resembles the 5′-gGGGAGGG-3′ sequence previously implicated in the response of the atrial natriuretic factor promoter to the α-adrenergic agonist, phenylephrine. Although an additional 1.5 fold increase in TK promoter activity was detected in the presence of the 37 bp A/G-rich oligonucleotide with phenylephrine treatment of transfected myocytes, this effect was not statistically significant. Furthermore, there was no difference in the gel mobility shift (C14) pattern obtained with the 37 bp A/G-rich oligonucleotide and nuclear protein isolated from neonatal rat cardiac myocytes grown in the presence or absence of norepinephrine. These data suggest that the A/G rich sequences in the rat FGF-2 gene 5′-flanking DNA, including the AGGG-repeat, are able to confer stimulatory activity on a promoter in a tissue- and species-independent manner, but alone are not able to induce a significant phenylephrine response in neonatal rat cardiac myocytes.
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Neurochemical research 23 (1998), S. 421-426 
    ISSN: 1573-6903
    Keywords: Oligodendrocytes ; electroporation ; gene transfer ; transfection
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The transient transfection of transgenes into oligodendrocytes offers an important tool for studying the function of proteins during myelin formation. Currently established procedures, however, have generally resulted in low survival rates and low levels of uptake of the transgene into primary oligodendrocyte progenitors. We describe an electroporation method which yields transient transfection of oligodendrocyte progenitors of up to 10–15% of the surviving cells, and provides approximately 104 surviving, transfected cells per electroporation reaction. In recent applications transgene expression persisted as the transfected progenitors progressed through subsequent stages of the oligodendrocyte lineage. This technique is expected to facilitate the study of the function of key proteins and lipids during the development of primary cultured oligodendrocytes.
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Antonie van Leeuwenhoek 73 (1998), S. 69-77 
    ISSN: 1572-9699
    Keywords: spermosphere ; rhizosphere ; bulk soil ; gene transfer ; seed coating
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Transfer of plasmid RP4 to indigenous bacteria in bulk soil could only be detected in soil with nutrient amendment. Lack of physiological active donor and recipient cells was apparently one of the limiting factors in un-amended bulk soil. Plasmid transfer was detected both in the spermosphere and rhizosphere of barley seedlings. Transfer occured from seed coated donor bacteria (i) to introduced recipient bacteria and (ii) to indigenous bacteria present in soil. Plasmid transfer was also detected from donor bacteria introduced to the soil to seed coated recipient bacteria. Transfer efficiencies in the rhizosphere were significantly below the transfer efficiencies obtained in the spermosphere. The transfer efficiencies detected in the barley spermosphere were among the highest reported from any natural environment.
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  • 17
    ISSN: 1572-994X
    Keywords: xenotropic endogenous MuLV ; gene transfer ; Bxv-1
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Development of methods for gene transfer into specific cell types or tissues is important for experimental research as well as clinical therapeutical approaches. We report here the cloning and characterization of the envelope (env) gene and the U3 region of a retrovirus from an infected human Small Cell Lung Cancer (SCLC) cell line. The replication of this murine retrovirus is also fully supported by other lung cancer cell lines of different histological origin. We present evidence that a long terminal repeat (LTR)-β-galactosidase (β-Gal) reporter construct performed as well as an analogous cytomegalovirus (CMV) promoter β-Gal construct in the human lung epithelial cell line A549 and in the human larynx carcinoma cell line HEp2.
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  • 18
    Electronic Resource
    Electronic Resource
    Springer
    Euphytica 103 (1998), S. 95-102 
    ISSN: 1573-5060
    Keywords: gene transfer ; physical mapping ; RFLPs ; wheat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract A physical deletion map of the Lr19 translocated chromosome segment was extended by mapping three additional Thinopyrum RFLP loci. The relative locations of the marker loci on the translocated segment were determined as: centromere, Sd1, Xpsr165, Xpsr105, Xpsr129, XcsIH81-1, Xwg380, Xmwg2062, Lr19, Wsp-D1, Sr25/Y. Various recombinants, putative recombinats and mutants of the Lr19 segment were also characterised with respect to the additional markers.
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  • 19
    ISSN: 1573-6822
    Keywords: DNA ; cellular uptake ; nuclear import ; microinjection ; gene transfer ; cationiclipid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Cationic lipids are widely used for gene transfer in vitro and show promise as vectors for in vivo gene therapy applications. However, there is limited understanding of the cellular mechanisms involved in nonviral gene transfer. We investigated two major steps that could be limiting barriers to cationic lipid-mediated gene transfer in vitro. We used a fluorescent plasmid to study the cellular uptake and the intracellular fate of lipoplexes during in vitro transfection of fibroblast cells and found that 100% of the cells take up lipoplexes. The intracellular staining observed with lipoplexes was clearly different from that obtained with endocytosed fluorescent dextran. This suggests that cells readily take up lipoplexes by a mechanism that could be different from endocytosis in our conditions. However, the escape of DNA from intracellular vesicles could be a major limiting barrier to gene transfer. Direct injection of plasmid DNA into the nucleus and cytoplasm of cells indicated that DNA traffic from the cytoplasm to the nucleus might be also an important limiting step.
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  • 20
    ISSN: 1573-904X
    Keywords: gene transfer ; airways ; cationic lipids ; surface charge ; co-lipid content ; topology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. Cationic lipids are capable of transferring foreign genes to the pulmonary epithelium in vivo. It is becoming increasingly clear that factors other than lipid molecular structure also influence efficiency of delivery using cationic lipid systems. This study is aimed at evaluating the effect of formulation variables such as cationic lipid structure, cationic lipid/DNA ratio, particle size, co-lipid content and plasmid topology on transgene expression in the lung. Methods. The effect of varying the surface and colloidal properties of cationic lipid-based gene delivery systems was assessed by intratracheal instillation into rats. An expression plasmid encoding chloramphenicol acetyl transferase (CAT) was used to measure transgene expression. Results. Cationic lipid structure, cationic lipid/DNA ratio, particle size, co-lipid content and topology of the plasmid, were found to significantly affect transgene expression. Complexation with lipids was found to have a protective effect on DNA integrity in bronchoalveolar lavage fluid (BALF). DNA complexed with lipid showed enhanced persistence in rat lungs as measured by quantitative polymerase chain reaction. Conclusions. Fluorescence microscopy analysis indicated that the instilled formulation reaches the lower airways and alveolar region. Data also suggests cationic lipid-mediated gene expression is primarily localized in the lung parenchyma and not infiltrating cells isolated from the BALF.
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  • 21
    ISSN: 1573-904X
    Keywords: gene therapy ; gene transfer ; cationic polymer ; chitosan ; polyethylenimine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. Chitosan, a natural cationic polysaccharide, is a candidate non-viral vector for gene delivery. With the aim of developing this system, various biophysical characteristics of chitosan-condensed DNA complexes were measured, and transfections were performed. Methods. Transmission electronic microscopy (TEM) visualizations, sedimentation experiments, dynamic light scattering (DLS), and zeta potential measurements were realized. Transfections were made by using the luciferase reporter gene. Results. In defined conditions, plasmid DNA formulated with chitosan produced homogenous populations of complexes which were stable and had a diameter of approximately 50−100 nm. Discrete particles of nicely condensed DNA had a donut, rod, or even pretzel shape. Chitosan/DNA complexes efficiently transfected HeLa cells, independently of the presence of 10% serum, and did not require an added endosomolytic agent. In addition, gene expression gradually increased over time, from 24 to 96 hours, whereas in the same conditions the efficacy of polyethylenimine-mediated transfection dropped by two orders of magnitude. At 96 hours, chitosan was found to be 10 times more efficient than PEI. However, chitosan-mediated transfection depended on the cell type. This dependency is discussed here. Conclusions. Chitosan presents some characteristics favorable for gene delivery, such as the ability to condense DNA and form small discrete particles in defined conditions.
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  • 22
    ISSN: 1573-904X
    Keywords: gene transfer ; colon 26 ; monocyte chemotactic and activating factor ; chemokine ; biological response modulater
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. In order to evaluate the possibility of synergistic antitumor gene therapy by the gene delivery of monocyte chemotactant protein-1 (MCP-1/MCAF/IE), the effect of a biological response modulater for macrophages on tumor progression of gene transfected tumor cells was studied. Methods. Cachexia-inducing adenocarcinoma cells (cell line colon 26, clone 20) were transfected with either a control plasmid or MCP-1 cDNA. Results. The production of MCP-1 reached 70-80 ng/ml in vitro when transfectant cells were cultured at a cell density of 1 × 105 cells/ml for 3 days. Transfection of MCP-1 cDNA did not affect the growth ratein vitro. Also, MCP-1-transfectants formed tumors after intra-footpad inoculation similar in size to the parental cells. The number of infiltrating macrophages in the primary tumor of the transfectant rapidly increased from the 3rd to 5th day after inoculation as revealed by immunohistochemical staining using an antibody against mouse macrophages. An earlier, greater, but no longer-lasting increase in tumor-infiltrating macrophages was induced in tumors by MCP-1 transfection was compared to that induced by the parent cells. On the 10th day after the inoculation, the tumor-infiltrating macrophages in mice inoculated MCP-1 transfectants were decreased to a level similar to that of the parent cells. Groups of mice were treated intraperitoneally with LPS at different times after the inoculation. Tumor cells producing high levels of MCP-1 were significantly lysed by macrophages treated with LPS, whereas parental or control transfected cells were not. Conclusions. Combination immunotherapy can provide a rationale for the application of MCP-1 treatment to increase immunological responses to cancer.
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  • 23
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 58 (1998), S. 272-281 
    ISSN: 0006-3592
    Keywords: gene transfer ; retrovirus ; cell cycle ; intracellular stability ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Recombinant retroviruses are currently used as gene delivery vehicles for the purpose of gene therapy. It is generally believed that the efficiency of retroviral transduction depends on the cell cycle status of the target cells. However, it has been reported that this is not the case for the transduction of human and murine fibroblasts, in contrast to other cell types such as lymphocytes. The predictions of a mathematical model that we constructed, offer an explanation of this contradiction, based on the dynamics of the underlying processes of target cell growth and the intracellular decay of retroviral vectors. The model suggests that the utility of synchronization experiments, that are usually employed to study cell cycle specificity, is severely limited when the time scales of the above kinetic events are comparable to each other. The predictions of the model also suggest the use of retroviral vectors as cell cycle markers, as an alternative way to detect cell cycle dependence of retroviral transduction. This method obviates the need for cell synchronization and therefore, it does not perturb the cell cycle or interfere with the life cycle of retroviral vectors. Moreover, it does not depend on the intracellular stability of retroviral vectors. Our results show that in contrast to previously reported results, transduction of murine fibroblasts is cell cycle dependent, and they are consistent with the current notion that mitosis is the phase that confers transduction susceptibility. © 1998 John Wiley & Sons, Inc. Biotechnol Bioeng 58:272-281, 1998.
    Additional Material: 7 Ill.
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  • 24
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    Springer
    Molecular and cellular biochemistry 172 (1997), S. 47-57 
    ISSN: 1573-4919
    Keywords: smooth muscle ; gene transfer ; DNA ; RNA ; ribozyme ; liposome ; lipoxygenase ; gene expression
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Chemically synthesized hammerhead-type ribozymes targeted against the porcine leukocyte-type 12-lipoxygenase (LO) have been developed and studied. One chimeric ribozyme consists of DNA in the non-enzymatic portions, and RNA in the enzymatic core as well as two phosphorothioate internucleotide linkages at 3′ terminus. The second ribozyme consists of ribonucleotide sequences generated by in vitro transcription. In this chapter we describe methodologies to first analyze the ribozyme catalytic activity in vitro by studying cleavage of target RNA in vitro. The subsequent sections will describe how to target the catalytic ribozyme and deliver it to porcine vascular smooth muscle cells (PVSMC) by a liposome-mediated method. Finally ways to evaluate its activity to inhibit expression of the 12-LO mRNA will be presented. These results demonstrate the feasibility of using ribozymes as novel candidates for therapeutic agents to block specific gene expression in vascular cells.
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  • 25
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    Springer
    Molecular and cellular biochemistry 172 (1997), S. 103-109 
    ISSN: 1573-4919
    Keywords: adult ventricular cardiomyocytes ; microinjection ; gene transfer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Among techniques commonly used to deliver bioactive molecules into living cells, microinjection is a very efficient method. Microinjection has been used extensively for gene transfer into different cell types. We applied the microinjection technique to the adult rat ventricular cardiac muscle cells (AVC) in primary culture and optimized microinjection parameters and the appropriate cell culture conditions. We also optimized the use of particular agents (i.e. 2,3-butanedione monoxime, verapamil) for the prevention of the cell damage caused by the micropuncture. We obtained the expression of a CMV-β-galactosidase reporter gene in up to 20% of the injected cells with efficient maintenance of long term cell viability. Under our experimental conditions direct microinjection is a very advantageous technique to transfer macromolecules into living adult cardiac muscle cells and a powerful system to study and manipulate the biochemistry and molecular biology of the cardiac myocyte.
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  • 26
    ISSN: 1573-4919
    Keywords: smooth muscle ; gene transfer ; DNA ; fibroblast growth factor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Manipulation of the genetic machinery of cells both in vitro and in vivo is becoming an ever more important means of elucidating pathways of molecular and cellular biochemistry. In addition, gene therapy has been proposed as a novel and potentially powerful treatment for both inherited and acquired diseases. Successful gene transfer and gene blockade generally depend on high efficiency delivery of exogenous DNA or RNA into living cells, and much effort has therefore been focused on the development of methods for achieving this delivery in a safe and effective manner. We describe here our application of fusigenic Sendai virus (HVJ)-liposome technology toward the effective delivery of DNA into vascular smooth muscle cells (VSMC) in cell culture. Cellular uptake and intracellular distribution of oligodeoxynucleotide (ODN) after transfection with HVJ-liposome complexes was characterized using fluorescent (FITC)-labeled ODN, and the biologic effect of HVJ-liposome mediated transfection was demonstrated via inhibition of DNA synthesis in cultured VSMC using antisense ODN against basic fibroblast growth factor.
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  • 27
    Electronic Resource
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    Springer
    Molecular and cellular biochemistry 172 (1997), S. 37-46 
    ISSN: 1573-4919
    Keywords: gene transfer ; gene expression ; adenovirus ; blood vessel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Adenovirus-mediated gene transfer is a promising method for studies of vascular biology and potentially for gene therapy. Intravascular approaches for gene transfer to blood vessels in vivo generally require interruption of blood flow and have several limitations. We have used two alternative approaches for gene transfer to blood vessels in vivo using perivascular application of vectors. First, replication-deficient adenovirus expressing nuclear-targeted bacterial b-galactosidase was injected into cerebrospinal fluid via the cisterna magna of rats. Leptomeningeal cells over the major arteries were efficiently transfected, and adventitial cells of large vessels and smooth muscle cells of small vessels were occasionally stained. When viral suspension was injected with the rat in a lateral position, the reporter gene was expressed extensively on the ipsilateral surface of the brain. Thus, adenovirus injected into cerebrospinal fluid provides gene transfer in vivo to cerebral blood vessels and, with greater efficiency, to perivascular tissue. Furthermore, positioning of the head may ‘target’ specific regions of the brain. Second, vascular gene delivery was accomplished by perivascular injection of virus in peripheral vessels. Injection of the adenoviral vector within the periarterial sheath of monkeys resulted in gene transfer to the vessel wall that was substantial in magnitude although limited to cells in the adventitia. Approximately20% of adventitial cells expressed the transgene, with no gene transfer to cells in the intima or media. These approaches may provide alternative approaches for gene transfer to blood vessels, and may be useful for studies of vascular biology and perhaps vascular gene therapy.
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  • 28
    ISSN: 1573-4919
    Keywords: cell division ; gene transfer ; mitogenic response
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Basic fibroblast growth factor (FGF-2) plays an important role in myocardial growth and development and in particular cardiac myocyte proliferation. FGF-2 exerts its effects by binding to cell surface receptors (FGFR-1) of the tyrosine kinase family. We have detected the presence of both long and short isoforms of FGFR-1 in embryonic and adult mouse heart. In this report, we have examined the ability of long and short FGFR-1 isoforms to signal a mitogenic response. Assessment of RNA from rat myoblast H9c2 cells by reverse transcriptase-polymerase chain reaction and RNA blotting revealed that they were deficient in transcripts corresponding to long and short FGFR-1 species. Hybrid genes containing the cDNAs coding for long and short FGFR-1 isoforms directed by the myosin light chain-2 promoter and simian virus 40 enhancer sequences, were used to transiently transfect H9c2 cells. Total tyrosine phosphorylation was increased 2.0 and 2.6 fold in H9c2 cells transfected with the long and short FGFR-1 isoforms, respectively, compared to 'control' transfected H9c2 cells. This was accompanied by a 2.1 and 2.0 fold increase in DNA synthesis, as measured by tritiated thymidine incorporation, in H9c2 cells expressing the long and short FGFR-1 isoforms, respectively. To assess effects on proliferation, H9c2 cells were stably transfected with the myosin light chain-2/FGFR-1 cDNA genes. The rate of proliferation was increased 1.6 and 3.1 fold in H9c2 cells stably expressing the long and short FGFR-1 isoforms, respectively, compared to 'control' H9c2 cells. In contrast to non transfected H9c2 cells, treatment of H9c2 cells stably expressing long FGFR-1 with FGF-2 for 24 h resulted in a slight increase (1.3 fold, p 〈 0.02) in cell number. However, a greater response (1.5 fold, p 〈 0.0005) was observed with H9c2 cells stably expressing short FGFR-1 after treatment with FGF-2. These results suggest that both long and short FGFR-1 isoforms are capable of signalling a mitogenic response.
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  • 29
    ISSN: 1432-2277
    Keywords: Key words Gene transfer ; adenovirus ; liver transplantation ; Adenovirus ; gene transfer ; liver transplantation ; Liver transplantation ; adenovirus ; gene transfer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract To establish an efficient technique for adenovirus-mediated gene transfer in liver transplantation, we evaluated the in situ perfusion of liver grafts. The grafts were perfused in situ with 1 × 1010 of E1-deleted, replication-defective adenoviral vectors encoding the LacZ gene driven by the human CMV promoter, either through the hepatic artery (group 1) or the portal vein (group 2). Group 3 animals served as negative controls; their liver grafts were perfused with lactated Ringer's solution through the portal vein. PCR confirmed the presence of viral DNA in every graft perfused with viral vectors. In X-gal staining, positive staining was observed almost exclusively at the portal triad in group 1, whereas in group 2 minimal staining was observed, predominantly in the parenchymal area. Protein production from the transfected gene was confirmed by a functional protein assay; the values were 0.16 % ± 0.07 % liver protein in group 1, 0.13 % ± 0.02 % in group 2, and 0.007 % ± 0.0003 % in group 3 on postoperative day 2. In conclusion, in situ perfusion of the viral vectors through the hepatic artery resulted in an effective expression of the transfected gene, predominantly at the portal triad.
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  • 30
    ISSN: 1573-9368
    Keywords: abalone ; gene transfer ; sperm-electroporation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract We investigated gene transfer in abalone via electroporated sperm. The mobility of sperm electroporated either in seawater or in marine invertebrate physiological solution was as good as that of the control group. The fertilization rate reached as high as 94.7--99.6% (93.0-- 99.7% for the control group) when 200 eggs were fertilized by 106 or 107 sperm treated with electroporation at 10 kV and 27 pulses for six cycles. Moreover, the fertilization rate of sperm electroporated in the presence of foreign DNA (opAFP-2000CAT) ranging from 0.1 to 3.2 μg and at voltages ranging from 2 to 10 kV, at 27 or 211 pulses for six or 12 cycles showed no differences from the control sperm. After DNase digestion, the genome of the electroporated sperm was analysed by polymerase chain reaction, and it was shown that a 138-bp product was amplified, corresponding to the transgene's amplification product. Southern blotting also showed that a positive band located at the same position as that of opAFP-2000CAT was found in the electroporated sperm after DNase treatment. Analysis by PCR of the genome isolated from a trochophore-stage abalone larva, derived from sperm electroporated with 3.2 g opAFP- 2000CAT, showed the existence of foreign DNA in 13 out of 20 examined samples (65%). The integration of the transferred DNA into the genome of transgenic abalone was also shown by Southern blot analysis. Furthermore, CAT activity was positive for the experimental larvae, but the level of CAT expression was lower than that of larvae derived from sperm electroporated with pCAT- Control vector, driven by SV40 promoter and enhancer sequences. These results demonstrate the potential for the use of sperm as mass gene transfer strategy in marine mollusks such as abalone
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  • 31
    ISSN: 1573-9368
    Keywords: cryIA(c) gene ; gene transfer ; toxic to pod-borers ; transgenicchickpea
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Two strains of chickpea (Cicer arietinum L.) ICCV-1 and ICCV-6, were used for transgenic plant generation. Embryo axis of mature seed devoid of the root meristem and the shoot apex was used as experimental material. The explants were cultured in medium containing MS macro salts, 4 × MS micro salts, B5 vitamins, 3.0 mg l−1 BAP, 0.004 mg l−1 NAA, 30 mg l−1 sucrose and cultured at 26 °C in dark, 24 h prior to bombardment. Gene delivery to the explants was carried out using a Bio-Rad Biolistic 1000/He particle gun. A chimaeric, truncated bacterial cryIA(c) gene construct was developed for plant expression with the CaMV35S promoter, nos terminator, an initiatory kozak sequence and a translational enhancer (STAR-P) sequence of tobacco mosaic virus. This cryIA(c) gene was cotransferred with a plasmid containing nptII gene as the selection marker. Transgenic kanamycin resistant chickpea plants were obtained through multiple shoot formation and repeated selection of the bombarded explants. Molecular analyses of the transformants revealed the presence of the transferred functional cryIA(c) gene in plant. Insect feeding assay indicated that the expression level of the cryIA(c) gene was inhibitory to the development of the feeding larvae of Heliothis armigera Hubner, the chickpea pod-borer
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  • 32
    ISSN: 1573-5117
    Keywords: transgenic fish ; gene transfer ; growth enhancement ; lopifection ; particle bombardment ; electroporation ; fish sperm ; fish embryos
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Recent advantages in transgenic fish research are reviewed, with special reference to the methods for gene transfer. These include microinjection, electroporation, particle bombardment, and lipofection. The success and problems associated with each of these methods, and the possible applications of transgenic fish research to aquaculture are discussed.
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  • 33
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    Pharmaceutical research 14 (1997), S. 190-196 
    ISSN: 1573-904X
    Keywords: gene transfer ; cationic lipid ; DNA complexes ; hydrophobic effect
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. We have demonstrated that a heteromolecular complex consisting of cationic lipids and DNA can be prepared and isolated (1). Cationic lipids bind DNA through electrostatic interactions. However, when sufficient lipids are bound to DNA the physical and chemical properties of the complex are governed by hydrophobic effects. Here we describe an approach where this hydrophobic complex is used as an intermediate in the preparation of lipid-DNA particles (LDPs). Methods. The approach relies on the generation of mixed micelles containing the detergent, n-octyl β-D-glucopyranoside (OGP), the cationic lipid, N-N-dioleoyl-N, N-dimethylammonium chloride (DODAC), and selected zwitterionic lipids, 1,2-dioleoyl-sn-glycero-3 -phosphoethanolamine (DOPE) or egg sphingomyelin (SM). Results. When these micelles were prepared at low detergent concentrations (20 mM OGP) and combined with pCMVβ DNA, LDPs spontaneously formed. The mean diameter of these particles as measured by quasielastic light scattering was 55−70 nm, a result that was confirmed by negative stain electron microscopy. Further characterization of these LDPs showed that DNA within the particles was inaccessible to the small fluorochrome TO-PRO-1 and protected against DNase I degradation. LDPs could also be prepared in high concentrations of OGP (100 mM), however particles formed only after removal of OGP by dialysis. Particles formed in this manner were large (〉2000nm) and mediated efficient transfection of Chinese hamster ovary cells. Transfection activity was greater when the lipid composition used consisted of SM/ DODAC. Small particles (〈100nm) prepared of SM/DODAC were, however, inefficient transfecting agents. Conclusions. We believe that LDP formation is a consequence of the molecular forces that promote optimal hydrocarbon-hydrocarbon interactions and elimination of the hydrocarbon-water interface.
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  • 34
    ISSN: 1573-904X
    Keywords: cationic lipid ; DNA ; in vivo ; gene transfer ; alkaline phosphatase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. A stable cationic lipid/DNA complex has been developed for in vivo gene transfer. The formulation capitalizes on a previously described procedure to obtain stable lipid/DNA complexes for in vitro gene transfer (1). Methods. Conditions for DNA/lipid complex formation were modified to yield a DNA concentration of 1 mg/ml. Heat stable alkaline phosphatase (AP) under a CMV promoter was used as a reporter gene. Results. The resulting complex was completely insensitive to serum inactivation. Tail vein injection of a 80 μg DNA into Balb C mice yielded significant levels of reporter enzyme activity in the lung, heart, spleen, muscle, and liver. Less AP activity was observed in the kidney. No AP activity was observed in blood, bone marrow or brain. A titration of the lipid (DOSPA) to DNA-nucleotide ratio showed the optimal molar ratio for in vivo gene transfer to be 1/1. Using this ratio in a dose response study showed approximately 80 μg of DNA/mouse yielded the highest level of gene expression. Using this dose at a 1/1 lipid to DNA nucleotide ratio, the time course for alkaline phosphatase activity was determined. Maximal AP activity was observed 24 hours after injection for all tissues. By day 5, the activity dropped approximately 10 fold for all tissues. By day 7, residual activity was detected in the lung, heart, and muscle. Histology of the lung showed both interstitial and endothelial cells to be transfected. In all other tissues, however, endothelial cells were the only transfected cell type. Conclusions. These results demonstrate that reformulation of an existing cationic lipid can result in the formation of a stable lipid/DNA complex, which is able to reproducibly transfect lung, heart, spleen, and liver upon intravenous administration.
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  • 35
    ISSN: 1573-904X
    Keywords: adenoviral vector ; Caco-2 ; gene transfer ; integrin ; intestinal epithelium ; vitronectin receptor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. Adenoviral (Ad) vectors have been used as efficient tools for gene therapy in various tissues, whereas in some differentiated epithelium transduction efficiency is almost abolished. Methods. Caco-2 cell monolayers were chosen as an in vitro model for the differentiated intestinal epithelium. Fluorescence-labeled adenoviral particles were used for binding studies to cell surfaces. Internalization receptors for adenoviral uptake were decteted by a fluorescence-labeled vitronectin antibody. Gene expression was studied by using the β-galactosidase reporter gene. All experiments were done on undifferentiated and differentiated Caco-2 cells. Furthermore, adenoviral particles were allowed to bind to differentiated Caco-2 monolayers followed by a trypsinization step that disintegrates the monolayers and result in a cell suspension. Gene expression was tested after reseeding the cells into dishes. Results. The results from adenoviral binding studies, vitronectin immunofluorescence detection and gene expression are in good agreement and indicate that virion binding as well as the expression of internalization receptors almost disappear in fully differentiated cells. Nonetheless, adenoviral binding to differentiated monolayers seems to be sufficient to cause up to 53% gene expression, but only if internalization of the vector can be induced by disintegrating the monolayers and releasing free vitronectin receptors. Conclusions. These findings indicate that gene transfer to the intestinal epithelium utilizing adenoviral vectors is poor and ineffective, because of the lack of sufficient internalization receptors. If these receptors can be exposed in differentiated epithelium, transduction can be made more efficicient. Alternatively, a viral vector must be developed whose uptake mechanism is independent of integrin receptor expression like the enteral virus Ad40, or Ad5 could be conjugated to ligands that trigger viral internalization by receptor-mediated endocytosis.
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  • 36
    ISSN: 1573-904X
    Keywords: gene transfer ; interferon-β ; Caco-2 cells ; non-polarized secretion ; gene therapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The intestinal epithelium is considered to be a feasible target for somatic gene therapy. To this end, Caco-2 cells derived from human colon carcinoma were transfected with a mouse interferon-β (IFN-β) expression vector and several stable sublines were established; this hetero-specific cytokine allows unexpected cellular effects to be avoided. Using the highest mouse IFN-β-producing sublines, the mode of IFN secretion was examined. Methods. The secretion polarity of mouse IFN-β in its gene-transduced Caco-2 sublines was studied in a bicameral culture system in which the chambers were separated by microporous filters. Results. Mouse IFN-β was secreted to the same extent from both apical and basolateral surfaces of the transduced cells regardless of cell aging. Conclusions. These results suggest that in the intestinal epithelium exogenous gene products such as IFNs can be delivered to both the luminal and blood sides in vivo. Thus, the intestinal epithelium may be suitable for systemic and local delivery of therapeutic proteins by gene transfer.
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  • 37
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    Breast cancer research and treatment 44 (1997), S. 93-114 
    ISSN: 1573-7217
    Keywords: cancer gene therapy ; gene transfer ; breast carcinoma ; molecular therapeutics ; molecular chemotherapy ; immunotherapy ; loss of heterozygosity (LOH) ; oncogenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
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  • 38
    ISSN: 1573-7217
    Keywords: gene transfer ; human breast epithelial cells ; retrovirus ; selectable marker
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The use of gene transfer procedures has greatlyfacilitated the investigation of cell lineage relationships andother developmental processes in a variety of primarytissues. In this report we describe the infectionand selection of primary human breast epithelial cellsusing retroviral vectors (Jzen-HSA-NEO and MSCV-HSA.NEO) containing thecomplete 228 bp coding sequence of a murinecell surface marker (Heat Stable Antigen, HSA) aswell as the neomycin resistance (neor) gene. Expressionof the transduced HSA gene was detectable usingeither flow cytometry or immunohistochemistry after staining infectedcells with an anti-murine HSA-specific antibody (M1/69). Expressionof the transduced neor gene conferred resistance toG418. In initial experiments with the MCF-7 breastcancer cell line, continued expression of both markerswas demonstrated in a high proportion of cellsfor at least 4 weeks after their infectionby positive M1/69 staining of cells that hadbeen selected by prior incubation in G418. Evidenceof gene transfer to early stage (〈 9days old) primary cultures of normal human breastepithelial cells (15 experiments with cells from 12normal individuals) was also obtained using an infectionprotocol in which these cells were exposed tohelper-free viral supernatants (2 incubations, 4 to 6hr each) after being subcultured for 12 to18 hr to increase their rate of proliferation.The presence of 5–50% (mean=26%) HSA+ cells was demonstrated in these experiments within 5days after their infection and the HSA+populationsincluded both myoepithelial and luminal phenotypes. The transduced(HSA+) cells within both of these subpopulations couldalso be separately isolated by FACS and subcultured.These results should provide an important starting pointfor future studies of genetically modified or markedprimary human breast epithelial cell populations.
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  • 39
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    Cancer and metastasis reviews 16 (1997), S. 421-432 
    ISSN: 1573-7233
    Keywords: cytokine ; tumor ; gene transfer ; immunotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The cytokine approach to gene therapy of cancer stems from early studies of direct, repeated injection of recombinant cytokines at the tumor site, and extension of the bystander effect that enables a few cytokine gene transduced cells in a tumor to bring about its total destruction. This effect can be extended through the immune system, since cytokine-activated regression of a small mass of tumor cells can afford systemic protection. Transduced cells used as a vaccine provide a local concentration of both cytokine and tumor antigens. Cytokines sustain antigen uptake and presentation by increasing the immunogenic potential of the environment through the recruitment of antigen presenting cells and leukocytes, and activation of a cascade of events which amplify and tone up the efficacy of a vaccine. The promises and difficulties of this approach are discussed by considering what is still missing from experimental studies and what can best be done as soon as possible in animals and humans to reach compelling conclusions.
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  • 40
    ISSN: 1573-5060
    Keywords: Agrobacterium tumefaciens ; Bacillus thuringiensis ; cotton ; gene transfer ; Gossypium hirsutum ; insect resistance ; protease inhibitors ; regeneration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The main goal of gene transfer into cotton is the development of insect-resistant varieties. The stakes are important since cotton protection against insects uses almost 24% of the world's chemical insecticides market, which is not without consequences on the environment. The first approach was to introduce and express in the cotton genome, genes from the bacterium Bacillus thuringiensis (B.t.) which produces entomopathogenic toxins. The development of an efficient Agrobacterium tumefaciens mediated transformation system was the first step. The expression of B.t. genes was studied and synthetic genes more adapted to a plant genome have been constructed. Studies on their expression in cotton is underway. The second focus was to develop strategies that would minimize the risks of inducing insect resistance. The main approach is to associate several genes coding for entomopathogenic proteins with different modes of action. Genes encoding protease inhibitors were chosen. One possibility is to associate a B.t. gene and a gene encoding a protease inhibitor. Several protease inhibitors were tested in artificial diets on major pests of cotton. The corresponding genes have been introduced into the cotton genome. These various orientations of the research program will be presented.
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  • 41
    ISSN: 0009-2940
    Keywords: Alkoxopalladium(II) ; Conformational analysis ; Hydrogen bonding ; Two-dimensional and cage structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of palladium acetate with two equivalents of di- and triethanolamines RN(CH2CH2OH)2 in the presence of a base affords the new chelate-stabilized alkoxo Pd(II) complexes [Pd(OCH2CH2N(R)CH2CH2OH)2] [R = Me (1), Et (2), n-Bu (3), benzyl (4) or CH2CH2OH (5)]. These N,O-ligated complexes are isolated in high yield as yellow, crystalline solids and are thermally stable despite the presence of several β-hydrogen atoms in the ligand system. Both complexes possess a square-planar palladium coordination geometry with the two oxygen atoms positioned mutually trans. The most notable difference in the molecular structures is that 1 forms a two dimensional network of intermolecular O-H≡O hydrogen bonds, whereas 5 forms intramolecular O-H⃛O hydrogen bonds, which cage the palladium center. In solution 1-4 exist as a diastereoisomeric mixture (a racemic enantiomeric pair SNSN, RNRN and a mesomeric form RNSN) in a 1:1 molar ratio, and this ratio is independent of temperature in nonalcoholic solvents, When complexes 1-4 are dissolved in protic solvents (e.g. MeOH) the diastereomeric excess is temperature-dependent due to an exchange process between the meso diastereoisomer and the (racemic) enantiomeric pair. Thermodynamic parameters for this process in a mixture of MeOH-toluene have been determined with NMR and show this process to be influenced by the steric nature of the alkyl substituent (R) on nitrogen. A conformational analysis based on 1H-NMR coupling constants within the N,O-chelate ring of complexes 1-4 provides details on the solution structure of the ring in both diastereoisomers.
    Additional Material: 9 Ill.
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  • 42
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 13-22 
    ISSN: 0009-2940
    Keywords: Carbamates ; Catalysis ; Substituted nitrobenzenes ; Palladium ; Reductive carbonylation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The palladium-catalyzed reductive carbonylation of ortho and para-substituted nitrobenzenes has proven to be an attractive route for the synthesis of functionalized carbamates. For the Pd(1, 10-phenanthroline)2(triflate)2 catalyst system, the scope of the reaction has been studied. Substrates with electron-donating substituents at the para position were found to decrease the catalytic activity, most probably as a result of their relatively low oxidizing capacity. the selectivity towards the desired carbamate, however, was increased for these substrates. Under the influence of electron-withdrawing substituents the azoxybenzene and azobenzene derivatives became important side products. Introduction of large steric hindrance at the ortho position of the nitro substrates gave rise to an interesting side reaction, viz. methoxylation of the aromatic ring. The methoxylation reaction appeared to occur on an intermediate species in the catalytic cycle. Several functionalities have shown to be resistant to the reaction conditions required for the conversion ot the nitro group. Especially with 4-nitrobenzoic acid, an extremely high activity and selectivity was found, thus yielding a very convenient synthesis for N-protected amines containing carboxylic acid function.
    Additional Material: 1 Ill.
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  • 43
    ISSN: 0009-2940
    Keywords: Isothiazole complexes ; Dinuclear silver(I) complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of isothiazole-based potential ligands bearing substituents with additional donor sites in the 5-position of the heterocycle was synthesized [3-Me-5-R-C3HNS; R = CH=N(CH2)2py (1), CH=NCH2py (2), CH2N(CH2CH2NEt2)2 (4), (CH2)2SMe (5)]. Upon reaction with AgO3SCF3 they formed complexes [(1)AgOSO2CF3]2 (6), [(2)AgOSO2CF3]2 (7), [(4)Ag]2+2(O3SCF-3)2 (8) and [(5)AgOSO2CF3]2 (9), respectively. 6, 8 and 9 were shown by X-ray structural analyses to consist of dimeric units L2Ag2+2, either discrete (8), coordinated by terminal CF3SO-3 units (6). In 8 and 9 the isothiazole moiety is bonded to the metal center via the ring-N. The coordination potential of the isothiazole heterocycle is discussed.
    Additional Material: 5 Ill.
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  • 44
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 115-118 
    ISSN: 0009-2940
    Keywords: Gold complexes ; Bromonium complex ; Halogenonium complex ; Halogen, two-coordinate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of (R3P)AuX (X = Cl, Br, I) with [(R3P)Au]+ BF-4 obtained from (R3P)AuCl and AgBF4 in tetrahydrofuran, lead to cationic binuclear gold(I) complexes of the general formula ([(R3P)Au]2X}+ BF-4. A number of chloro- (R = Ph, o-Tol, Mes, Bzl, Et), bromo- (R = Ph, o-Tol, Mes) and iodo-bridged (R = Ph, Mes) complexes of this type have been isolated and identified on the basis of their analytical and spectroscopic data. The crystal structure of bis[(triphenylphosphane)gold(I)]bromonium tetrafluoroborate was determined by single-crystal X-ray diffraction. The cations contain two-coordinate bromine atoms with an Au-Br-Au angle of 96.83(3)°.
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  • 45
    ISSN: 0009-2940
    Keywords: Arene complexes ; Ruthenium compounds ; Electrophilic substitution ; Lithiation ; Catalysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiral or achiral (arene)(COD)Ru complexes can be made by replacing the η6-ligands of (η4-1,5-COD)(η6-1,3,5-cyclooctatriene)Ru (1) or (η4-1,5-COD)(η6-naphthalene)Ru (2) by a suitable arene. This well known reaction has been extended to mono- and dibromoarenes and we report a novel route to substituted (arene)(COD)Ru species, utilizing (bromoarene)-(COD)Ru as starting materials. These facilitate a rapid bromine-lithium exchange reaction with nBuLi at low temperatures and the lithiated species react readily with alkyl chloroformates as electrophiles. By using chiral electrophiles [alkyl = (-)-menthyl] enantiomerically pure or diastereomeric complexes containing CO2R* groups are formed, depending on the symmetry of the original complex. A diastereomeric 1:1 mixture was separated by recrystallization. All (arene)-(COD)Ru complexes tested so far are useful as catalysts for the hydrogenation of simple alkenes at room temperature.
    Additional Material: 3 Ill.
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  • 46
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 145-154 
    ISSN: 0009-2940
    Keywords: Fluorocarbons ; C-F bond activation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The main reaction pathways which lead to the breaking of C-F bonds in perfluoroalkanes and -arenes are discussed. Emphasis is placed on recent developments and on the mechanistic patterns that emerge.
    Additional Material: 2 Tab.
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  • 47
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The metal-vapor reactions of Co atoms with 1,3-tBu2CpH (1a), 1,3-tBu2CpH (1a), 1,2,4-tBu3CpH (1b) and EtMe4CpH (1c) are described. With 1a the two mononuclear complexes [(η5-tBu2Cp) (η4-tBu2-1,3-cyclopentadiene)Co] (2a) and [(η5-tBu2Cp)2Co] (3a) were isolated, together with the dinuclear cobalt cluster [{(η5-tBu2Cp)Co}2H3] (4a) and trace amounts of the tetranuclear cluster [{(η5-tBu2Cp)CoH}4] (5a). The molecular structures of 3a and 4a were determined by X-ray diffraction. Reaction of 1b with Co atoms afforded a single product, the dinuclear cluster [{(η5-tBu3Cp)Co}2H3] (4b), whose molecular structure was determined by single-crystal X-ray diffraction. Both, 4a and 4b exhibit extremely short Co-Co distances [2.244(1) (4a) and 2.242(1) Å (4b)], as found for the Me5Cp analog [{(η5-Me5Cp)Co}2H3] (4c). Reaction of an isomeric mixture of Me4EtCpH (1c) with Co atoms furnished the mononuclear sandwich [ (η5-Me4EtCp)(η4-Me4Et-1,3- cyclopentadiene)Co] (2b), the trinuclear hydridocobalt cluster [{(η5-Me4EtCp)Co}3H4] (6a) and the tetranuclear hydridocobalt cluster [{(η5-Me4EtCp)Co}4H4] (5c). The molecular structure of 5c was determined by X-ray crystallography and revealed a tetrahedral arrangement of the cobalt atoms. The electrochemical behavior of the dinuclear complexes 4a-4c was studied by cyclic voltammetry. Reversible redox couples were found for all three compounds, with a correlation between the degree of alkyl substitution and their respective cathodic shifts. Compounds 4a and 4b react with CO to yield the mononuclear and dinuclear complexes [ (η5- CpR)Co(CO)2] (R=1,3-tBu2, 1,2,4-tBu3) (7a and 7b) as well as [{(η5-CpR)CO}2(CO)2] (8a and 8b). Reaction of the trinuclear hydridocobalt cluster 6a and its Me5Cp analog 6b with AgBF4 in the presence of PEt3 yielded the heteronuclear clusters [{η5-Me4CPR)Co}3AgP(Et)3H4]+[BF4]- (R=Et, Me) (9a and 9b). 9a was structurally characterized by X-ray crystallography.
    Additional Material: 8 Ill.
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  • 48
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 45-48 
    ISSN: 0009-2940
    Keywords: Metallated methyl isopropenyl ether ; Tetrahydrofurans ; 1-Oxabicyclo[4.3.0]heptanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl isopropenyl ether (1) has been metallated at low temperature with a 1:1 molar mixture of n-BuLi/t-BuOK in THF-hexane, and subsequently functionalized with a variety of electrophilic reagents. At temperatures higher than - 30°C, the metallated methyl isopropenyl ether (2) decomposes with formation of allene. When the suspension of 2 is allowed to warm up to room temperature in the presence of an additional equivalent of n-BuLi, the intermediary allene is converted into 1-propynyllithium (2c), which reacts with propylthiocyanate to give 1-propylthio-1-propyne (4). Some of the functionalization products were subjected to acidic hydrolysis affording the expected methyl ketones.
    Additional Material: 2 Tab.
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  • 49
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 55-62 
    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).
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  • 50
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 405-408 
    ISSN: 0009-2940
    Keywords: Hexahydro-closo-hexaborates ; Boron ; Bridging ligands ; NMR spectroscopy ; Gold ; Copper ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By reaction of (PPh3)3 CuCl and PPh3AuCl with [B6H6]2- in organic media, dinuclear complexes are formed containing the hexaborate as a bridging ligand coordinated to the metal centers by opposite B3 facets of the B6 cluster in a trihapto mode. This is verified by single-crystal X-ray structural analysis of the isotypical (Paā) compounds [Cu2μ-bis-η3-B6H6)(PPh3)2] (1) and [Au2(μ-bis-η3-B6H6)(PPh3)2)] (2) which showed the metal centers to be very close to the B3 plane [1.92 (1), 2.10 (2) Å. The 11B NMR spectra of the two compounds feature doublets, at δ= -15.32 in 1 and at -11.51 in 2, which are significantly shifted downfield in comparison to [B6H6]2- (δ= -17.2).
    Additional Material: 2 Ill.
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  • 51
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 425-429 
    ISSN: 0009-2940
    Keywords: Silver complexes ; Crown compounds ; Thioethers ; 1,3-Dithioles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coordination chemistry of two crown thioethers 2,5,8,10,12-pentathiabicyclo[7.3.0]dodeca-1)9)-ene-11-thione (L) and -11-one (L') with Ag1 has been investigated by structural methods. Both thioethers act as tridentate ligands coordinating the silver ion in a trigonal fashion. In the case L, the 11- thione sulfur is coordinated additionally by another silver ion, to yield a polymeric chain with a distorted-tetrahedral geometry about the metal ion. Despite differing only in its carbonyl chalcogen, L' forms six-coordinated, monomeric complexes.
    Additional Material: 3 Ill.
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  • 52
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 433-442 
    ISSN: 0009-2940
    Keywords: Metallobiosites ; Metalloproteins ; Metalloenzymes ; Dinucleating ligands ; Transition metals ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Awareness of the asymmetric nature of numerous dinuclear metallobiosites and of the ability of the individual metal ions to have quite distinct roles in the functioning of the metalloenzyme concerned has led to a search for carefully designed unsymmetric dinucleating ligands that will give dinuclear complexes capable of acting as models for the metallobiosites. This review surveys progress made in the design and synthesis of complexes capable of serving as models for donor atom, coordination number and geometric asymmetries found at dinuclear metal centres.
    Additional Material: 2 Ill.
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  • 53
    ISSN: 0009-2940
    Keywords: Alkali metal organophosphanylamide ; Carbon-potassium bonding ; Phosphazane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The metalation of bis(diphenylphosphanyl)amine [HN-(PPh2)2,1 with KOtBu at 95°C in toluene affords a pale yellow precipitate of potassium bis(diphenylphosphanyl)amide (3a). On addition of liquid N,N,N′,N“,N“-pentamethyldiethylenetriamine (PMDTA, 4) the precipitate dissolves in toluene at 115°C to give a yellow solution, from which yellow-green blocks of [(Ph2P)2NK·PMDTA] (3b) are obtained. X-ray analysis reveals that the coordination sphere of potassium consists of the chelating triamine ligand and [N(PPh2)2]- as N-donor as well as η1 and η2 C-donor with two phenyl fragments. No phosphorus coordination of [N(PPh2)2]- is observed.
    Additional Material: 2 Ill.
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  • 54
    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.
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  • 55
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 283-289 
    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.
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  • 56
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 295-298 
    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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  • 57
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 335-340 
    ISSN: 0009-2940
    Keywords: Allylsilanes ; Superbases ; Metalations ; Stereoselectivity ; Cyclizations ; Silicon ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When treated with two equivalents of a butyllithium/potassium tert-butoxide mixture, terminal olefins carrying unprotected hydroxy or carboxy groups generate allylmetal intermediates which can be trapped with chlorotrimethylsilane to afford functionalized (Z)-2-alkenyltrimethylsilanes. One equivalent of the superbasic reagent suffices if the unsaturated alcohols are first protected as acetals before being subjected to the metalation/silylation/hydrolysis sequence.
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  • 58
    ISSN: 0009-2940
    Keywords: Metallacycloalkanes ; Metallacycloalkenes ; Osmium ; Iron ; Cyclic ketones ; Metallacycles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of the bis(triflates) [F3CSO3-(CH)m-O3SCF3] [m = 5-10, 12, 14, 16 (1a-i) with Na2[Os(CO)4] in dimethyl either affords the osmacycloalkanes 2a, 2b and 2f-i (m = 5, 6, 10, 12, 14, 16), diosmacycloalkanes 3a-i (m = 5-10, 12, 14, 16), and triosmacycloalkanes 4a-i (m = 5-10, 12, 14, 16). The structure of 3f was investigated by an X-ray structural analysis. This 22-membered disomacycle crystallizes in the space group Pā with Z = 1. If the unsaturated cis-4-octen-1,8-diyl bis(trifluoromethanesulfonate) (5) is treated with Na2[Os(CO)4] the diosmacyclooctadeca-5,14-diene 6 is obtained. By treating the bis(triflates) 1a, b with Na2[Fe(CO)4] the corresponding ferracycloalkanes are formed only in situ. Insertion of carbon monoxide into the M-C σ bonds leads to the cyclic ketones 7a, d and to the diketone 8d.
    Additional Material: 4 Ill.
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  • 59
    ISSN: 0009-2940
    Keywords: Pyrrolidinephosphanes ; 3-Hydroxypyrrolidine ; 3-Diphenylphosphanylpyronlidine ; Salt effects ; Polymorphism ; Homogeneous catalysis ; Palladium ; Asymmetric catalysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of both enantiomers of 3-diphenylphosphanulpyrrolidiine (2) and several N-substituted derivatives together with two PdIi complexes of this ligand is reported. Form L-malic acid and L-hydroxyproline both enantiomers of 3-hydroxypyrrolidine are prepared without any problems due to epimerization. KPPh2 in the presence of LiCl is shown to be the most effective reagent for the synthesis of 2. The reported X-ray structure determination sof Pdl2 complexes show a rather rigid bicyclic hetero-norbornane skeleton. The flexibility of the other parts of the molecules is obvious in several polymorphs revealed by this method. This polymorphism is additionally investigated by a 31P-CP-MAS study. From solution 1-, 13C- and 31P-NMR studies it is concluded that the bicyclic hetero-norbornane skeleton is retained in solution.
    Additional Material: 3 Ill.
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  • 60
    ISSN: 0009-2940
    Keywords: Trichlorosilylation ; Dichlorophosphanes ; Silylphosphanes ; Amino(silyl)phosphanes ; Silicon /Reductions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of hexachlorodisilane and of trichlorosilane/triethylamine with alkyl-and dialkylaminodichlorophosphanes RPCl2 1a-i [R = iPr: a; (Me3Si)2CH: b; R=1-adamantly: c: R=tBu: d; R=Et2N: e; R=iPr2M: f] furnish bis(trichlorosilyl)-phosphanes RP(SiCl3)2 3a-f. However, when less bulky substituents are attached to the phosphorus atom, so that there is little steric crowding, the double reductive silylations leading from 1 to 3 are accompanied by side reactions and decomposition of 3. Therefore, only 3b, 3c, 3d, and 3f wre isolated in a pure state. These compounds are more readily prepared by the; trichlorosilane/triethylamine method. 1H-, 31P- and 29Si-Nmr spectra confirm their constitution. The structure of solid 3f, the first aminobis(trichlorosilyl)phosphane, was determined by X-ray crystallography. 3f contains a phosphorus atom in a pyramidal environment surrounded by two silicon atoms and a planar nitrogen atom of the diisopropylamino group.
    Additional Material: 2 Ill.
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  • 61
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 417-420 
    ISSN: 0009-2940
    Keywords: Gallium ; Low-valent compounds ; Gallium-gallium bond ; Terminal triphenytriazenido ligand ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrakis[bis(trimethylsilyl)methyl]digallane (4) 1 reacts with 1,3-diphenyltriazene to yield two compounds, which were both characterized by a crystal structure determination. The gallium-gallium bond is retained in the yellow derivate [(H5C6)2N3](R)Ga-Ga(R)[N3(C6H5)2 2 [R = CH(SiMe3)2], which is formed by a ligand exchange reaction and shows two terminal chelating triazenido ligands besides two bis(trimethylsilyl)methyl groups; the Ga—Ga bond length is 245.79(6) pm. The second product is the orange dialkyl(diphenyltriazenido)gallium derivative R2Ga[N3(C6H5)2] 3, where the triazene has reacted as an oxidant by the cleavage of the Ga—Ga bond and probably by release of elemental hydrogen.
    Additional Material: 2 Ill.
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  • 62
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 463-472 
    ISSN: 0009-2940
    Keywords: Hypervalent compounds ; Tellurium ; Polycations ; Molecular Orbital Theory ; Band structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Approximate MO and band structure calculation are used to analyze the bonding in the recently synthesized paramagnetic, semiconducting phase [Te15Br4]2+. The [Te15Br4]2+ chains are very similar to those in the tellurium subhalide Te2Br. The electronic structure and bonding within these chains is analysed and the possibility of hypervalency in both [Te15Br4][MoOBr4]2 and Te2Br is discussed. The bonding in the classically hypervalent molecule TeBr42- and a model Te3Br24- is compared to that of the infinite system. Our calculations indicate that both [Te15Br4][MoOBr4]2 and Te2Br contain weakly hypervalent Te atoms and that the interesting electronic properties of [Te15Br4][MoOBr4]2 arise within the distinct sublattices, which do not interact significantly.
    Additional Material: 12 Ill.
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  • 63
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 479-488 
    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.
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  • 64
    ISSN: 0009-2940
    Keywords: Rhenium ; Technetium ; 8a-Amino-6-methyl-ergoline ; Chelates ; Structure elucidation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Current research in radiopharmaceutical chemistry is aimed at the design of technetium-based receptor-binding radiotracers because of the excellent nuclide properties of the isotope 99mTc. Tc tracers and the corresponding complexes of rhenium, as the inactive surrogate of Tc, are required to imitate organic agonists or antagonists of the receptor. We have started studies with ergolines, which are known to be dopamine substitutes. The present report deals with the functionalization of 8α-amino-6-methyl-ergoline (2) with a 2-mercaptoacetyl group, and the subsequent synthesis of the first rhenium complex containing a pendent ergoline moiety [Re- O(SSS)(RS)] (HSSSH = HS-CH2CH2-S-CH2CH2-SH and RSH = 8a-amino-N-(2-mercaptoacetyl)-6-methyl-ergoline) (4). The molecular structure of the rhenium complex was determined by X-ray crystal structure analysis.
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  • 65
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 859-862 
    ISSN: 0009-2940
    Keywords: Yttrium ; Lanthanum ; Samarium ; Lanthanides ; Aminotroponiminate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of N-isopropyl-2-(isopropylamino)troponimine, [(i-Pr)2ATI]H, with KH in THF affords [(i-Pr)2ATI]K. This is a useful starting material for the preparation of the mono-, bis- and tris-substituted compounds [[i-Pr)2ATI]YCl2-(THF)2}2, [(i-Pr)2ATI2Y[O(2,6,t-Bu2C6H3)] and [(i-Pr)2-ATI]3Ln (Ln = Y, La, Sm), which can be obtained from ([i-Pr)2ATI]K and LnX3 and LnX3 (X = Cl, I), or Y[O(2,6-t-BuC6H3)]3. All compounds have been characterized by spectroscopic methods. The monosubstituted yttrium complex {[(i-Pr)2ATI]YCl2(THF)2}2 has also been investigated by single crystal X-ray diffraction.
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  • 66
    ISSN: 0009-2940
    Keywords: C-H activation ; Alkyne complexes ; Cyclopentadienyl cobalt ; Fluxionality ; Hydrido complexes ; Clusters ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vicinal C-H bonds of the cycloalkenes CnH2n (n = 5-8) were activated upon treatment under mild conditions with reactive sources of the (C5H5)CO fragment. With [C5H5)CO(C2H4)2] (2a), the trinuclear cluster complexes [H2((C5H5)CO)3(μ3-C2(CH2)n-2)] (5a: n = 5; 5c: n = 5d: n = 8) were formed. Using the more reactive [(C5H5)2Co]/K, 5a-5dwere obtained, along with small amounts of the tetranuclear [{(C5H5)CO}4r{μ4-C2(CH2)n-2}] (8a-c: n = 5-7). X-ray structure analyses of 5c, d and 8b, c were performed. A μ-‖ (orμ3-η1:η2:η1) coordination of the cycloalkyne ligands was found in the trinuclear cluster complexes. The tetranuclear 8b, c had the cycloalkynes quadruply bridging (μ4-η1:η2:η2:η1_ a butterfly arrangement of the metal atoms. The acetylenic carbon-carbon bonds are considerably lengthened upon coordination [1.392(4), 1.398(3) å in 5c d; 1.464(8), 1.499(5) Å in 8b, c]. Three dynamic processes - alkyne “walk” on top of the CO3 triangle, μ2-hydride migration, and μ2/μ3-hydride exchange - are operational in the trinuclear 5a-d. Dynamic NMR data for 5a are consistent with a “windshield-wiper” mechanism for the alkyne migration. Hydride exchange is associated with a higher energy barrier, and is probably and independent dynamic process.
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  • 67
    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.
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  • 68
    ISSN: 0009-2940
    Keywords: Biaryls ; Boron ; Chirality ; Cooperative Effects ; Lewis acids ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A number of Lewis acid binaphthyl systems, substituted in 2-or 2,2′-position, are synthesized by lithiation of 2,2′-dibromo-1,l ′-binaphthyl (5), followed by addition of various electrophiles. Stepwise lithiation and subsequent borylation with trimethyl borate leads to the bromoboronic acid 6, which can be stabilized by esterification with pinacol giving 7. By increasing the reaction mixture to 2 equiv. of n-butyllithium and 2 equiv. of methyl borate the path to the binaphthylmonoboronic acid ester 9 is opened up. A further increase in the quantity of electrophile also leads to the binaphthylbisboronic acid ester 12. The 2,2′-disubstituted silyl, germyl, and stannyl derivatives 13a-15a are accessible in good yields. Treatment with boron halides leads exclusively to methyl/halogen exchange, giving the bidentate Lewis acids 13b-15b, the former of which can be bridged by oxygen.Only in case of the bis(tributylstannyl)binaphthyl 16a does ipso substitution occur in the presence of boron trichloride, giving the bis(dichloroboryl)-substituted binaphthyl 16b which can then be hydrolysed to 11. The structures of the majority of the compounds were investigated by X-ray diffraction. In case of the 2,2′-disubstituted compounds 13a-15a the naphthyl groups are orientated perpendicular to each other. The intra- and intermolecular interactions are dominated by this binaphthyl system. In case of the oxygenbridged compounds 13c and 14c the angle between the naphthyl planes decreases to about 70°. This also has an effect on the packing of the molecule; in this instance the orientation of two naphthyl in neighbouring molecules is nearly parallel. The structure of the diboronic acid is dominated by intra- and intermolecular hydrogen bonding.
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  • 69
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 951-954 
    ISSN: 0009-2940
    Keywords: Phosphane-boranes ; Medium-sized rings ; Ring opening and closure ; Temperature-dependent NMR studies ; Phosphorus ; Boron ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A phosphane-borane (3) with the P-B bond integrated into a seven-membered ring was prepared from 4-pentenyl-diphenylphosphane (4) by hydroboration using 9-borabicyclononane (9-BBN). The product was confirmed to have a ring structure in the solid state by single crystal X-ray diffraction. The P-B distance of 2.057(2) Å is indicative of a standard donor-acceptor bond similar to the type found in homologous five- and six-membered rings. The room-temperature 31P-NMR signal of the compound in various solvents (δ ≈ - 15) is not compatible with the cyclic structure and suggests that ring opening occurs as the compound is dissolved. Variable-temperature NMR work corroborated this assumption, and the enthalpy of ring closure was determined to be ΔH = -30.5(4) kJmol-l. In CD2C12 at -90°C, δ31P is shifted to +3.5 ppm to low field, suggesting virtually complete ring closure under these conditions.
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  • 70
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 963-968 
    ISSN: 0009-2940
    Keywords: Fluorine ; Macrocycles ; Complexes ; Sodium ; Barium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two new fluoro macrocycles BenzoFN2O3 and F(N2O2)2C2H4 were synthesized in the reactions of 1,3-bis(bromomethyl)-2-fluorobenzene with benzo-diaza-15-crown-5 and 1,2-bis(diaza-12-crown-4)ethane, respectively, in 30% yield each. Close CF...metal ion interactions in the respective alkaline metal complexes in solution are evidenced by characteristic shifts of the 19F-NMR resonances of up to δ = 18.7 relative to the free ligand and by a decrease of the 1J(CF) coupling constant of up to 20 Hz, which is most pronounced in BenzoFN2O3 · Li+ and F(N2O2)2C2H4 · K+. In BenzoFN2O3· Li+ a1J(19F-7Li) of 15.5 Hz was observed, which is indicative very close CF...Li+ interactions in solution. In the X-ray crystal structures of BenzoFN2O3 · Na+ [CF⃛Na+ 246.8(2) pm], 26-fluoro-4,7,13,16-tetraoxa-1, 10-diazatricyclo[ 8.8.7.1 20,24 ] - hexacosa-20,22,24(26)triene · Na+ (CF⃛Na+ 267.1(2) pm) and 21 -fluoro-3,6,9,12,15,18-hexaoxabicyclo[ 18.3.1 1,20]heneicosa- l(24),20,22-triene. Ba2+ [CF⃛Ba2+ 299.0(3) pm] short CF⃛metal interactions were found. Such close CF⃛metal ion interactions do not result in a lengthening of the C-F bonds, which is not a sign of weak CF⃛metal ion interactions, since a Cambridge Structural Database search revealed that a shortening of the C-O bond length is also not observed in crown ether complexes of alkaline metals.
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  • 71
    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.
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  • 72
    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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  • 73
    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.
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  • 74
    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.
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  • 75
    ISSN: 0009-2940
    Keywords: Boron ; Diazaboroles ; Carbenes ; Heterocycles ; Imidazoles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Bromo-2,3-dihydro-1H-1,3,2-diazaboroles (3a-c) were synthesized by cyclocondensation of dilithiated 1,4-diazabutadienes (5a-c) with boron tribromide in hexane. 3a was also obtained by sodium amalgam reduction was conducted in ether solvents, diboroxane (2) resulted as the main product. Compound 3a and 1,3-dialkyl-4,5-dimethylimidazol2-ylidenes (6a, b) underwent halide displacement to afford the borolylimidazolium salts 7a, b. Compounds 2, 3a-c, and 7a, b were characterized by elemental analyses and spectroscopic methods (1H, 11B, 13C NMR; Ir; MS). The molecular structures of 2 and 7a were established by single-crystal X-ray diffraction analyses.
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  • 76
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 725-728 
    ISSN: 0009-2940
    Keywords: Dendrimers ; Metal complexes ; Nanostructures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Strong multiple complexation of transition metal ions, Cu(II), Zn(II) and Ni(II) with different generations of well-defined poly(propylene imine) dendrimers as multi(tridentate) ligands has been used to construct nanoscopic assemblies of defined structure and size incorporating a distinct number of metal ions from 2 up to 32.
    Additional Material: 5 Ill.
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  • 77
    ISSN: 0009-2940
    Keywords: Germanium ; Digermenes ; Tin ; Germylenes ; Stannylenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of GeCl2 · dioxane with the Grignard reagent RMgBr (R=2-tBu-4,5,6-Me3C6H) furnishes the tetraaryldigermene R2Ge=GeR2 (8). X-ray structure-analysis of 8 reveals a short Ge=Ge double bond, a nearly planar environment of both germanium atoms and extremely widened C—Ge—C angles of 128°. In solution, 8 dissociates into two germylene molecules R2Ge, which can be trapped with oxygen or by [4+1] cycloaddition reactions with 1,4-dihetero-1,3-dienes. A similar cycloadduct of a stannylene wa obtained by thermolysis of (R′2Sn)3 (R′=2,4,6-iPr3C6H2), in the presence of a 1,4-diazabutadiene and characterized by an X-ray structure-analysis.
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  • 78
    ISSN: 0009-2940
    Keywords: Silicenium ion ; Iminosilane ; Aluminate ; Silicon ; Aluminium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lithiated text-butylaminolfluorosilanes react with aluminum trichloride in ether, eliminating LiF to give AlCl3 adducts of iminosilanes  -  aminosiliceniotrichloroaluminates {R2Si-NCMe3·AlCl3}, which thermally form the dimethylazomethine- aluminium trichloride, Me2C=NH·AlCl3.
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  • 79
    ISSN: 0009-2940
    Keywords: Titanocene complexes ; S ligands ; Organic polysulfanes ; Ligand transfer reactions ; Sulfur heterocycles ; Chalcogens ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of Cp2Ti(CO)2 (3) with the di- and polysulfanes 1,2,4-(CH2)2S3, C4S6 (9), C,7H10S3 (11), 1,2,4,6-(CH2)3S4 (16), C6H10S6(19), and S6 affords the titanocene chelate complexes Cp2TiS3(CH2)2 (8), (Cp2Ti)2C4S6 (10), Cp2TiS3C7H10 (13), Cp2TiS2C7H10 (14), Cp2TiS4(CH2)3 (17), Cp,2TiS6C6H6H10 (20), and Cp2TiS8 (23). 14 is also obtained from Cp2TiCl2 (1) and the geminal dithiol of norbornene. The analogous reaction with the dithiol of dicyclopentadiene yields Cp2TiS2C10H12 (15). In ligand transfer reactions, 8 reacts with SCl2 to give 1,2,3,5-tetrathiane (25), 10 provides 9 on reaction with Cl2, 13 when treated with S2Cl2 affords C7H10S5 (12), 15 reacts with S2Cl2Cl2 to give C10H12S4. 17 and SCl2 yield 1,2,3,5,7-pentathiepane (18), 20 is converted to C6H10S7 (22) on reaction with SCl2, and 23 yields S10 and 1,2,-C6H4(SCl)2, respectively. With phosgene, thiophosgene, and thionyl chloride, compound 15 yields the corresponding dithiocarbonate 26, the trithiocarbonate 27 and the trisulfane 2-oxide 28. The structure of 27 was determined by X-ray crystallography.
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  • 80
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 801-806 
    ISSN: 0009-2940
    Keywords: Unsymmetrical phthalocyanines ; Hemiporphyrazines ; Macrocyclic bisdienes and bisdienophiles ; Diels-Alder reactions ; Ladder polymers ; Cycloaddition ; Macrocycles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The specific synthesis of a metal-free bisdienophilic phthalocyanine 193, suitable for repetitive Diels-Alder reactions, is reported. This was achieved by condensation of 191,3,3-trichloro-6/7-nitroioindolenine (191) and 4,9-dibutoxy-2,3,5,8-tetrahydro-1,3-diimino-1H-5,8-epoxybenz[f]isoindoline (2). The ability of 3 to undergo Diels-Alder reactions was tested by reaction with an excess of 1,2,3,4-tetraphenylcyclopentadienone (5). Experimental data of the hemiporphyrazines 9, 10, and 11, which can be used as precursors for the synthesis of ladder polymers, are also given in the Experimental Section.
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  • 81
    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.
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  • 82
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1021-1027 
    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.
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  • 83
    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.
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  • 84
    ISSN: 0009-2940
    Keywords: Planar-tetracoordinate carbon ; Dynamic organometallic systems, μ-alkyne complexes ; π-Agostic systems ; Zirconium ; Metallocenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The benzonitrile hydrozirconation product Cp2ZrCl(N—CHPh) 8 was treated with propynyl lithium to yield the (propynyl)(benzaldimido)ZrCp; complex 9. Subsequent treatment with trityl tetraphenylborate generated [Cp2Zr(C—C—CH3)-BPh-4] that instantaneously added to 9 to eventually form the (μ-aldimido)(μ-η1:η2-hexadiyne)ZrCp2 cation 11. The X-ray crystal structure analysis showed that 11 contains a planar-tetracoordinate carbon atom that is stabilized by forming a three-center-two-electron bond with the two adjacent metal atoms. Similarly, complex 9 reacted with [Cp2Zr(CH3)+CH3B(C6F5)3 1 to yield the planar-tetracoordinate carbon containing (μ-aldimido)(μ-η1:η2-2-butyne) Cp; cation 12. Both complexes 11 and 12 exhibit dynamic NMR spectra due to their rapid reorganization of the dimetallabicyclic frameworks (ΔG* = 10 kcal mol-1) in addition to an anchimerically assisted C—N bond rotation (ΔG* =15 kcal mol-1).
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  • 85
    ISSN: 0009-2940
    Keywords: Porphyrinatomanganese(IV) ; Monooxygenase model ; Dichloro monoxide ; Catalytic alkene epoxidation ; Catalytic alkane oxygenation ; Catalytic alkane chlorination ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The isolation at -78°C and characterization of the novel crystalline reactive porphinatomanganese(IV) complex Mn-(TDCPP)(OCl)2 (5) is described. 5 is compared with the porphinatomanganese(IV) complexes Mn(TDCPP)(C6H5IOCl)2 (2), Mn(TDCPP)(C6F510C1)CI (3) and Mn(TDCPP)(OCH3)2, (4). The stoichiometric reaction of 5 with triphenylphosphane yields 2.5 equivalents of triphenylphosphane oxide and 1.0 equivalent of Mn(TDCPP)Cl (1). Complex 5 epoxidizes stilbene, and oxygenates and chlorinates cyclohexane.
    Additional Material: 2 Tab.
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  • 86
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1135-1139 
    ISSN: 0009-2940
    Keywords: Arene complexes ; Chromium ; Allenes ; Rearrangements ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Cr(CO)3-complexed η6-phenylpropargylic alcohols 3 react in a displacement rearrangement with thionyl chloride or chlorodiphenylphosphane to give the chloro- or phosphoryl allenyl substituted η6-phenyl complexes 4 and 6, respectively. In the X-ray crystal structure of the novel organometallic allenic derivatives 4b and 6b the vicinal chloro or phosphoryl substituent and the benzene(tricarbonyl)chromium fragment are arranged coplanarily. Palladium/copper-catalyzed couplings of the chloroallene 4b with terminal alkynes disclose a facile access to ynallene derivatives 8, novel carbon-rich organometallic π-systems.
    Additional Material: 1 Ill.
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  • 87
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1141-1145 
    ISSN: 0009-2940
    Keywords: Trichlorophosphoranylidenesulfamoyl chloride ; Vibrational spectroscopy ; Conformational properties ; Quantum chemical calculations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Raman (3500-50 cm-l) and infrared (4000-400 cm-l) spectra of the title compound, ClSO2N=PCl3, were recorded for the solid and liquid phase. Additionally, the Raman spectrum of the compound dissolved in CCl4 was obtained and qualitative depolarization values were determined. The spectra of the liquid and solid phase were interpreted in terms of the existence of only one conformation possessing C1 symmetry, as predicted by quantum chemical calculations. A complete vibrational assignment is proposed based on the relative intensities, on group frequencies along with support from the normal coordinate analysis. The experimental fundamental vibrational modes are compared to those obtained from theoretical approaches employing the ab initio MP2/6-31G* method and a density functional approximation (B3PW91/6-31G*).
    Additional Material: 3 Ill.
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  • 88
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1147-1150 
    ISSN: 0009-2940
    Keywords: Icosahedral heteroboranes ; Ab initio calculation ; Bonding models ; Aromaticity ; Nucleus Independent Chemical Shift [NICS] ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ab initio theoretical studies on X2B10H10 (X = CH, SiH, N, P and Sb) have been done for all the three possible isomers. Unlike lower-vertex heteroboranes, all the hetero derivatives have shown similar trends in the relative stabilities, the 1,12-isomer being more stable followed by 1,7- and 1,2-isomers, except for N and Sb. No conventional 1,2-isomer for N could be found. Instead, a new nido isomer which is 18.1 kcal/mol higher in energy than the most stable isomer has been located. Any hetero group substitution to icosahedral R12H122- is found to be thermodynamically destabilizing. However, the Nucleus Independent Chemical Shift criterion shows that all compounds, except for 8, have similar aromaticity.
    Additional Material: 2 Tab.
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  • 89
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1159-1166 
    ISSN: 0009-2940
    Keywords: Aminosilantes ; Structure elucidation ; Molecular conformations ; Configuration determination ; Nitrogen Planarity/Silanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structural chemistry of a series of triaminosilanes XSi(NR2)3 has been investigated in order to determine the ground-state configuration and conformation of these molecules. Theoretical studies and analogy with the isoelectronic XP(NR2)3 (X = CH2, O, Se, NSiMe3 etc.) and P(NR2)3 molecules suggest structures of Cs or C3 symmetry, with small energy differences between them. The molecular structure of HSi(NMe2)3 (1) has been determined by a single-crystal X-ray diffraction study at low temperature. Surprisingly, the molecules have a non-standard conformation with an irregular orientation of the three NMe2 groups. The hydrido-, chloro-, methyl-, and vinyltris(morpholino)silanes XSi[N(CH2CH2)2O]3 (X = H, Cl, Me, Vi; 2-5) were prepared from the corresponding chlorosilanes and morpholine (2, 3) or lithium morpholide (4,5). Their variable-temperature NMR spectra were studied and the molecular structures determined by single crystal X-ray diffraction. Compound 2 has a molecular geometry approaching mirror symmetry with one morpholino group significantly different from the other two. This structure resembles that of isoelectronic tris(amino)phosphines. Compounds 3-5 have structures with a propeller-like arrangement of the three morpholino rings approaching C3 symmetry for this part of the molecules. The chloro compound 3 shows the shortest Si-N bond lengths (average 1.690 Å), followed by 2 (1.708Å),5 (1.709Å) and 4 (l.712Å). The configuration of all nitrogen atoms is almost planar, with sums of the angles close to 360°, and the morpholino rings adopt a chair conformation. According to the solution NMR spectra the ring inversion is slow at low temperature, but the rings rotate freely about the Si-N bonds on the NMR time scale. The molecular structures are discussed in terms of steric and electronic effects of the substituents. Other model compounds, including (Me2N)3SiC6H4-4-Br (6), MeSi[N(CH2CH2)2NMe]3 (7) and PhSi[N(CH2)4]3 (8), could not be crystallized, but were characterized by their analytical and spectroscopic data.
    Additional Material: 7 Ill.
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  • 90
    ISSN: 0009-2940
    Keywords: Lead ; Tetrachloroaluminate ; Arenes ; o-Xylene ; Bis(arene) Complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(o-xylene)lead(II) bis(tetrachloroaluminate), obtained from lead(II) chloride and aluminium trichloride in o-xylene, has been shown by X-ray crystallography to be a mononuclear lead complex with point group symmetry C2 The two aromatic ligands are arranged similarly to those in monomeric plumbocene. The coordination sphere is completed by two bidentate AlCl4-ions. The lead center uses about a quarter of its bonding capability for each of the four ligands
    Additional Material: 1 Ill.
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  • 91
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1751-1759 
    ISSN: 0009-2940
    Keywords: Amido complexes ; Titanium ; Zirconium ; Alkylmetal compounds ; Amido complexes ; Titanium ; Zirconium ; Alkylmetal compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The novel tridentate diamidoamine ligands [RC(2C5H4N)(CH2NSiMe3)2)2- (R = H, CH3) have been synthesized and coordinated to TiIV giving the pentacoordinate complexes [MX2(RC(2-C5H4N)(CH2NSiMe3)2}] (M = Ti, Zr; X = Cl, Br). The crystal structure analysis of [TiBr2{HC(2-C5H4N)(CH2)2}] (M = Ti, Zr; X = Cl, Br). The crystal structure analysis of [TiBr2{HC(2-C5H4N)(CH2NSiMe3))] (10b) confirmed the involvement of the pyridyl function in the coordination to the meta centre occupying an apical position in the trigonal bipyramidal ligand polyhedron. alkylation of [TiCl2{H3CC(2-C5H4N)(CH2NSiMe3)2)] (12a) with one or two molar equivalents of [RMgCl](R = PhCH2, Me3SiC2) yielded the mono- and dialkyl complexes [TiClR{H3CC(2-C5H4N)(CH2NSiMe3)2)] and [TiR2(H3CC(2-C5H4N)(CH2NSiMe3)2)] and [TiR2(H3CC(2-C5H4N)(CH2NSiMe3)2}] in good yields. Depending on the steric demand of the alkyl group coordination or decoordination of the pyridyl group leads to four- or five-coordinate species. A crystal structure analysis of the pentacoordinate complex [TiCl(CH2SiMe3){H3CC(2-C5H4N)(CH2NSiMe3)2}] (16) was carried out.
    Additional Material: 3 Ill.
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  • 92
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 93
    ISSN: 0009-2940
    Keywords: Phthalocyanines ; Sol-gel processes ; Titanium alkoxides ; Supported catalysts ; Heterogenous catalysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cobalt(II) 2,9,16,23-tetrasulphophthalocyanine and cobalt(II) 2,9,16,23-tetra(chlorosulphonyl)phthalocyanine were supported on TiO2 by reaction of the phthalocyanines with Ti(OR)4 followed by sol-gel synthesis. The thus obtained solid materials are stable in sulfide-containing media and are therefore suitable as catalysts for HS oxidation. The structure of the samples was characterized by electron microscopy diffraction. The morphology of the matrix strongly depends on the cobalt phthalocyanine derivative. The pathalocyanines in the titania matrices are monomeric or dimeric depending both on the type of substituents of the CoPc derivative and on the titanium alkoxide used as precursors.
    Additional Material: 5 Ill.
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  • 94
    ISSN: 0009-2940
    Keywords: Dichlorogermylene ; Trichlorogermylphosphanes ; Insertion ; Silver bromide complex ; Carbene homologues ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chlorophosphanes RR'PCl (1a: R,R' = 1b: R = tBu, R' = iPr, 1c: R = iPr, R' = Et2N, 1d: R = Et2N react with the dichlorogermylene dioxane complex 2 furnishing trichlorogermylphosphanes RR'PGeCl3 4a-d. In the cases of 1c/4c and 1d/4d the insertion reaction remain incomplete; similarly, 4a always contains, shortly after isolation in pure state, small amounts of 1a that can be detected by NMR. A provided by the reaction of trichlorosilylphosphane tBu(Et2N)PSiCl3 (5d) with GeCl4. The alkyl(dialkylamino) trichlorogermylphosphane 4d exists only in an equilibrium with chlorophosphane 1d, which coordinates GeCl2 leading to the dichlorogermylene complex 3d. A 1:1 mixture of 4a with 1a is formed by the novel cleavage (“chlorogermylation”) of the P-P bond of tetraisopropyldiphosphane with germanium tetrachloride. Di-tert-butyl(trichlorogermyl)phosphane 4e (R, R' = tBu) reacts with silver bromide providing a crystalline silver complex 7. A structure determination by X-ray diffraction reveals that 7 is [Ag4Br4(tBu2PCl)2(tBu2PGeCl3)2]. 2C7H8. Two of the Ag atoms of the cubane-like (AgBr)4 core of 7 are coordinated by chlorophosphane 1e, the other two by trichlorogermylphosphane 4e.
    Additional Material: 1 Ill.
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  • 95
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1647-1654 
    ISSN: 0009-2940
    Keywords: Iron ; Carbene complexes ; (2-Methoxythenyl)methoxycarbene complexes ; Aminolysis ; (2-Aminoethenyl) methoxycarbene complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cationic (2-methoxyethenyl)methoxycarbene iron complexes 2, [Cp(CO)2Fe(C(OMe)CH=CR(OMe))+][PF6-], are obtained by the addition of methanol to the corresponding (alkynyl)-methoxycarbene complexes 1, [Cp(CO)2Fe(C(OMe)C≡CR)+][PF6-]. Primary amines, H2NR', react with these 1,3-dimethoxy-substituted (alkenyl)carbene complexes, 2, through an addition/elimination process to yield cationic (2-aminoethenyl)methoxycarbene iron complexes, 3, [Cp(CO)2Fe(C(OMe)CH=CR(NHR'))+][PF6-] in an isolated yield of 71-90%. The complexes 3a-c were characterized by X-ray structural analyses. Thus, previously isolated products, from the reaction, of the (alkynyl)methoxycarbene complexes 1a and 1c, with aniline at room temperature, are assigned to the structures 3c and 3e. The spectroscopic and structural data obtained are discussed.
    Additional Material: 3 Ill.
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  • 96
    ISSN: 0009-2940
    Keywords: Hydroformylation ; High-pressure NMR ; Homogeneous catalysis ; Rhodium ; Polyphosphane ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rhodium-catalyzed hydroformylation of 1-hexene in THF with the linear triphosphane PhP(CH2CH2PPh2)2 [PP,] has been studied both in situ and in high-pressure autoclaves. Sapphire NMR tubes with titanium valves have proved useful for studying the in situ reactions under conditions of relatively high syngas pressure (30-90 atm H,/CO) and temperature (60-100 C). Under conditions conducive to effective hydroformylation, the catalyst precursor [ (PP,)Rh(CO)]+ is quantitatively converted to the dicarbonyl [ (PP,)Rh(CO),]+, which is also the termination product of the catalysis. Irrespective of the syngas composition and of the total pressure, the dicarbonyl complex is the only phosphorus-containing species detectable on the NMR time-scale during the course of the isomerization and hydroformylation of the alkene. The PP2-Rh catalytic system exhibits some peculiar features that may be summarized as follows. (i) Very high partial pressures of CO (120 atm) neither inhibit the hydroformylation nor affect the n/i selectivity; (ii) alkene hydrogenation occurs neither at very high partial pressures of H, (120 atm) nor in the absence of added CO; (iii) the isomerization rate is slightly faster than that of hydroformylation; (iv) terminal and internal alkenes (2-, 3-hexenes) are hydroformylated with comparable rates. Various control experiments have been carried out using in-situ NMR, as well as batch experiments under different reaction conditions or with different catalyst precursors. Despite these extensive studies, unambiguous conclusions about the catalysis mechanism have not been reached. In particular, the possibility that different catalysts may be operative depending on the reaction conditions cannot be ruled out. The hydroformylation results rule out the involvement of phosphane-free “Rh-CO” catalysts, even under conditions of very high partial pressure of CO, and point to “(PP,)Rh(CO),” catalysts with small steric hindrance over the whole range of syngas pressures investigated.
    Additional Material: 4 Ill.
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  • 97
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 98
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1721-1730 
    ISSN: 0009-2940
    Keywords: Perhalometallocenes ; Cylopentadienes ; Perhalogenated ; Halogen-metal exchange reactions ; Sandwich complexes ; Ligand effects ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coordination chemistry of perhalocyclopentadienyl ligands, first developed in the early 1970's as a part of a research program directed towards the synthesis of oxidation-resistant fuel additives, has been revived in the last ten years. This renewed interest stems from the discovery that the coordinated cyclopentadienyl ligand allows multiple functionalizations. Thus, the high versatility of this important class of ligands can be broadened even further, which may be important with regard to industrial applications of metallocenes.
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  • 99
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1745-1749 
    ISSN: 0009-2940
    Keywords: Density functional calculations ; Tetra(amino)methane ; Tetra(amino)silane ; Transition states ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In all-electron density functional calculations on mono- and tetraaminosubstituted methane and silane the coordination around the nitrogen center is found, in complete agreement with experiment, to be less pyramidal in the silicon compounds. The calculated barrier to inversion at nitrogen is only 0.6 kcal/mol in silylamine, while in methylamine it is 5.5 kcal/mol. The larger flexibility is attributed to the greater ionic character of the Si-N bond compared to that of the C-N bond. In tetra(amino)methane, inversion of one amino group leads to a local minimum (calculated inversion barrier: 6.4 kcal/mol), while a corresponding structure (or barrier) does not exist for the silicon compound. Due to the steric influence of the amino groups, the barrier to rotation around the C-N bond is larger in the tetrasubstituted compound (6.4 kcal/mol compared to 2.3 kcal/mol in methylamine). While the average binding energy of the amino groups is similar in both tetra(amino)compounds, the binding energy of the fourth ligand is about 25% larger in the silicon compound for both homolytic and heterolytic bond cleavage. This difference arises from the relative stabilization of the tri(amino)-methyl species, due to some n contribution to the C-N bond.
    Additional Material: 4 Ill.
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  • 100
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1771-1776 
    ISSN: 0009-2940
    Keywords: Chelates ; P ligands ; Phosphaferrocene ; Carbonyl complexes ; Heterocycles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dicyclohexyl-acid diphenylphosphanyl-substituted phosphaferrocenes 2 and 3 were synthesized by substitution of the amino group in 2-dimethylaminomethyl-3,4,-dimethylphosphaferrocene 1 · Homologization of 2-formyl-3,4-dimethylphosphaferrocene 4 by one CH2 unit via Wittig olefination provided access to the phosphanylethyl derivative 9. Ligands 2, 3 and 9 formed P, P-chelate complexes with tetracarbonyl metal fragments in good yield. X-ray crystal structure determinations were carried out for the five-ring chelate complex 2. Mo(CO)4 (≡ l0), and the six-ring chelate complex 9 . Mo(CO)4, (≡ 13).
    Additional Material: 1 Ill.
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