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  • Electronic Resource  (261)
  • AV-Medium
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  • 2010-2014
  • 2000-2004  (261)
  • Analytical Chemistry and Spectroscopy  (101)
  • chemotherapy  (81)
  • kinetics  (79)
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  • Electronic Resource  (261)
  • AV-Medium
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  • 101
    ISSN: 1573-7373
    Keywords: recurrent choroid plexus papilloma ; chemotherapy ; CCNU ; survival
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract A pregnant 33-year old woman developed nystagmus and cerebellar ataxia. A tumor in the roof of the fourth ventricle was diagnosed. The tumor was subtotally removed using microneurosurgical techniques. The histopathological diagnosis was choroid plexus papilloma (CPP). Twenty-one months later, the tumor recurred and was reoperated. Histologically the tumor displayed now increased mitotic activity and pleomorphism. Radiation therapy of the neuroaxis was performed. Within 59 months, the CPP recurred 3 more times with neuroradiological evidence of extensive spinal seeding. After several palliative irradiations, including 2 gamma-knife boosts, the patient was referred to chemotherapy. She was treated with CCNU (Lomustin) 100 mg/m2 orally (12 cycles, cumulative dosis 1440 mg/m2). Within 42 months, there was no new local recurrence and spinal seeding showed significant regression. Clinically the patient improved and stabilized, but needs continuous support because of persisting severe gait ataxia. The course of disease in our patient provides evidence for therapeutic efficacy of CCNU in recurrent CPP.
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  • 102
    ISSN: 1573-7373
    Keywords: glioma ; chemotherapy ; docetaxel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The objective of the study was to assess the efficacy of docetaxel in recurrent supratentorial malignant gliomas. The sample size of the study was determined by the Gehan's method for a response rate of 20% and a β error of 5%. In the first step 14 patients (age 27–69, median 50; Karnofsky index 50–90, median 75) with recurrent malignant glioma after surgery, radiotherapy and nitrosourea, were enrolled (12 glioblastomas, 2 anaplastic astrocytomas). Docetaxel at the initial dose of 80 mg/m2 was administered every 3 weeks until progression or unacceptable toxicity. A total of 41 cycles was administered. Patients received a median of two cycles (range 1–6). No complete or partial response was observed. Therefore, according to the design of the study, no additional patients were enrolled and the trial was terminated. Two stabilizations were observed (14 and 15 weeks). Median TTP was 7 weeks (44 days). Median overall survival from recurrence was 26.5 weeks (6.4 months). Grade 3–4 neutropenia was observed in 8 patients (57%) but no life-threatening toxicity was observed. Other toxicities were uncommon and mild. Dose reduction was performed in 5 patients. This study suggests that docetaxel displayed no significant activity in patients with malignant recurrent gliomas.
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  • 103
    ISSN: 1573-7373
    Keywords: glioblastoma multiforme ; chemotherapy ; radiotherapy ; phase II trial
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Recent publications support the use of preradiation chemotherapy in the treatment of selected primary brain tumors. In the pediatric population, this treatment strategy often delays radiotherapy and may improve the outcome in patients. This manuscript describes the use of a preradiation chemotherapy approach for adult patients with newly diagnosed glioblastoma multiforme. The main objective of this trial was to determine the feasibility of delivering up to 3 monthly cycles of a 72 h continuous simultaneous intravenous infusion of BCNU (40 mg/m2/day) and cisplatin (40 mg/m2/day). Patients were evaluated for tumor response or progression after each cycle. Following the completion of the chemotherapy treatments or evidence of tumor progression, patients underwent external beam radiotherapy. A dose of 45 Gy was delivered to the pretreatment tumor volume plus surrounding edema and a margin of 3.0 cm. An additional 14.4 Gy was delivered to the preoperative volume plus a 2 cm margin. Fifty patients were enrolled, 47 were eligible and analyzable. Overall, 79% of patients were able to complete at least 2 cycles of treatment, exceeding the predefined measure of feasibility. One patient achieved a complete response, 10 patients a partial response and 18 patients had stable disease at completion of the chemotherapy treatments. Twenty-four patients experienced grade 4 toxicity, mostly hematologic. All patients were able to undergo radiotherapy following chemotherapy. These results indicate that a preradiation strategy is feasible. Although responses to the chemotherapy were seen, a phase III trial is needed to determine whether this approach provides an advantage over standard treatment; such a phase III trial has been undertaken by ECOG.
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  • 104
    ISSN: 1573-7373
    Keywords: chemotherapy ; estramustine ; estramustine-binding protein ; glioma ; rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Estramustine is a chemotherapeutic drug, used in the treatment of prostatic carcinoma. In the prostate, it binds specifically to a 46 kDa glycoprotein called estramustine-binding protein (EMBP), which consists of three polypeptide components; C1, C2, and C3, each coded for by a specific gene. Expression of EMBP and binding of estramustine has also been detected in malignant glioma in both rats and humans. Elevated levels of this protein in astrocytoma have proved to correlate with poor prognosis. In the present work, expression of all three polypeptide components of EMBP was confirmed in an orthotopic rat glioma model with nested reverse transcriptase PCR and Western blot (molecular weights of 8, 10, and 12 kDa). Specific binding of estramustine with a K d of 40 for male and 50 for female rats, and a total number of binding sites of 0.7 and 0.4 pmol/mg proteins for male and female rats respectively, was demonstrated with Scatchard plot analysis. These binding characteristics are similar to those of prostatic EMBP. Further studies to elucidate how EMBP expression affects the effect of estramustine treatment, and its putative prognostic value is of special clinical interest. The confirmation of BMBP expression in BT4C rat glioma demonstrates its suitability as a model system for such studies.
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  • 105
    ISSN: 1573-7373
    Keywords: glioma ; chemotherapy ; prognosis ; interferon-β ; MCNU
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Combined treatment with interferon-beta, MCNU (Ranimustine), and radiotherapy was assessed in patients with malignant glioma who had not received previous cytotoxic drug therapy. Forty-three patients up to 75 years old with histopathologically confirmed malignant glioma were studied. All patients had tumors measurable by neuroimaging, a Karnofsky performance score exceeding 40, and an expected survival exceeding 2 months. A response rate of 49% (21/45) was observed, including 6 complete remissions (14%) and 15 partial remissions (35%). Of the 43 patients who completed initial therapy, 19 were given sequential maintenance therapy. Survival time was much longer with than without maintenance therapy. Toxic side effects were moderate and did not substantially affect patients' general condition. We concluded that this combination therapy had a pronounced effect on untreated malignant glioma, particularly in patients whose initial therapy was followed up with maintenance therapy.
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  • 106
    Electronic Resource
    Electronic Resource
    Springer
    Tropical animal health and production 32 (2000), S. 361-374 
    ISSN: 1573-7438
    Keywords: cattle ; chemotherapy ; diminazene ; homidium ; Kenya ; oxytetracycline ; transhumance ; treatment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Information was collected on the use of veterinary drugs by Maasai pastoralists in an area of Kenya where tsetse flies and trypanosomosis occur. Three herds of cattle were followed for between 4 and 5 years and records were kept of every veterinary drug treatment given by the livestock owners. Almost all treatments were either with the trypanocides homidium or diminazene, or with oxytetracycline by intramuscular injection. The rate of trypanocide use varied between 0.66 and 1.56 treatments per animal per year, while oxytetracycline use was between 0.20 and 1.00 treatments per animal per year. Farmers were injecting these drugs in the absence of veterinary supervision, obtaining their supplies mainly from local village shops or informal traders. Underdosing with trypanocides appeared to be uncommon and the indications were that farmers generally gave the drugs at dosage rates above the recommended standard dose. Accurate information on the dose rates of oxytetracycline could not be obtained, but it was noted that in most cases farmers gave a single injection rather than a course of treatment. In a proportion of cases, trypanocides and antibiotics were mixed together before injection. The farmers administered the drugs when disease was recognized and were rarely using trypanocides as prophylactics. Although necessity forces the livestock owners to obtain and use these drugs without veterinary supervision, there are concerns with regard to the possibility of drug misuse and the development of drug resistance.
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  • 107
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neuro-oncology 46 (2000), S. 97-103 
    ISSN: 1573-7373
    Keywords: boswellic acids ; glioma ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Conventional malignant glioma therapy (surgery, radiation therapy and chemotherapy) does not yield satisfying results. The prognosis of the glioma patient depends more on the histological grading of the tumor and patient's age than on the therapy. Especially the adjuvant chemotherapy failed to date to influence survival time in glioma patients significantly. To improve results in malignant glioma therapy additional therapeutic regimes are necessary. In an earlier study we were able to show a significant reduction on perifocal edema by an extract from gum resin (EGR) accompanied with a clinical improvement in patients with malignant glioma. Also a decrease of urinary LTE4-excretion as a metabolite of leukotriene synthesis in brain tumors was observed. Furthermore we had found a proliferation inhibiting activity of the extract form EGR, the boswellic acids in cell cultures. The purpose of this experimental study was to elucidate the effects of the boswellic acids, which are constituents of an extract from gum resin on tumor growth in vivo. Female wistar rats weighing 200–250 g were treated with the drug 14 days after inoculation of C6 tumor cells into their right caudate nucleus and randomization into 4 groups. The treatment groups received different dosages and were compared to a control group without any additional treatment. Survival time of the rats in the highest dosage group (3 × 240 mg/kg body weight) was more than twice as long as in the control group (P 〈 0.05). In a second experiment the inhibition of tumor cell proliferation was examined. The C6 tumor cells were implanted into the caudate nucleus. Drug treatment was started immediately after implantation and stopped after 14 days. The animals were sacrificed and the brains were examined microscopically. Comparing low and high dosage of EGR treatment a significant difference in tumor volume was detected (P 〈 0.05). The proportion of apoptotic tumor cells in animals with high dose treatment was significantly larger than in the low dose (treatment) group (P 〈 0.05). These data demonstrate an influence of EGR in rat glioma growth and might represent a new therapeutic option on glioma treatment in man in future. Further experimental work on human gliomas is needed to definitively answer this question.
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  • 108
    ISSN: 1573-7373
    Keywords: astrocytoma ; 201thallium SPECT ; MRI ; MR spectroscopy ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Purpose To compare chemotherapy treatment monitoring in astrocytoma by 201thallium single photon emission computed tomography (SPECT) and photon magnetic resonance spectroscopy (1H-MRS) with magnetic resonance imaging (MRI), and to evaluate the influence of morphological tumor changes on cerebral 201thallium uptake and metabolic changes in 1H-MRS. Materials and methods Six patients with highly malignant astrocytomas were followed with quantitative 201thallium SPECT, MRI, and 1H-MRS during chemotherapy. Maximum follow-up included six examinations per patient by either method during 18 months. Criteria were set for: (1) regression (≥ 25% tumor reduction), (2) status quo (〈 25% reduction and 〈 25% increase), and (3) progression of disease (≥ 25% tumor increase). Results were compared with the clinical state of disease. Changes of tumor volume, contrast enhancement, necrosis, hemorrhage and edema on MRI were compared to changes in 201thallium uptake volumes and 1H-MRS metabolite ratios. Results Six patients were followed with a total of twenty-four examinations with 201thallium SPECT, MRI and 1H-MRS, respectively, between February 1997 and October 1998. Five patients developed clinical progression of disease, 4 out of 5 cases showed SPECT progression, 4 out of 5 cases MRI progression, and 1 out of 2 interpretable cases 1H-MRS progression at final assessment before clinical deterioration. During the phase of clinically stable disease; (A) the criterion for regression or status quo was met in 10 out of 13 assessments with SPECT, 11 out of 13 with MRI, and 8 out of 9 interpretable 1H-MRS; (B) the criterion for progression was met in 3 out of 13 with SPECT, 2 out of 13 with MRI, and 1 out of 9 interpretable 1H-MRS. The accuracy of SPECT, MRI, and 1H-MRS in identifying changes of tumor burden concordant with patients' clinical course was 78%, 83%, and 82%, respectively. SPECT regression was associated with MRI decrease of tumor size, contrast enhancement, edema and hemorrhage. SPECT progression was associated with MRI increase of the same parameters and the increase of necrosis. 1H-MRS regression was associated with decrease of edema. 1H-MRS progression was associated with increase of tumor size, hemorrhage, and increase or decrease of contrast enhancement. Conclusions Both 201thallium SPECT and 1H-MRS evaluation showed sensitivity for detection of astrocytoma progression. We did not find a higher accuracy of SPECT or MRS than of MRI in astrocytoma chemotherapy monitoring. Treatment induced MRI changes were associated with 201thallium uptake variations. 1H-MRS was difficult to apply for astrocytoma treatment monitoring. Improvements regarding size of measurement area such as multivoxel MRS and fat suppression pulses appeared desirable, and also the use of functional techniques with superior resolution such as dual isotope SPECT. However, our results suggest that 201thallium SPECT and 1H-MRS can provide additional information to MRI for chemotherapy efficacy evaluation in selected cases.
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  • 109
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neuro-oncology 48 (2000), S. 249-250 
    ISSN: 1573-7373
    Keywords: anticonvulsant drugs ; chemotherapy ; gliomas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The reduced bioavailability of chemotherapeutic agents is one of the reasons that explains the limited efficacy of adjuvant chemotherapy in high grade glioma patients. We report how even the results of high dose sequential chemotherapy can be influenced by antiepileptic drugs.
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  • 110
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neuro-oncology 49 (2000), S. 105-115 
    ISSN: 1573-7373
    Keywords: glioma ; MRP ; chemotherapy ; RT-PCR ; immunohistochemistry ; antisense oligonucleotide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Drug resistance is a major clinical problem in the chemotherapy of human gliomas. The multidrug resistance-associated protein (MRP), a membrane transporter related to non-P-glycoprotein multidrug resistance, is overexpressed in some drug-selected cancer cell lines. To investigate whether MRP is involved in the intrinsic drug resistance of human gliomas, surgical specimens of 20 gliomas (11 glioblastomas, 6 anaplastic astrocytomas, and 3 astrocytomas), 3 normal brain specimens, and 4 glioma cell lines (U87MG, U251MG, U373MG, and T98G) were analyzed. The expression of MRP was studied by RT-PCR and immunohistochemistry in the surgical specimens. The MRP expression levels in the cell lines were assessed by the quantitative RT-PCR and Western blot analyses. Sensitivity to adriamycin (ADM), etoposide (VP-16), cisplatin (CDDP), and 1-(4-amino-2-methyl-5-pyrimidinyl) methyl-3-(2-chloroethyl)-3-nitrosourea (ACNU), were determined by MTT assay, and antisense treatment was evaluated in the cell lines. The expression of MRP was detected in 9 of 11 glioblastomas and 3 of 6 anaplastic astrocytomas. The quantitative analyses of the cell lines revealed that the MRP mRNA and protein levels were increased 4.5-fold in the T98G cells as compared to U87MG. T98G cells showed the highest resistance to all drugs. Western blot analysis revealed that treatment with the antisense oligonucleotide reduced the level of MRP expression to 25% of the sense oligonucleotide treatment in T98G cells. The sensitivity to ADM, VP-16 and CDDP was significantly increased in the antisense-treated cells as compared with the sense-treated cells. These results suggest that the MRP expression may be related to the intrinsic multidrug resistance in human gliomas.
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  • 111
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neuro-oncology 49 (2000), S. 165-170 
    ISSN: 1573-7373
    Keywords: brain tumor ; chemotherapy ; hydroxyurea ; meningioma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Meningiomas represent 18–20% of all intracranial tumors and have a 10-year recurrence rate of 20–50%, despite aggressive surgery and irradiation. In addition, many tumors are not amenable to surgery due to their deep location or proximity to delicate structures. Chemotherapy is being explored as another potential treatment option for unresectable or refractory meningiomas. Hydroxyurea is an agent that inhibits ribonucleotide reductase and can induce apoptosis in meningioma cell cultures and animal models. We have placed 17 patients with unresectable or residual meningioma on hydroxyurea chemotherapy (20 mg/kg/d orally). The mean age of our cohort was 57.2 years; 13 patients were female. Eleven patients had actively growing tumors or neurological progression at the onset of chemotherapy. Sixteen patients were evaluable for response. Fourteen of the 16 patients (88%) responded with stable disease ranging from 20 to 144+ weeks (median 80 weeks; 10 patients still accruing time). Three of the responders progressed after 20, 36, and 56 weeks, respectively. Two patients had progressive disease after 10 weeks. Toxicity was hematologic in most patients; leukopenia was most common. Nine patients (53%) required dosage reductions (250–500 mg/d) secondary to hematologic toxicity. Hydroxyurea appears to have modest activity against meningiomas and should be considered in patients with unresectable tumors or large residual tumors following surgical resection.
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  • 112
    ISSN: 1573-7373
    Keywords: accelerated radiation therapy ; ACNU ; Ara-C ; chemotherapy ; high-grade glioma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Purpose To evaluate activity and toxicity of simultaneous ACNU and Ara-C with concurrent accelerated hyperfractionated radiotherapy in the treatment of high-grade glioma. Patients and Methods Thirty patients aged 23–71 years (median 47.5), 16 patients with glioblastoma multiforme (GBM) and 14 patients with grade-III glioma, received 93 courses of ACNU/Ara-C (median 4 courses) at following dose levels (ACNU/Ara-C in mg/m2/day): 70/90 (11 courses), 75/100 (36 courses) and 90/120 (46 courses). ACNU was administered IV on day 1 of each cycle, Ara-C as a 2 h-intravenous infusion on days 1–3. Patients received concomitant radiation therapy with 2 daily fractions of 1.75 Gy up to 57 Gy (median). Results Median survival of all patients was 13 months, 11 months for GBM and 〉 28 months for grade-III glioma; 31% (9 patients) survived longer than 24 months. The percentage of grade IV hematological toxicity was dose-dependent: 33% at the 70/90 dose level, 40% at 75/100 and 58% at 90/120. Six patients required platelet transfusion, 1 patient red blood cells; no febrile neutropenia occurred. Among 18 patients evaluable for response, 3 (17%) showed PR, 8 (44%) NC and 7 (39%) PD at completion of chemoradiation. No acute or late neurological toxicity occurred in this study. Younger age (p = 0.0001) and grade-III histology (p = 0.0009) were important prognostic factors for prolonged survival. Conclusion This chemoradiation regimen is active in malignant gliomas and can be safely recommended at a dose level using 70 mg/m2 ACNU together with 90 mg/m2 Ara-C.
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  • 113
    Electronic Resource
    Electronic Resource
    Springer
    Journal of applied spectroscopy 67 (2000), S. 981-989 
    ISSN: 1573-8647
    Keywords: nonlinear regime of stimulated Raman scattering ; fluctuation ; Stokes radiation ; kinetics ; spectrum ; distribution function
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Statistical properties of the Raman scattering of an intense step pulse are investigated by numerical solution of the equations of a semi-classical theory with assignment of a random Gaussian distribution of the initial polarization over the sample. The probability density functions of the intensity, energy, delay time, and width of a Stokes pulse and also of the position, height, and width of the spectral peaks of the first incidental Stokes component with the preservation of the phase memory of scattering centers are calculated. The influence of collisional dephasing on the fluctuation of these characteristics is considered.
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  • 114
    Electronic Resource
    Electronic Resource
    Springer
    Powder metallurgy and metal ceramics 39 (2000), S. 540-544 
    ISSN: 1573-9066
    Keywords: compaction ; facing ; cumulative charge ; powder ; composite ; heterogeneous structure ; particle ; kinetics ; surface ; die ; model ; xeroradiogram
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract An experimental and numerical (finite element method) study is carried out for the effect of forming scheme on property distribution for cumulative charge facings made from composite heterogeneous powder material. An experimental procedure is developed for studying powder particle flow kinetics. It is shown that use of composite punches and partition of the moulded material into a number of sub-divisions with their successive compaction achieves a more uniform density distribution for an article. It is demonstrated how the direction of the force of friction on the die walls during compaction affects the compaction of articles with faces that are not perpendicular to the direction of the pressing. The results obtained make it possible to select the optimum compaction regime taking account of production features connected with powder material composition as well as service characteristics.
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  • 115
    Electronic Resource
    Electronic Resource
    Springer
    Pharmaceutical research 17 (2000), S. 701-706 
    ISSN: 1573-904X
    Keywords: vapor sorption ; molar heat of adsorption ; kinetics ; isothermal microcalorimetry ; recrystallization ; hydration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. In this study, instrumentation for measuring vapor sorptionenthalpies and sorption uptakes simultaneously with an isothermalmicrocalorimeter is introduced. Various pharmaceutical modelsubstances undergoing phase transitions when exposed to humid conditions(25°C), were employed to evaluate the usefulness and sensitivity ofthe constructed experimental method. Methods. The sample is placed in the sample vessel of a RH cell andthe moisture content of the air flow is controlled. From the RH cellthe air flow is conducted into a subsequent perfusion cell in which asaturated salt solution has been loaded. The RH cell and perfusioncells are positioned in the sample sides of two twin calorimetric units.Depending on the moisture content in the outlet flow leaving thepreceding RH cell, the heat flow signal from the subsequent perfusioncell will vary. By means of blank measurement with identical settings,the rate of water sorption can be calculated and, by integration, theamount of sorbed water is obtained. Results. Amorphous lactose and cefadroxil undergo recrystallizationwhen the moisture level in the surroundings exceeds the thresholdvalues specific to each compound. During the sorption phase, heat isevolved fairly linearly as a function of consumed moisture, and alsoafter the recrystallization, the heats indicate linear behavior. The heatvalues for the desorption phase of amorphous lactose and the adsorptionof crystalline lactose coincide. With the different anhydrous forms oftheophylline, the hydration takes place more rapidly in the metastableform I, and generally, the process is more energetic in form I. In allcases, the gravimetric results agree with the water sorption uptakescalculated from the calorimetric data. Conclusions. The technique introduced offers a rapid and sensitivemethod to gain new insights into the transitions in which vapors areinvolved. In addition, different kinds of surfaces with various energeticscan now be studied more closely.
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  • 116
    ISSN: 1573-515X
    Keywords: gaseous ; kinetics ; mercury ; methods ; speciation ; waters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Mercury evasion from water is commonly modeled using measurements of dissolved gaseous mercury (DGM). We developed a method using a recently available automated field-ready mercury vapor analyzer to rapidly measure the concentrations of DGM in surface waters. We summarize here results of laboratory tests of the method, field intercomparisons with a manual method, and selected data from recent sampling campaigns in Florida and Michigan. The method uses the 1.5 lpm flow of a Tekran® Model 2537A mercury analyzer to purge and analyze discrete water samples, generating near real time (5-min) data on DGM in samples and blanks. Application of the Tekran allowed for detailed analysis of DGM removal kinetics and short-term diel studies characterizing the influence of sunlight and precipitation on DGM production in surface waters. Gas removal kinetics for dozens of samples indicates a first-order rate constant, and supports a 20-min. purge time for surface water samples from Florida (40-min for Michigan samples). Blanks are measured during a second such purge. Our results indicate that DGMs determined by both automated and manual methods are generally comparable, and that DGM in Florida samples is unstable during storage (loss rate constant ∼0.1--0.2 h-1), probably due to oxidation. This suggests that rapid in-field analysis is preferred to storage with delayed analysis. Our data indicate that DGM at the Florida site is influenced by inputs of reactive Hg in rainwater, and by production of surface DGM during photoreduction of oxidized Hg in the water column.
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  • 117
    ISSN: 1573-689X
    Keywords: bedside wellness system ; chemotherapy ; fatigue ; emesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Background: The bedside wellness system (BSW) is effective for decreasing stress and improving mental well-being and should help relieve the side effects and mental disorders of patients during cancer chemotherapy. Methods: The study was a randomized clinical trial. After giving informed consent, patients were randomly assigned to the BSW intervention or control groups. The patients were given the Hospital Anxiety and Depression Scale (HADS) test before the trial to evaluate their emotional baseline. The Cancer Fatigue Scale, which was developed at our institute, and face visual analog scale were used to measure the emotional state and subjective feelings before and after the trial. The degree of emesis was measured using a visual analogue scale after the experience. We set up the system in a room in the outpatient clinic of the National Cancer Center New Hospital Building. Results: The decreases in the fatigue score and emesis score 3–5 days after chemotherapy were statistically significant (both p 〈 0.05) and carry-over effects were detected. Conclusions: BSW intervention therapy is an effective way to treat fatigue and emesis. This virtual reality system is a new therapeutic method that can be used in palliative medicine.
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  • 118
    Electronic Resource
    Electronic Resource
    Springer
    Cellular and molecular neurobiology 20 (2000), S. 217-230 
    ISSN: 1573-6830
    Keywords: arabinose ; mannitol ; blood–brain barrier ; brain ; drug ; chemotherapy ; osmosis ; shrinkage ; permeability ; tumor ; bulk flow ; tight junctions ; capillary
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract 1. Osmotic opening of the blood–brain barrier by intracarotid infusion of a hypertonic arabinose or mannitol solution is mediated by vasodilatation and shrinkage of cerebrovascular endothelial cells, with widening of the interendothelial tight junctions to an estimated radius of 200 Å. The effect may be facilitated by calcium-mediated contraction of the endothelial cytoskeleton. 2. The marked increase in apparent blood–brain barrier permeability to intravascular substances (10-fold for small molecules) following the osmotic procedure is due to both increased diffusion and bulk fluid flow across the tight junctions. The permeability effect is largely reversed within 10 min. 3. In experimental animals, the osmotic method has been used to grant wide access to the brain of water-soluble drugs, peptides, antibodies, boron compounds for neutron capture therapy, and viral vectors for gene therapy. The method also has been used together with anticancer drugs to treat patients with metastatic or primary brain tumors, with some success and minimal morbidity.
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  • 119
    ISSN: 1573-7217
    Keywords: cerbB2 ; chemotherapy ; neoadjuvant ; prognosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Recent advances in the detection and treatment of breast cancer have led to an intensive search for new markers of both prognosis and chemoresponsiveness. The oncogene cerbB2 has proved to be one of the most promising markers currently under study, both as a predictor of chemoresponsiveness and as a marker of poor prognosis. In addition the increasing use of neoadjuvant chemotherapy has led to the loss of standard prognostic criteria. In order to study the potential role of cerbB2 expression as an indicator of chemoendocrine resistance and poor prognosis, both before and after chemotherapy, we obtained tumour sections from 283 women enrolled onto a neoadjuvant trial. In this trial patients were randomised to receive either primary surgery followed by adjuvant chemoendocrine treatment or neoadjuvant chemoendocrine therapy followed by surgery. CerbB2 status was determined immunohistochemically on all of these patients. Thirty-eight percent of the tumours were cerbB2 positive. There was no significant difference in expression between the adjuvant (41%) and neoadjuvant arms (35%). CerbB2 positive patients were much more likely to have shown non-response to chemoendocrine therapy (p〈0.001) and had a worse DES (p〈0.05). The best prognosis was seen in cerbB2 negative patients receiving neoadjuvant chemoendocrine therapy who showed a significantly better DFS (p〈0.05), than the cerbB2 negative patients receiving adjuvant therapy.
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  • 120
    ISSN: 1573-7217
    Keywords: breast cancer ; locally advanced ; neoadjuvant ; chemotherapy ; paclitaxel ; cisplatin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Background.In an earlier study, we have demonstrated a high response rate in metastatic breast cancer using paclitaxel (P) and cisplatin (C). A phase II study using the same regimen (PC) has been conducted in locally advanced breast cancer (LABC). Methods.A total of 72 consecutive patients with non-inflammatory LABC (T2 ≥ 4 cm, T3 or T4, N0–N2, M0). Patients were scheduled to receive 3–4 cycles of the neoadjuvant PC (paclitaxel 135 mg/m2 and cisplatin 75 mg/m2 on day 1) every 21 days. Patients were then subjected to surgery and subsequently received 6 cycles of FAC (5-fluorouracil 500 mg/m2, doxorubicin 50 mg/m2, and cyclophosphamide 500 mg/m2) or 4 cycles of AC (doxorubicin 60 mg/m2, and cyclophosphamide 600 mg/m2). Patients then received radiation therapy, and those with hormone receptor positive tumors were given adjuvant tamoxifen intended for 5 years. Results.The median age was 39 years (range, 24–78). Clinically, 7%, 58%, and 35% of patients had T2 ≥ 4 cm, T3, and T4, respectively. Disease stage at diagnosis was IIB (33%), IIIA (27%), and IIIB (40%). Complete and partial clinical response to PC was demonstrated in 13 (18%), and 52 (72%) patients, respectively. Of those patients with evaluable pathologic response (68 patients), complete pathologic response (pCR) was achieved in 15 (22%) patients. At a median follow-up of 22 (± 3.5) months, 58 (81%) were alive with no recurrence, nine (12%) were alive with evidence of disease, and five (7%) were dead. None of the patients achieving pCR has developed any relapse. The median overall survival has not been reached for all 72 patients with a projected 3-year survival (± SE) of 90% (± 4%). The median progression-free survival (PFS) was 42.1 (± 4.8) months with a projected PFS of 74% ± 7% at 3-years (for 68 patients). Conclusions.PC regimen in LABC produced a high pCR. The contribution of the other added modalities to survival could not be assessed.
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  • 121
    ISSN: 1573-7217
    Keywords: adjuvant treatment ; breast cancer ; chemotherapy ; immunotherapy ; radiotherapy ; randomized trial
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract With a median follow-up of 14 years, the combination of polyadenylic–polyuridylic acid plus locoregional radiotherapy (257 patients) has significantly improved disease-free survival (p = 0.03) and significantly reduced the incidence of metastases (p = 0.04) when compared to CMF alone (260 patients), in women with operable breast cancer. The trial does not, however, permit an appreciation of the respective role of radiotherapy and PolyAU in these results.
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  • 122
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    Genetica 108 (2000), S. 229-237 
    ISSN: 1573-6857
    Keywords: autoregulation ; dimerization ; kinetics ; post-transcriptional regulation ; transposable elements (TEs)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Kinetic modeling of the self-regulatory mechanisms of transposable elements (TEs) involving interactions of one or a few gene products makes predictions that are often at odds with observed results. In particular, explanations of TE autorepression at high copy number that invoke a decrease in number of active monomers through dimerization, amyloidization, and protein-mRNA binding to create an inactive state are not supported by analysis of the corresponding kinetic models. This is also true for similar mRNA–mRNA binding models. Self-repression in marineras well as other TEs can, however, be explained by a host-independent model in which inactive dimers compete with monomers for TE binding sites at the ends of the element. This model would also allow heterodimer poisoning to down-regulate transposition in the presence of divergent nonautonomous elements, since nondivergent monomers would be required at both TE ends for transposition.
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  • 123
    ISSN: 1573-6881
    Keywords: Permeability transition ; ADP/ATP translocase ; kinetics ; adenosine diphosphate ; carboxya tractyloside ; bongkekic acid ; mitochondria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Physics
    Notes: Abstract Low levels of ADP binding at the ADP/ATP translocase caused inhibition of the Ca2+-inducedpermeability transition of the mitochondrial inner membrane, when measured using the shrinkage assay on mitochondria, which have already undergone a transition. Inhibition was preventedby carboxyatractyloside, but potentiated by bongkrekic acid, which increased the affinity forinhibition by ADP. This suggests that inhibition was related to the conformation of thetranslocase. Ca2+ addition was calculated to remove most of the free ADP. Ca2+ added after ADPinduced a slow decay of the inhibition, which probably reflected the dissociation of ADP fromthe translocator. We conclude that the probability of forming a permeability transition pore(PTP) is much greater when the translocase is in the CAT conformation than in the BKAconformation, and, in the absence of CAT and BKA, the translocator is shifted between theBKA and CAT conformations by ADP binding and removal, even in deenergized mitochondria with no nucleotide gradients.
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  • 124
    ISSN: 1573-7217
    Keywords: advanced breast cancer ; cyclophosphamide ; docetaxel ; epirubicin ; G-CSF ; second-line ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Purpose.A phase II study was performed to investigate the efficacy and tolerance of alternating docetaxel and epirubicin/cyclophosphamide plus recombinant human granulocyte colony-stimulating factor (G-CSF) in patients with advanced breast cancer who failed previous non-anthracycline/taxane-containing palliative chemotherapy. Patients and methods.Between November 96 and June 98, a total of 45 patients participated in this trial. Chemotherapy consisted of docetaxel 100 mg/m2 given as a 1-h infusion on day 1, and epirubicin 100 mg/m2 plus cyclophosphamide 800 mg/m2 both adminstered on day 21. G-CSF 5 μg/kg/day was given subcutaneously from days 22–28 during each cycle. Treatment courses were repeated every 42 days for a total of three courses unless prior evidence of progressive disease. Results.The overall response rate was 57.8% (95% confidence interval, 42.1–72.3%), including seven complete (15.5%) and 19 partial remissions (42.3%); nine patients (20%) had stabilization of disease and 10 (22.3%) progressed. The median time to treatment failure was 7.0 months (range 1.5–26.0), and the median overall survival time 15.0 months (range 2.0–37.0+) with 12 patients (27%) currently still alive with metastatic disease. Myelosuppression was commonly observed with WHO grade 3/4 neutropenia in 20 patients (44%) complicated by septicemia in five (11%). Severe nonhematologic toxicity included stomatitis in five patients (11%), skin and peripheral neurotoxicity each in one patient; alopecia was seen in all 45 patients with complete hair loss in 26 (58%). Conclusions.Our data suggest that alternating docetaxel and epirubicin/cyclo-phosphamide plus G-CSF is an effective and tolerable second-line combination regimen for the treatment of advanced breast cancer.
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  • 125
    ISSN: 1573-7217
    Keywords: breast cancer ; chemotherapy ; cohort study ; radiotherapy ; second primary cancer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Objectives and methods.The risk of second primary malignancies (SMN) was studied in a cohort of 4,416 one-year survivors of a breast cancer. The role of the menopausal status and of the initial treatment modalities (surgery, radiotherapy, and chemotherapy) was investigated. Results.Excluding second primary breast cancer and non-melanoma skin cancer, a total of 193 (4.4%) patients developed a SMN between 1973 and 1992, compared with 136 expected (Standardised Incidence Ratio, SIR = 1.4, 95% CI (1.2–1.6)). No trend towards either an increase or a decrease was noted in the SIR with time after treatment (p = 0.2). The greatest increase in the relative risk concerned soft tissue cancers (SIR = 13.0, 95% CI: 6.8–22.3), followed by leukaemia (SIR = 3.1, 95% CI: 1.7–5.0), melanoma (SIR  =  2.7, 95% CI: 1.4–4.8), kidney (SIR = 2.5, 95% CI: 1.2–4.5), ovary (SIR = 2.0, 95% CI: 1.2–3.1) and uterine tumours (SIR = 1.9, 95% CI: 1.4–2.5). The SIR was 3.0 (95% CI 1.8–4.7) in women under 40 at the time of the breast cancer, 1.9 (95% CI : 1.4 – 2.4) in those aged 40–49 and 1.2 (95% CI 1.0–1.4) in those aged 50 or more. In the 2,514 women who had received radiotherapy as initial treatment without chemotherapy, the SIR for all SMN was 1.6 (95% CI: 1.1–2.3) fold higher than in those who had not received radiotherapy as initial treatment. Conclusion.In conclusion, this study confirms the increased risk of second malignancies in women treated for a breast cancer, and particularly in those who were younger at the time of treatment for breast cancer. Our results also suggest that radiotherapy may play a role in the onset of these second lesions.
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  • 126
    ISSN: 1573-7225
    Keywords: breast neoplasms ; chemotherapy ; female ; hormonal therapy ; invasive carcinoma ; multiple primary neoplasms ; radiation therapy ; thyroid neoplasms
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Background:Breast and thyroid cancer have been observed to occur more frequently than expected as multiple primary tumors in women. The study presented herein focuses on the effects of age at diagnosis and treatment for the first cancer on the development of the second cancer. Methods:This retrospective cohort study used a study population consisting of 38,632 women diagnosed with primary invasive breast cancer and 2189 women diagnosed with primary invasive thyroid cancer between 1974 and 1994. Cases were identified from records of the Cancer Surveillance System of western Washington and followed for subsequent cancer development through 1995. Results:Seventy-one women were diagnosed during their lives with both breast and thyroid cancers. Including cancers diagnosed during the same month as or after the initial cancer, the relative risk (RR) of breast cancer among women with thyroid cancer was 1.5 (95% confidence interval [CI] 1.1–2.0), and the RR of thyroid cancer among women with breast cancer was 1.5 (95% CI 1.1–2.2). Among women with thyroid cancer, risk of breast cancer was greatest when the latter cancer was diagnosed under 45 years of age (RR = 2.3, 95% CI 1.1–4.4). First course of treatment, including radiation or hormonal therapy to treat thyroid cancer, and radiation, chemotherapy, or hormonal therapy to treat breast cancer, did not alter a woman's risk of developing the second cancer. Conclusions:The data suggest that the incidence of breast and thyroid cancer may be related, and that in particular women with thyroid cancer may be at a moderately increased risk of developing breast cancer before age 45.
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  • 127
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    Cancer and metastasis reviews 19 (2000), S. 67-73 
    ISSN: 1573-7233
    Keywords: chemotherapy ; angiogenesis ; durg treatment ; dose scheduling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The mechanism of action of anticancer chemotherapeutic agents is mainly thought to be due to a direct inhibition of tumor cell proliferation. The enhanced endothelial cell proliferation rate in tumor specimens raised the question whether therapeutic effects of chemotherapeutic agents might be at least partially attributed to an inhibition of tumor angiogenesis. Meanwhile, numerous anticancer chemotherapeutic agents were tested for their antiangiogenic potential. A few agents seem to exert consistent inhibition of tumor angiogenesis even in drug-resistant tumors. Most recent investigations on the antiangiogenic efficacy of different application schedules suggested the use of a tightly spaced, continuous application of appropriate anticancer chemotherapeutic agents. These application schedules are able to exert a strong antiangiogenic effect as indicated by an increase of apoptosis of tumor endothelial cells. Future clinical trials have to determine the therapeutic benefit of novel combination chemotherapy and alternative application schedules.
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  • 128
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    Reviews in endocrine & metabolic disorders 1 (2000), S. 225-231 
    ISSN: 1573-2606
    Keywords: thyroid neoplasms ; chemotherapy ; anaplastic carcinoma ; lymphoma ; therapeutics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
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  • 129
    ISSN: 1573-2614
    Keywords: Neuromuscular relaxants ; rocuronium ; kinetics ; distribution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Medicine
    Notes: Abstract Objective.To determine the relationship between the rate ofrocuronium injection and the onset time of neuromuscular block. Methods.After intravenous induction, 60 female patients (ASA I–II) wereassigned randomly into 3 groups for rocuronium administration within1–15, 15–30 or 30–60 seconds. Acceleromyography of the thumbwas performed using train-of-four (TOF) stimulation. Times to 50% and 90%twitch depression of the first twitch of the TOF stimulation (T1) wererecorded. Results.Injection time significantly influences time to 50%relaxation, but not time to 90% relaxation. Body mass index is negativelycorrelated with time to 50% and 90% relaxation. Conclusions.Weconclude that rate of injection influences only the initial phase ofdevelopment of the block and that slower injection times do not significantlyaffect time to 90% relaxation at the adductor pollicis muscle.
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  • 130
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    Journal of clinical monitoring and computing 16 (2000), S. 351-360 
    ISSN: 1573-2614
    Keywords: carbon dioxide ; oxygen ; kinetics ; non-steady state ; cardiac output ; PEEP ; pulmonary embolism ; pulmonary gas exchange monitoring
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Medicine
    Notes: Abstract Traditionally, the study of CO2 and O2 kinetics in the body has been mostly confined to equilibrium conditions. However, the peri-anesthesia period and the critical care arena often involve conditions of non-steady state. The detection and explanation of CO2 kinetics during non-steady state pathophysiology have required the development of new methodologies, including the CO2 expirogram, average alveolar expired PCO2, and CO2 volume exhaled per breath. Several clinically relevant examples of non-steady state CO2 kinetics perturbations are examined, including abrupt decrease in cardiac output, application of positive end-expiratory pressure during mechanical ventilation, and occurrence of pulmonary embolism. The lesser known area of non-steady state O2 kinetics is introduced, including the measurement of pulmonary O2 uptake per breath. Future directions include the study of the respiratory quotient per breath, where the anaerobic threshold during anesthesia is identified by increasing respiratory quotient.
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  • 131
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    Digestive diseases and sciences 45 (2000), S. 359-365 
    ISSN: 1573-2568
    Keywords: functional liver blood flow ; splanchnic hemodynamics ; intrahepatic shunts ; kinetics ; kinetic models
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Sorbitol and indocyanine green (ICG) have high hepatic extraction fractions (E sorb and E ICG) in normal subjects. A curved relationship has been observed between E sorb and E ICG in liver disease. According to one interpretation, the decrease of E sorb is a result of intrahepatic shunting and 1 − E sorb is the fraction of shunted flow (the shunt hypothesis). Under the further assumption that capillarization of functioning sinusoids prevents hepatic uptake of plasma protein-bound ICG and allows uptake of water-soluble sorbitol, the difference Esorb − EICG has been suggested as a measure of capillarization. We propose an alternative hypothesis: that the sinusoidal permeability–surface area products for sorbitol and ICG are reduced in proportion by liver disease (proportional reduction hypothesis). Based on the sinusoidal perfusion model, predictions were produced from both hypotheses for the relation between E sorb and E ICG and the additional effects of capillarization were described. By use of liver vein catheterization, E sorb and E ICG were simultaneously measured during continuous infusions in 53 human subjects with varying degrees of liver disease. The data were in better agreement with the predictions of the proportional reduction hypothesis than with the shunt hypothesis. Even though both intrahepatic portosystemic shunts and sinusoidal capillarization are known to occur in cirrhosis and also may have influenced our data, they appeared to be of minor importance from a kinetic point of view. These findings favor the proportional reduction hypothesis and do not support the use of systemic nonrenal clearance of sorbitol as a measure of “functional liver blood flow.”
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  • 132
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    Water resources management 14 (2000), S. 417-434 
    ISSN: 1573-1650
    Keywords: adsorption ; feldspar ; industrial effluent ; pollution control ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Geography
    Notes: Abstract Feldspar, among many natural substances such as termitemount-clay, saw-dust, kaolinite and dolomite, offers asignificant removal ability for sulfate, phosphate, and coloredsubstances. Optimization of experimental parameters such assolution pH and flow rate reveals, that the maximum efficiency forremoval of phosphate, sulfate, and colored substances is about42, 52, and 73% respectively. X-ray diffraction, adsorptionisotherm and recovery studies suggest, that the removal processof anions occurs via ion exchange in conjunction with surfaceadsorption. Furthermore, reaction rate studies indicate thatthe removal of the selected pollutants by feldspar follows first-order kinetics. Although the percent removal, under the optimized conditions, is higher for laboratory prepared solutions, efficiency is a little less for industrial effluentsdue to interferent effects.
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  • 133
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    Journal of thermal analysis and calorimetry 62 (2000), S. 353-363 
    ISSN: 1572-8943
    Keywords: controlled environment ; high-T c superconductors ; kinetics ; microgravimetric investigations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Many properties of oxide superconductors depend on the oxygen concentration and its distribution in the samples. The microgravimetric method is very useful to study of oxide superconductors, as it allows investigations in vacuum and controlled environments in classical applications: thermogravimetric analysis for the study of solid-state reactions, determinations of oxygen contents in redox reactions and the combined measurement of mass and additional parameters, e.g. evolved gas analysis etc. Single-phase samples of high-temperature superconductors were synthesized from stoichiometric mixtures of high-purity oxides and carbonates. Appropriate amounts of the precursor powders were homogenized manually or by a mechanical ball mill and subsequently calcined at temperatures in the 800 to 950°C range with intermediate grinding to ensure homogenous reaction. The lattice parameters of all preparations were controlled, in both initial and final experiments, by the X-ray powder method (CuKα radiation), using a Stadi P (Stoe) diffractometer with a position-sensitive detector. It is well known that temperature and mass can be measured with an accuracy higher by orders of magnitude than it is still possible for the thermoanalyst to determine the transformation temperatures or the mass changes due to overlapping partial reactions. Applications of Cahn microbalance to study of high-temperature superconductors are presented.
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  • 134
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    Journal of thermal analysis and calorimetry 62 (2000), S. 747-755 
    ISSN: 1572-8943
    Keywords: benzoic acid ; europium complex ; kinetics ; non-isothermal ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition of Eu2(BA)6(bipy)2 (BA=C2H5N– 2, benzoate; bipy=C10H8N2, 2,2'-bipyridine)and its kinetics were studied under the non-isothermal condition by TG-DTG, IR and SEM methods. The kinetic parameters were obtained from analysis of the TG-DTG curves by the Achar method, the Madhusudanan-Krishnan-Ninan (MKN) method, the Ozawa method and the Kissinger method. The most probable mechanism function was suggested by comparing the kinetic parameters. The kinetic equation for the first stage can be expressed as: dα/dt=Aexp(–E/RT)3(1–α)2/3.
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  • 135
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    Journal of thermal analysis and calorimetry 63 (2000), S. 397-413 
    ISSN: 1572-8943
    Keywords: Cu–5 at%Zn ; DSC ; F.C.C. (Face Centered Cubic) ; kinetics ; short-range-order ; solute-vacancy complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A modified first order kinetic law, which describes the roles of bound and unbound vacancies, is proposed in order to predict defect decay and short-range-order kinetics of quenched binary alloys during linear heating experiments. The model has been applied to differential scanning calorimetry (DSC) curves of Cu–5 at%Zn quenched from different temperatures. Activation energy for migration of solute-vacancy complexes was also assessed from the kinetics of short-range-order using DSC traces. A value of 89.5±0.32 kJ mol–1 was obtained. The relative contribution of bound and unbound vacancies to the ordering process as influenced by quenching temperature was determined. In conjunction, a parametric study of the initial total defect concentration and effective energy for defect migration was performed in order to envisage their influence on the calculated DSC profiles.
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  • 136
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    Journal of thermal analysis and calorimetry 60 (2000), S. 25-33 
    ISSN: 1572-8943
    Keywords: DSC ; kinetics ; thermal decomposition ; 2,4,6-trinitrotoluene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An autocatalytic model involving the limited solubility of volatile catalytic products was applied to the thermal decomposition of 2,4,6-trinitrotoluene. The critical supersaturation of the thermal decomposition products with the catalytic properties was higher at a low heating rate. Decrease of the sample mass led to an increased critical supersaturation of the decomposition products. This is probably a result of the greater contribution of products adsorption on the aluminium pan surface. It is presumed that the differences observed in the rate constant are connected with the uncontrolled critical supersaturation of the volatile thermal decomposition products.
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  • 137
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    Structural chemistry 11 (2000), S. 341-346 
    ISSN: 1572-9001
    Keywords: Positronium chemistry ; kinetics ; spin-exchange reactions ; high- and low-spin 3d complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Continuing in our work on the correlations between the rate constants, k CR, of the ortho into para-positronium conversion reactions, CR, promoted by complexes of various 3d ions and the metal electron delocalization β caused by the ligands, the relationship between the parameters of the correlation lines pertinent to highand low-spin complexes of CrII, MnII, and CoII ions was ascertained. Moreover, it was experimentally verified, for the first time, that the statistical probability of the CR promoted by paramagnetic compounds with S = 1/2 is three times larger than that of the CR caused by compounds with S 〉 1/2.
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  • 138
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    Investigational new drugs 18 (2000), S. 157-186 
    ISSN: 1573-0646
    Keywords: Advances ; chemotherapy ; non-small lung cancer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
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  • 139
    ISSN: 1573-0646
    Keywords: Malignant melanoma ; prostate cancer ; chemotherapy ; clinical trial
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Introduction: CI-980 is a novel chemotherapeutic agent thatinhibits polymerization of tubulin. Preclinical studies haveindicated a high level activity of this agent against various tumorcell lines. Methods: 13 malignant melanoma patients who hadfailed prior chemotherapy and/or immunotherapy and 13 hormonerefractory prostate cancer patients, including 4 who had receivedprior chemotherapy, were treated in 2 separate NCI-supportedclinical trials. Subjects received a recommended phase II dose ofCI-980 of 4.5 mg/m2/day by continuous infusion for 72 hoursevery 3 weeks. Results: No activity was seen in either study.Toxicity was tolerable with neutropenia being the most common,significant toxicity. Among the melanoma patients, 15% and 31%developed grade 3 and grade 4 neutropenia, while 7% and 38% ofthe prostate patients developed grade 3 and grade 4 neutropenia,respectively. Conclusions: CI-980 at this dose and scheduleis ineffective against malignant melanoma and hormone refractoryprostate cancer.
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  • 140
    ISSN: 1573-0646
    Keywords: 9-aminocamptothecin ; chemotherapy ; phase II trial ; squamous cell carcinoma ; head and neck cancer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Fourteen patients with squamous cell carcinoma of the head and neck received 9-AC/DMA infusions of 850 mg/M2/day over 72 hours. Eligibility criteria included good performance status, advanced disease incurable by conventional means, no prior treatment of metastatic disease, and measurable lesions for objective response assessment. The infusions wererepeated at 21 day intervals until progression or prohibitive toxicity occurred.A median of 3 cycles (range 1–7) was given. No objective responses wereobserved. Median survival of the group was 6 months. Toxicity was hematologicwhich was modest and promptly reversible. 9-AC/DMA is inactive against this tumortype at the dose and schedule employed in this study.
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  • 141
    ISSN: 1573-0646
    Keywords: transitional cell carcinoma ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Purpose: A phase II trial of pyrazoloacridine(PZA) was conducted to assess its activity andtoxicity in patients with advanced transitional cellcarcinoma (TCC) refractory to or progressing after oneprior cisplatin-, carboplatin- or paclitaxel- basedregimen. Patients and methods: PZA at a dose of750 mg/m2 was administered to 14 patients as athree-hour intravenous infusion on day 1 every 21days. Premedication consisted of lorazepam 0.5-1.0 mgprior to each cycle to alleviate central nervoussystem toxicity. Reduction of subsequent doses wasmade for hematologic or central nervous systemtoxicity. Results: Among fourteen patients evaluable forresponse, no responses were observed (0% responserate; 95% confidence interval 0% to 23%). Themedian duration of survival for all patients was 9months with a median follow-up of 8.5 months. Toxicityto PZA included grade 3 or 4 neutropenia in 8/14(57%) and grade 3 or 4 thrombocytopenia in 2/14(14%). Non-hematologic toxicity was mild. Conclusions: PZA at this dose and schedule does nothave significant single-agent acitvity in patientswith TCC who have failed one prior regimen.
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    Hyperfine interactions 128 (2000), S. 481-493 
    ISSN: 1572-9540
    Keywords: muon catalyzed fusion ; triple mixture ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract In this paper, we solve numerically kinetic equations for the chain reactions of μCF in triple H/D/T mixture. Regarding the computational results, we show that μCF efficiency decreases by adding hydrogen H to D/T mixture. This is in contradiction to the usual belief which expects the increase of μCF efficiency in H/D/T mixture. Our results are confirmed by the first and recent experiment on μdt cycling rate in the triple mixture.
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    Reaction kinetics and catalysis letters 69 (2000), S. 169-176 
    ISSN: 1588-2837
    Keywords: Al3+-exchanged pillared clay catalyst ; 2-methoxyethanol ; esterification ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The pillared clay catalyst, which was obtained by exposing activated clay powder to sulfuric acid and aluminium salts and calcining in air at 373 – 673 K, was found to be highly active for the title reaction. The activity is mainly attributed to the Lewis acid sites and also to a small number of Brönsted acid sites, whose number and strength increases with the extent of pillaring. The kinetic equation of surface esterification is y = 2.57x - 1.47.
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  • 144
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    Reaction kinetics and catalysis letters 70 (2000), S. 119-124 
    ISSN: 1588-2837
    Keywords: Tenoxicam ; photodegradation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Photodegradation of tenoxicam was investigated under different reaction conditions. After 60 min of exposure to UV light, the photodegradation was extensive, and the maximum and minimum in the UV-visible spectrum were shifted to shorter and longer wavelengths, respectively. Ethanol exerted a photostabilizing effect on tenoxicam. Tenoxicam is more stable in acidic and basic media than in neutral solution. Increasing light intensity or temperature causes an increase in the rate of photodegradation. The photodegradation of tenoxicam was found to follow first-order kinetics under all these conditions.
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  • 145
    ISSN: 1588-2837
    Keywords: Ferrites ; aniline alkylation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Kinetic parameters such as the activation energy (Ea) and Arrhenius frequency factor (A) for the N-methylation of aniline using methanol over Zn-Co ferrites have been calculated. The Ea value is found to be lower than the existing best alkylating systems such as γ-alumina and magnesium oxide.
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  • 146
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    Reaction kinetics and catalysis letters 71 (2000), S. 343-347 
    ISSN: 1588-2837
    Keywords: Deoximination ; chromium (VI) ; kinetics ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Oxidative deoximination of aldoximes and ketoximes by pyridium fluorochromate proceeds by nucleophilic attack of the chromate oxygen on the oxime carbon to give a cyclic intermediate in the rate-determining step.
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  • 147
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    Reaction kinetics and catalysis letters 70 (2000), S. 147-151 
    ISSN: 1588-2837
    Keywords: Oxo-functionalization ; [RuIII(amp)(pic)(H2O)] ; t-BuOOH ; kinetics ; cyclohexane cyclohexene ; toluene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A novel mixed-ligand [RuIII(amp)(pic)(H2O)] complex (1) (H2amp = N-(hydroxyphenyl)salicyldimine; pic = picolinate) has been synthesized and characterized by physico-chemical methods. Complex 1has been found to be an effective catalyst in oxo-functionalization of C-H bond of organic substrates by using tert-butyl hydroperoxide (t-BuOOH) as a terminal oxidant. Formation of a high valent Ru(V)-oxo species as catalytic intermediate is proposed to be the source of oxygen atom in the oxidised product.
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  • 148
    ISSN: 1588-2837
    Keywords: Fe(CN)5(4-tbupy)3- ; kinetics ; electrolytes ; substitution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The ligand substitution reaction [Fe(CN)5(4-tbupy)]3- + pyrazine (4-tbupy=4-tertbutylpyridine) was studied in aqueous concentrated electrolyte solutions at 298 K. Plots of ln(k/kw) against (γ-γw), where the subscript w refers to pure water and γ is the surface tension of the appropriate salt solution, gave a common straight line for all the electrolytes studied and permits to estimate the activation volume.
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  • 149
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    Reaction kinetics and catalysis letters 69 (2000), S. 39-46 
    ISSN: 1588-2837
    Keywords: Coke formation ; kinetics ; USHY zeolites ; ethene ; propene ; 1-butene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A simplified three-parameter model for the interpretation of the kinetic data of coke formation during transformation of light olefins is presented. This model has been applied to the transformation of ethene, propene and 1-butene over fresh and regenerated zeolite USHY at 623 K. The proposed model covers both the coverage of the acid sites and the autocatalytic growth of coke.
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  • 150
    ISSN: 1588-2837
    Keywords: Dichlorocyclopropanation ; 4-vinyl-1-cyclohexene ; phase transfer catalysis ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of regioselective dichlorocyclopropanation of 4-vinyl-1-cyclohexene has been studied under controlled phase transfer catalysis conditions, using aqueous sodium hydroxide as the base and 2-benzylidine-N,N,N,N′,N′,N′-hexaethylpropane-1,3-diammonium dibromide (Dq-Br) as a new phase transfer reagent. The reaction was carried out at 40 °C under pseudo-first order conditions by employing aqueous sodium hydroxide and chloroform in excess and was monitored by gas chromatography. The effect of various experimental parameters on the rate of the reaction has been studied and based on the experimental results, a suitable mechanism is proposed.
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  • 151
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    Reaction kinetics and catalysis letters 69 (2000), S. 247-252 
    ISSN: 1588-2837
    Keywords: Phosphorous acid ; oxidation ; kinetics ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of lower phosphorus oxyacids by benzyltrimethylammonium chlorobromate (BTMACB) proceeds by a mechanism involving a hydride-ion transfer from oxyacids to the oxidant in the rate-determining step.
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  • 152
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    Reaction kinetics and catalysis letters 70 (2000), S. 139-145 
    ISSN: 1588-2837
    Keywords: Oxidation of sulfides ; kinetics ; Ni-oxide system ; reaction mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Catalytic oxidation of sulfide ions in aqueous solutions by air oxygen has been investigated using a Ni-oxide system as a catalyst. The kinetics and the selectivity of the oxidation process were studied by varying the pH, catalyst amount and reaction temperature. A reduction/oxidation mechanism of the reaction has been supposed comprising interaction between the surface active oxygen of the catalyst and HS− and reoxidizing of the reduced catalyst by the dissolved oxygen. The results obtained show that the Ni-oxide system is a promising catalyst for practical application.
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  • 153
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    Reaction kinetics and catalysis letters 70 (2000), S. 235-241 
    ISSN: 1588-2837
    Keywords: Methanol ; isobutanol ; ethers ; γ-Al2O3 ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetic of methanol (MeOH) and isobutanol (iBuOH) coupling to ethers has been studied. Catalytic tests were carried out in the gas phase in a fixed-bed flow microreactor, in the temperature range of 463-533 K, under atmospheric pressure, using γ-Al2O3 as the catalyst. The quasi-homogeneous model for the process was assumed. The reaction rates were described by simple kinetics.
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  • 154
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    Reaction kinetics and catalysis letters 70 (2000), S. 319-324 
    ISSN: 1588-2837
    Keywords: Atmospheric chemistry ; kinetics ; OH-radical ; CH2F2
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The rate constant value of k 1 = (6.05 ± 0.20)×109 cm3 mol−1 s−1 (with ± 1σ error) has been determined for the reaction OH + CH2F2 (1) by applying the discharge-flow/resonance-fluorescence method at 298 K.
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  • 155
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    Reaction kinetics and catalysis letters 71 (2000), S. 47-54 
    ISSN: 1588-2837
    Keywords: Alkylbenzenes ; hydrogenation ; nickel ; kinetics ; stereochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Experimental data on gas-phase hydrogenation of several alkylbenzenes (toluene, ethlylbenzene, o-, m-, p-xylenes, mesitylene) over nickel catalyst are summarized. Rate dependence as a function of the chemical nature of substituent and position in the aromatic ring is discussed. The stereochemical distribution for dialkylbenzene and trialkylbenzene is addressed.
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  • 156
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    Reaction kinetics and catalysis letters 71 (2000), S. 295-300 
    ISSN: 1588-2837
    Keywords: Sintering ; kinetics ; Pt/Al2O3
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The variation of dispersion of Pt on Al2O3 support with sintering time is measured and the value of equilibrium dispersion of Pt is obtained directly. It is found that a General Power Law Expression can fit the experimental data well.
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  • 157
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    World journal of microbiology and biotechnology 16 (2000), S. 601-605 
    ISSN: 1573-0972
    Keywords: Growth phases identification ; kinetics ; Rhizopus oryzae ; solid-state fermentation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract A general equation correlating the variation rate of the fermenting medium weight (dry matter) and the cell biomass growth rate in solid-state fermentation tests is proposed with the main purpose of identifying the microbial growth phases.
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  • 158
    ISSN: 1573-2746
    Keywords: 8-hydroxyquinaldine ; electropolymerization ; adsorption ; glassy carbon ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The kinetics and thermodynamics of the electropolymerization of the chelating agent 8-hydroxyquinaldine on GCE's (Glassy Carbon Electrodes') surface from aqueous phosphate buffers are reported. Thermodynamic functions related to the adsorption of the monomer on the GCE's surfaces were determinated. No contribution from GCE surface's functional group to the electropolymerization reactions was reported. The effects of monomer concentration, pH, and temperature on the electrochemical growth of poly 8-hydroxyquinaldine were investigated. The results suggest that the propagation of the electropolymerization process takes place via a free radical chain reactions. Furthermore, the results indicate that the electrochemical growth of the polymeric films is dictated by pre-polymerization adsorption on the electrode surface.
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  • 159
    ISSN: 0935-6304
    Keywords: Capillary HPLC ; gradient elution ; temperature programming ; phenolic compounds ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---This paper describes a liquid chromatographic method using a reversed phase capillary column coupled to an UV detector for the quantitation of thirteen pollutant phenols. Chromatographic separation was carried out with gradient elution at 25.0 ± 0.1°C. The two major anisocratic elution modes (gradient elution and temperature programming) were evaluated. The detection limit range was 10-81 pg (100 nL injected). The chromatographic method combined with liquid-liquid extraction was applied to analysis of these compounds in river water. Recoveries of 75-103% were achieved for most of them.
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  • 160
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    Journal of High Resolution Chromatography 23 (2000), S. 389-392 
    ISSN: 0935-6304
    Keywords: Capillary SFC ; zinc dialkyldithiophosphates ; lubricating oils ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
    Additional Material: 5 Ill.
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  • 161
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    Journal of High Resolution Chromatography 23 (2000), S. 393-396 
    ISSN: 0935-6304
    Keywords: Supercritical fluid chromatography (SFC) ; micropacked capillary columns ; waxes ; restoring ; objects of art ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
    Additional Material: 2 Ill.
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  • 162
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    Journal of High Resolution Chromatography 23 (2000), S. 379-385 
    ISSN: 0935-6304
    Keywords: Aroma ; “lulo del Chocó” ; Solanum topiro ; volatiles ; glycosidically bound volatiles ; glycoside TFA derivatives ; enantioselective gas chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The volatile constituents of lulo del Chocó (Solanum topiro) fruit pulp obtained by liquid-liquid extraction were analyzed by capillary GC and capillary GC-MS. In total, 30 components were identified with methyl salicylate, hexadecanoic acid, hexanal, guaiacol, ethyl butanoate, and ethyl acetate being the major components. Chirospecific MDGC analysis revealed the predominance of (R)-ethyl-3-hydroxybutanoate (ee 40%) and the presence of racemic mixtures both of δ-octalactone and of δ-decalactone. For γ-hexalactone, γ-octalactone, and γ-decalactone enantiomeric distributions of 22.4 : 77.6, 22.9 : 77.1, and 20.0 : 80.0, (R) : (S), respectively, were determined. Glycosidically bound aroma compounds were identified by capillary GC and capillary GC-MS after isolation of the glycosidic fraction obtained by Amberlite XAD-2 adsorption and methanol elution followed by hydrolysis with a commercial pectinase enzyme. In total 13 bound aroma compounds (aglycones) were identified. These aglycones mainly consisted of compounds exhibiting aromatic structures. Additionally, with the aid of capillary GC and capillary GC-MS (EI and NCI) of trifluoroacetylated derivatives we identified eight glucosides: the novel 3,6-epoxy-7-megastigmen-5,9-diol β-D-glucopyranoside and the hexyl, benzyl, linalyl oxide (furanic), 2-phenylethyl, vomifolyl (isomer 1), (6S,9R)-vomifolyl, and scopoletin β-D-glucopyranosides.
    Additional Material: 1 Ill.
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  • 163
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    Journal of High Resolution Chromatography 23 (2000), S. 409-412 
    ISSN: 0935-6304
    Keywords: Cyclodextrin ; capillary electrophoresis ; system peak ; CHES 1 ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a running buffer containing cyclodextrins (CDs) and 2-[N-cyclohexylamino]-ethanesulfonic acid (CHES), positive system peaks were observed in the analysis of a ganglioside mixture by CE-UV. These system peaks were related to CDs in the running buffer because these peaks were also detected when a plug of solution devoid of CDs but having the same CHES concentration and pH as the running buffer was injected. Neutral CDs were separated owing to the formation of inclusion complexes with the anionic CHES ion. One possible explanation for the positive system peaks is that the anionic CD-CHES inclusion complex is displaced by co-ions with higher UV absorptivity.
    Additional Material: 3 Ill.
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  • 164
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    Journal of High Resolution Chromatography 23 (2000), S. 565-566 
    ISSN: 0935-6304
    Keywords: Liquid chromatography ; zinc dithiocarbamate ; vulcanization accelerator ; rubber gloves ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
    Additional Material: 2 Ill.
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  • 165
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    Journal of High Resolution Chromatography 23 (2000), S. 603-608 
    ISSN: 0935-6304
    Keywords: Solvation parameter model ; ystem constants for poly(dimethyldiphenylsiloxane) HP-5 and poly(ethylene glycol) HP-INNOWax stationary phases ; temperature ; molecular interaction ; retention models ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
    Additional Material: 1 Ill.
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  • 166
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    Journal of High Resolution Chromatography 23 (2000), S. 561-564 
    ISSN: 0935-6304
    Keywords: Retention factors ; Cinnamomi ramulus ; high-performance liquid chromatography ; capillary electrophoresis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
    Additional Material: 3 Ill.
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  • 167
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    Journal of High Resolution Chromatography 23 (2000), S. 590-594 
    ISSN: 0935-6304
    Keywords: Ion chromatography ; graphitic carbon stationary phases ; anions ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Inorganic anions could be separated on porous graphitic carbon stationary phases in ion chromatography. Ion exchange between eluent anions and sample anions on the stationary phase was confirmed by the retention behavior and the possibility of indirect photometric detection. The elution order of anions was different from that observed for commercially available anion exchangers. Chloride, nitrate, and sulfate contained in tap water could be determined in 7 min.
    Additional Material: 6 Ill.
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  • 168
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    Journal of High Resolution Chromatography 23 (2000), S. 485-488 
    ISSN: 0935-6304
    Keywords: Pyrethroids ; solid-phase microextraction ; water analysis ; temperature ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Synthetic pyrethroids are increasingly being used for insect control on field crops because of their advantageous environmental properties such as short field life, broad spectrum of insecticide activity, and relatively low mammalian toxicity. In the present work, experimental conditions were optimized for trace analysis of pyrethroids in water by using solid-phase microextraction followed by capillary gas chromatography. Effects of temperature, SPME-fiber diameter, and matrix were studied. SPME used off-line with a gas chromatograph electron-capture detection (GC-ECD) showed a linear response over a wide concentration range. Our results showed a strong temperature effect on pyrethroid extraction yield. The detection limit after 5 min of SPME-fiber exposure to the samples changed from 1 ppb (at 30°C) to 0.1 ppt (at 90°C), which is a 10000 increase in pyrethroid detection. The standard deviations of the analyte peak area ratios were typically in the range of 1-7% at 30°C and of 3 to 15% at 90°C. Best conditions for pyrethroids analysis were achieved using high temperature solution and a 100 μm polydimethylsiloxane fiber. No matrix (river water) influence was observed on detection of the investigated pyrethroids.
    Additional Material: 6 Ill.
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  • 169
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    Journal of High Resolution Chromatography 23 (2000), S. 19-26 
    ISSN: 0935-6304
    Keywords: Microfabrication ; monolith ; electrochromatography ; peptides ; reactive ion etching ; reversed phase ; nanocolumns ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monolith columns are generally fabricated by polymerization of monomers within a column. This paper reviews an alternative strategy in which the bed is microfabricated in an inorganic material by ablation. Channels of 1.5 μm width and 10 μm depth were sculpted in quartz by deep reaction ion etching. Using this approach chromatographic beds were constructed in which cubic support structures were created and arranged in rows to mimic particles in a conventional column. Beds ranging from hundreds of thousands to millions of “particles” with volumes of 15 nL to 15 μL were produced. Columns that had been derivatized with an octadecyl silane stationary phase were used to separate both low molecular weight analytes and peptides in the CEC mode. Plate height in the CEC mode was 1.2 μm at maximum efficiency.
    Additional Material: 9 Ill.
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  • 170
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    Journal of High Resolution Chromatography 23 (2000), S. 39-43 
    ISSN: 0935-6304
    Keywords: Monoliths ; CIM® monolithic column ; dynamic binding capacity ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The characterization of CIM® DEAE monolithic columns in terms of dynamic binding capacity is presented in this paper. Breakthrough experiments were performed for capacity determination. Bovine serum albumin (BSA) was used as a model protein. It is shown that CIM® monolithic columns have good batch-to-batch reproducibility as well as long-term stability. The experiments performed under different linear velocities demonstrated that the dynamic capacity is unaffected at least up to a linear velocity of 2450 cm/h. Furthermore, the breakthrough curve slope is constant, indicating that the capacity would remain constant at even higher linear velocities. The adsorption isotherm of BSA dissolved in 20 mM Tris-HCl buffer shows a constant capacity of around 30 mg/mL of support down to a concentration of 20 μg/mL. The capacity is substantially influenced by the ionic strength; however, 20% of the maximal capacity is still preserved at 0.3 M NaCl.
    Additional Material: 5 Ill.
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  • 171
    ISSN: 0935-6304
    Keywords: Monolith ; factor VIII ; affinity chromatography ; combinatorial peptide library ; peptide synthesis ; recombinant proteins ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: FVIII is a very complex molecule of great therapeutic significance. It is purified by a sequence of chromatographic steps including immunoaffinity chromatography. A peptide affinity chromatography method has been developed using peptides derived from a combinatorial library. Spot technology using cellulose sheets has been applied for this purpose. The dual positional scanning strategy was used for identification of the amino acids in random positions. Approximately 5000 possible candidates found in the first screening round were reduced to a panel of 36. Six candidates have been selected empirically. Five peptides seem to be directed against the light chain of FVIII, one peptide seems to be directed against the heavy chain. The peptides have been immobilized on conventional beaded material and CIM polymethacrylate monoliths. Much better performance with respect to capacity and selectivity has been observed with the monolithic material. Exposure of the ligand and its ensuing accessibility are responsible for these properties.
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  • 172
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    Journal of High Resolution Chromatography 23 (2000), S. 67-72 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; monolithic column ; electroosmotic flow ; retention mechanism ; aromatic compound ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new kind of monolithic capillary electrochromatography column with poly(styrene-co-divinylbenzene-co-methacrylic acid) as the stationary phase has been developed. The stationary phase was found to be porous by scanning electron microscopy and the composition of the continuous bed was proved by IR spectroscopy to be the ternary polymer of styrene, divinylbenzene, and methacrylic acid. The effects of operating parameters, such as voltage, electrolyte, and organic modifier concentration in the mobile phase on electroosmotic flow were studied systematically. The retention mechanism of neutral solutes on such a column proved to be similar to that of reversed-phase high performance liquid chromatography. In addition, fast analyses of phenols, chlorobenzenes, anilines, isomeric compounds of phenylenediamine and alkylbenzenes within 4.5 min were achieved.
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  • 173
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    Journal of High Resolution Chromatography 23 (2000), S. 73-80 
    ISSN: 0935-6304
    Keywords: Continuous-bed ; sol-gel ; octadecylsilica ; mixed-mode stationary phase ; large-pore ; column technology ; capillary electrochromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Sol-gel bonded packing materials in continuous-bed columns have been prepared for capillary electrochromatography (CEC). Three packing materials were investigated: small-pore Spherisorb ODS1 (3 μm, 80 Å) with octadecyl as stationary phase, small-pore mixed-mode Spherisorb ODS/SCX (3 μm, 80 Å) with octadecyl and propyl sulfonic acid as stationary phases, and large-pore Nucleosil ODS (7 μm, 1 400 Å) with octadecyl as stationary phase. The characteristics of these columns were compared in terms of electroosmotic flow, efficiency, inertness, and retention factors. In contrast to columns containing sol-gel bonded ODS, columns containing sol-gel bonded mixed-mode ODS/SCX generated nearly pH independent electroosmotic flow (EOF) over pH 2-9. Columns containing sol-gel bonded large-pore ODS produced nearly three times lower reduced plate height than those containing small-pore ODS. Efficiencies of 220,000 plates per meter and 175,000 plates per meter were obtained from columns containing sol-gel bonded 7 μm, 1 400 Å ODS and columns containing sol-gel bonded 3 μm, 80 Å ODS, respectively, which are among the highest reported efficiencies for continuous-bed columns. In CEC, over one million plates per meter and pH independent EOF are expected from continuous-bed columns containing sol-gel bonded 1.5 μm particles with large pores and mixed-mode stationary phases.
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  • 174
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    Journal of High Resolution Chromatography 23 (2000), S. 81-88 
    ISSN: 0935-6304
    Keywords: Monolithic chromatography columns ; capillary electrochromatography (CEC) ; micro high performance liquid chromatography ; sol-gel based columns for chromatography ; fritless capillary chromatography columns ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Particle-loaded (3 μm, octadecylsilica) monolithic sol-gel columns have been prepared and selected characteristics measured. Several electrical properties may be calculated from simple current measurements in the column as a whole. Resistivity in the packed segment is approximately three times that in open segments, resulting in a 60% increase in field strength in the packed regions compared to the capillary with no packing. The surprisingly high specific permeability of these sol-gel columns is characteristic of 8-μm particles, which allows their operation in the microLC mode at pressures as low as 69 kPa where their efficiency is about 50,000 plates per meter and in the CEC mode where efficiency is about 106,000 plates per meter at 5 kV. There is a relatively rapid loss of efficiency with increasing linear velocity beyond 0.2 mm/s in microLC mode, which may be due to additional diffusion processes in the inter-particulate voids. A rapid loss of efficiency above 0.5 mm/s is also observed in the CEC mode, for the same reasons. Chromatographic retention behavior in either separation mode is characteristic of conventional octadecylsilica particles, indicating that analytes have significant access to the surface within the pores of the immobilized bonded phase.
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  • 175
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    Journal of High Resolution Chromatography 23 (2000), S. 89-92 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; packed columns ; fritless columns ; stationary phases ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Fritless packed silica gel columns were prepared using sol-gel technology. A part of a 75 μm i.d. fused silica capillary was filled with a mixture of tetramethoxysilane and poly(ethylene glycol). After gelling at 40°C and heating at 300°C, the resultant silica gel was derivatized with dimethyloctadecylchlorosilane. A scanning electron micrograph of a cross-section of the capillary column showed that the gel took the form of a spherical particle aggregate and adhered to the column inner wall. The column performance was evaluated for electrochromatography using acetonitrile-50 mM HEPES buffer (pH 6.6) (60/40 or 40/60, v/v) as the mobile phase. An electroosmotic flow of 1.0 mm/s was generated with (60/40, v/v) acetonitrile/HEPES buffer at a field strength of 546 V/cm. Using a sol-gel-derived packed column at an electroosmotic flow of 0.5 mm/s, efficiencies of up to 1.1×105 plates/m were obtained for retained solutes.
    Additional Material: 4 Ill.
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  • 176
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    Journal of High Resolution Chromatography 23 (2000), S. 93-99 
    ISSN: 0935-6304
    Keywords: HPLC ; monolithic column ; silica rod column ; fast separations ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The application of a new silica-based, monolithic-type HPLC-column for fast separations is presented. The column is prepared according to a new sol-gel process, which is based on the hydrolysis and polycondensation of alkoxysilanes in the presence of water soluble polymers. The method leads to “rods” made of a single piece of porous silica with a defined pore structure, i. e. macro- and mesopores. The main feature of silica rod columns is a higher total porosity, about 15% higher than of conventional particulate HPLC columns. The resulting column pressure drop is therefore much lower, allowing operation at higher flow rates including flow gradients. Consequently, HPLC analysis can be performed much faster, as it is demonstrated by various applications.
    Additional Material: 9 Ill.
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  • 177
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    Journal of High Resolution Chromatography 23 (2000), S. 3-18 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; monolithic columns ; synthetic polymers ; stationary phase ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monolithic materials have quickly become a well-established stationary phase format in the field of capillary electrochromatography (CEC). Both the simplicity of their in situ preparation method and the large variety of readily available chemistries make the monolithic separation media an attractive alternative to capillary columns packed with particulate materials. This review summarizes the contributions of numerous groups working in this rapidly growing area, with a focus on monolithic capillary columns prepared from synthetic polymers. Various approaches employed for the preparation of the monoliths are detailed, and where available, the material properties of the resulting monolithic capillary columns are shown. Their chromatographic performance is demonstrated by numerous separations of different analyte mixtures in variety of modes. Although detailed studies of the effect of polymer properties on the analytical performance of monolithic capillaries remain scarce at this early stage of their development, this review also discusses some important relationships such as the effect of pore size on the separation performance in more detail.
    Additional Material: 16 Ill.
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  • 178
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    Journal of High Resolution Chromatography 23 (2000), S. 100-105 
    ISSN: 0935-6304
    Keywords: Preparative chromatography ; silica monoliths ; PrepROD™ ; productivity ; SMB-chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The use of monolithic silica sorbents for the isolation of substances by preparative liquid chromatography is demonstrated. Preparative liquid chromatography is recognized as a valuable technique for the isolation and purification of substances in the pharmaceutical and fine chemicals industry. The system technology has meanwhile reached a high standard, and the greatest future improvements are expected to arise from new and improved adsorbents. Monolithic silica sorbents offer some unique features for preparative liquid chromatography. They exhibit high efficiencies even at high flow rates due to their fast convective mass transfer and can therefore be used at very high mobile phase velocities, leading to high productivity and hence to maximum process economy. The benefits of this new type of adsorbent are illustrated for an example in batch-chromatographic mode and an example using the continuous simulated moving bed (SMB) technology.
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  • 179
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    Journal of High Resolution Chromatography 23 (2000), S. 106-110 
    ISSN: 0935-6304
    Keywords: Silica ; monolithic column ; aging ; mesopores ; pore size distribution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Mesopore formation in silica gels having continuous macropores has been investigated. The macroporous wet silica gel prepared by the sol-gel process including phase separation was aged in a basic solvent making use of hydrolysis of urea in a closed condition. The mesopore structure was finally obtained by subsequent evaporation drying of solvent and heat-treatment at 600°C for 2 h. The dissolution-reprecipitation kinetics at the interfaces between wet gel skeletons and an external solvent affected the size and volume of pores formed within the skeletons. Below 120°C, mesopores suitable for various chromatographic applications have been formed typically within 24 h. On the other hand, at 200°C, the pore size attained the macropore dimensions (〉50 nm), and the whole macroporous morphology was significantly modified.
    Additional Material: 7 Ill.
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  • 180
    ISSN: 0935-6304
    Keywords: Monolithic column ; silica monolith ; HPLC ; capillary liquid chromatography ; capillary electrochromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Two types of monolithic silica columns derivatized to form an ODS phase, one prepared in a fused silica capillary (SR-FS) and the other prepared in a mold and clad with an engineering plastic (poly-ether-ether-ketone) (SR-PEEK), were evaluated. The column efficiency and pressure drop were compared with those of a column packed with 5-μm ODS-silica particles and of an ODS-silica monolith prepared in a mold and wrapped with PTFE tubing (SR-PTFE). SR-FS gave a lower pressure drop than a column packed with 5-μm particles by a factor of 20, and a plate height of 20 μm at a linear velocity below 1 mm/s. SR-PEEK showed higher flow-resistance than the other monolithic silica columns, but they still showed a minimum plate height of 8-10 μm and a lower pressure drop than popular commercial columns packed with 5-μm particles. The evaluation of SR-FS columns in a CEC mode showed much higher efficiency than in a pressure-driven mode.
    Additional Material: 6 Ill.
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  • 181
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    Journal of High Resolution Chromatography 23 (2000), S. 119-126 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; retention volume ; real gas carrier ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The problem of the calculation and interpretation of the net retention volume with a real gas as carrier is revisited. The properties of the carrier are described by a first order virial equation of state. The net retention volume of a solute is related to the mean flow rate of the carrier, therefore determination of the mean flow rate of a real gas carrier is reviewed. It is shown that the mean flow rate cannot be calculated from the mean column pressure. With a real gas carrier the local capacity factor depends on the local pressure of the real gas. The basic relationship between the net retention volume and the function describing this pressure dependence is also reviewed. Precise formulae as well as practical approximations are presented for the calculation of the mean flow rate, of the mean column pressure, and of a representative pressure related to the mean capacity factor.
    Additional Material: 3 Tab.
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  • 182
    ISSN: 0935-6304
    Keywords: Chemiluminescence ; diol compound ; oxalate ; post-column reaction ; ruthenium complex ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---In this paper we propose a new post-column detection method for polyols containing 1,2-diol, 1,3-diol, and saccharides. The polyols are oxidized in a photochemical reactor to yield oxalate with subsequent chemiluminescence detection using [Ru(III)(bpy)3]3+. A mixing solution of eluate and oxidizing reagent is delivered to a reaction coil, which is then irradiated with ultraviolet light to promote the oxidation reaction. The detection limits for 1,2-ethanediol (ethylene glycol) and 1,3-propanediol were 38 pmol and 23 pmol, respectively.
    Additional Material: 5 Ill.
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  • 183
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    Journal of High Resolution Chromatography 23 (2000), S. 131-137 
    ISSN: 0935-6304
    Keywords: On-line coupled LC-GC ; nitrogen selective detection ; NPD ; carbazoles ; PANH ; personal exposure measurement ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A coupled LC-GC method for the analysis of carbazole-type PANH has been developed and evaluated. Group separation and isolation of carbazoles from interfering acridines in a complex sample matrix was accomplished by using a back-flush technique and an in situ end-capped dimethylaminopropyl silica column in the HPLC part of the system. On-line injection of the carbazole fraction into the GC column was performed with a loop-type interface utilizing concurrent solvent evaporation technique. An LOD of 1-3 pg of individual carbazole compounds was achieved by nitrogen selective detection using an NPD. The method is shown to be robust and is demonstrated by application to personal exposure measurement in an aluminum reduction plant.
    Additional Material: 4 Ill.
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  • 184
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    Journal of High Resolution Chromatography 23 (2000), S. 138-142 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; nucleosides ; short-end injection ; phenyl-bonded silica ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The influence of several experimental parameters (pH, ionic strength, organic modifier content of hydro-organic buffer) upon EOF, migration time, and retention factor has been studied in CEC with a phenyl-bonded silica column on a model mixture of five nucleosides. This paper illustrates the current interest in CEC as a method of resolving complex mixtures of neutral and ionic solutes and demonstrates the potential of the short-end injection method as a means of reducing analysis time.
    Additional Material: 4 Ill.
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  • 185
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    Journal of High Resolution Chromatography 23 (2000), S. 143-148 
    ISSN: 0935-6304
    Keywords: Analysis of anthraquinones ; capillary electrophoresis ; high-performance liquid chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The separation and determination of twelve anthraquinones, viz. anthraquinone 1, chrysphanol 2, aloe-emodin 3, alizarin 4, anthraquinone-2-carboxylic acid 5, purpurin 6, sennoside B 7, sennoside A 8, emodin 9, quinalizarin 10, rhein 11, and anthraflavic acid 12, were achieved by capillary electrophoresis (CE) and high-performance liquid chromatography (HPLC). Detection at 260 nm with a buffer solution containing 30 mM sodium borate (adjusted to pH = 10.56 with 0.05N NaOH) and acetonitrile (9 : 1) in CE or with a linear gradient elution containing 20 mM KH2PO4 with 0.05% phosphoric acid (pH = 2.91) and methanol in HPLC was found to be the most suitable approach for this separation. Contents of six components (2, 3, 7, 8, 9, 11) in crude Rhei Rhizoma extract could easily be determined within 39 min by CE or 63 min by HPLC. The effects of buffers on this separation and the validation of the two methods were studied.
    Additional Material: 5 Ill.
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  • 186
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    Journal of High Resolution Chromatography 23 (2000), S. 156-157 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; trichlorophenols ; ammonia ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
    Additional Material: 1 Tab.
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  • 187
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    Journal of High Resolution Chromatography 23 (2000), S. 149-155 
    ISSN: 0935-6304
    Keywords: Capillary GC ; fast GC ; on-column injection ; narrow-bore column ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---In this work a fast gas chromatography set-up with on-column injection was optimized and evaluated with a model mixture of C8-C28 n-alkanes. Usual injection volumes when using narrow-bore (e. g., 0.1 mm i.d.) analytical columns are ca. 0.1 μL. The presented configuration allows introduction of 10-30-fold larger sample volumes without any distortion of peak shapes. In the set-up a normal-bore retention gap (1 m×0.32 mm i. d.) was coupled to a narrow-bore (4.8 m×0.1 mm i. d.×0.4 μm film thickness) analytical column using a low dead volume column connector. The effects of the experimental conditions such as inlet pressure, sample volume, initial injection temperature, and oven temperature on a peak focusing are discussed. H-u curves for helium and hydrogen are used to compare their suitability for high speed gas chromatography and to show the dependence of separation efficiency on the carrier gas velocity at high inlet pressures. In the fast gas chromatography system a baseline separation of C10-C28 n-alkanes was achieved in less than 3 minutes.
    Additional Material: 4 Ill.
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  • 188
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    Journal of High Resolution Chromatography 23 (2000), S. 182-188 
    ISSN: 0935-6304
    Keywords: Comprehensive two-dimensional gas chromatography ; GC×GC ; thermal modulation ; oil analysis ; petroleum analysis ; analysis of middle-distillate oil fractions ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Comprehensive two-dimensional gas chromatography (GC×GC) is an utterly suitable separation technique for the analysis of complex samples, such as oil fractions. Once the two columns and the operating conditions are properly tuned, the technique is able to provide a detailed characterization of such materials. Some considerations applying to the tuning of a GC×GC system for a specific separation are presented and discussed. The authors present a number of different column sets and conditions which allow the separation of a non-aromatic hydrocarbon solvent, a kerosene, the light end of a crude oil, and an olefinic fraction, respectively. The highly structured GC×GC chromatograms, together with chemical knowledge about the samples, provide a much more comprehensive characterization of the samples than hitherto possible.
    Additional Material: 7 Ill.
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  • 189
    ISSN: 0935-6304
    Keywords: Comprehensive two-dimensional gas chromatography ; thermal desorption modulator ; temperature programming ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---In comprehensive two-dimensional gas chromatography, two individual separations are coupled by means of a rotating thermal desorption modulator interface. The injection pulse introduced via the interface onto the second column should be as short as possible. Parameters affecting the modulator operation are studied. In the set-up used in this study, the temperature of the second column can be programmed independently from that of the first column. Optimization of the second-dimension separation to minimize peak broadening and maximize resolution is discussed and an elegant approach to determine second-dimension retention times using a non-constant modulation frequency is demonstrated. The high separation power of the comprehensive system is demonstrated by the analysis of technical and biota samples containing chlorinated biphenyls and toxaphene.
    Additional Material: 7 Ill.
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  • 190
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    Journal of High Resolution Chromatography 23 (2000), S. 197-201 
    ISSN: 0935-6304
    Keywords: Multidimensional gas chromatography ; comprehensive two-dimensional gas chromatography ; GC×GC ; oxygenates ; MTBE ; reformulated gasoline ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Comprehensive two-dimensional gas chromatography (GC×GC) has been applied to the quantitation of oxygenates in reformulated gasoline. Target oxygenates were C1-C4 alcohols, tert-pentanol, methyl tert-butyl ether (MTBE), diisopropyl ether (DIPE), ethyl tert-butyl ether (ETBE), and tert-amyl methyl ether (TAME). These were separated from the gasoline matrix using a volatility-based selectivity in the first chromatographic dimension, followed by a mixed-phase polarity/shape selectivity in the second dimension. The high resolving power of this stationary phase combination completely separated all oxygenates except DIPE, ETBE, and TAME, which exhibited coelution with other nonpolar gasoline components. Oxygenates quantitation was achieved with the use of an internal standard, an FID detector, and calibration curves. Quantitation results are in good agreement with ASTM and EPA standard methods. When coupled with our previous method for BTEX and aromatics, a single GC×GC method can now quantitate MTBE, alcohols, BTEX, and aromatics in a one-hour analysis.
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  • 191
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    Journal of High Resolution Chromatography 23 (2000), S. 474-478 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Solid-phase extraction, on-line derivatization, and measurement by ion trap mass spectrometry (ITD-MS) were used to investigate the biological degradation of pharmaceutical residues (clofibric acid, ibuprofen, diclofenac). The results of the single steps of sample pretreatment and analytical determination are reported. MS/MS measurements were performed on an ITD-MS by selecting collision induced dissociation of the molecular ions (M+) as parent ions to defined daughter ions. A pilot sewage plant and biofilm reactors operating under oxic and anoxic conditions were run as model systems with synthetic sewage water containing 10 to 50 mg/L dissolved organic carbon (DOC) and pharmaceuticals in concentrations of 10 μg/L. Clofibric acid displayed its persistent character in all cases. The pilot sewage plant and the oxic biofilm reactor showed comparable results for diclofenac and ibuprofen, which both were partly degraded. These results can explain the occurrence of these substances in sewage effluents and in the aquatic environment. A high degree of degradation was found especially for ibuprofen in the oxic biofilm reactor, which was attributed to adaptation of the biofilm to the residue. Two metabolites of ibuprofen could be identified on the basis of their mass spectra and comparison with literature data, viz. hydroxyibuprofen and carboxyibuprofen.
    Additional Material: 8 Ill.
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  • 192
    ISSN: 0935-6304
    Keywords: Silicone oil ; supercritical fluid chromatography (SFC) ; micropacked columns ; MALDI-TOF ; GC/MS ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
    Additional Material: 4 Ill.
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  • 193
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    Journal of High Resolution Chromatography 23 (2000), S. 511-514 
    ISSN: 0935-6304
    Keywords: CZE ; indirect UV detection ; metal ions ; ecological samples ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
    Additional Material: 5 Ill.
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  • 194
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    Journal of High Resolution Chromatography 23 (2000), S. 297-303 
    ISSN: 0935-6304
    Keywords: Sample preparation ; gas extraction techniques ; membrane-type techniques ; water analysis ; soil analysis ; gas chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---This review focuses on the role of so-called solventless methods of sample preparation in contemporary environmental analysis. The basic classification of this group of methods as well as the principal features and advantages of the techniques in current use are discussed.
    Additional Material: 2 Ill.
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  • 195
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    Journal of High Resolution Chromatography 23 (2000), S. 253-258 
    ISSN: 0935-6304
    Keywords: Comprehensive gas chromatography ; cryogenic modulation ; semi-volatile aromatics ; thermal sweeper ; peak widths ; peak asymmetries ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The two current technologies for achieving comprehensive gas chromatography (GC×GC) - the thermal sweeper and the cryogenic modulator - are compared in an interlaboratory study using a multicomponent semi-volatile aromatic compound sample. The same column set (phases, film thickness, dimensions of columns) and conditions of oven temperature program were used. Carrier gas flow settings however were different for the data reported here. The thermal sweeper has a longer overall length due to the extra ca. 30 cm length of narrow bore tubing used for the modulator/accumulator section. Data reveal that the two methods behave in an analogous manner in respect of delivering GC×GC results, with key peak parameters of peak widths and symmetry measures showing good correlation. Retention time dissimilarity on the first dimension columns in the two systems arises from different flow rates used, however the second column retention is similar, and this is due to the resulting different elution temperatures that peaks elute on the first dimension in each system. Overall, the two approaches to GC×GC appear to produce equivalent results within the scope of the application studied. Each system does have its experimental limitations; the thermal sweeper has what may be called a ‘thick film effect’, where at high temperature it can be difficult to sufficiently trap the migrating bands in the accumulator column, and the pulsing of solutes in the cryogenic system may suffer from a ‘thick wall effect’ if a column with too thick a wall dimension is used at low oven temperature.
    Additional Material: 4 Ill.
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  • 196
    ISSN: 0935-6304
    Keywords: Proteomics ; protein analysis ; multidimensional HPLC ; ion-exchange chromatography ; reversed phase chromatography ; comprehensive HPLC ; two-dimensional HPLC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The interactive modes of High Performance Liquid Chromatography (HPLC) of proteins provide a platform for the construction of a multidimensional HPLC system coupled to mass spectrometry. We present a system composed of both anion and cation exchanger columns, in the first dimension, and n-octadecyl bonded 1.5 μm nonporous silica columns in the second dimension. Both columns are operated under gradient conditions. A system suitability test with standard proteins showed that the total analysis can be performed within about 20 minutes. The fractions taken from the ion exchanger column are directly analyzed within one minute on the reversed phase column at a high flow rate. Two reversed phase columns are applied and operated alternatively: while the first column performs the separation within one minute, the analytes leaving the first dimension are enriched in an on-column focusing mode on top of the second column. The sample clean-up and enrichment is performed on a novel type of restricted access cation exchanger column with internal sulfonic acid groups and external diol groups. The columns exhibit a molecular weight exclusion limit for globular proteins of about 15 kDa. Our next studies will be directed towards the analysis of proteins and peptides from extracts of fibroblasts.
    Additional Material: 4 Ill.
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  • 197
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    Journal of High Resolution Chromatography 23 (2000), S. 343-347 
    ISSN: 0935-6304
    Keywords: SPME ; desorption ; fiber conditioning ; field sampling ; sample preparation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
    Additional Material: 3 Ill.
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  • 198
    ISSN: 0935-6304
    Keywords: Silver ion high-performance liquid chromatography (Ag-HPLC) ; conjugated linoleic acid (CLA) ; p-methoxyphenacyl derivatives ; single-column Ag-HPLC ; fatty acid analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
    Additional Material: 5 Ill.
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  • 199
    ISSN: 0935-6304
    Keywords: Artemisia palustris ; Asterothamnus centrali-asiaticus ; capillary gas liquid chromatography ; Compositae (Asteraceae) ; Heteropappus hispidus ; seed oil ; silver ion thin layer chromatography ; trans-fatty acids ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Seed oils from the Compositae plant family are known to contain a variety of unusual fatty acids. Subsequent to the recent discovery of γ-linolenic acid in Saussurea and Youngia, further Mongolian Compositae species were investigated for their seed oil fatty acid composition. A number of δ3trans-fatty acids (16 : 1δ3t, 18 : 1δ3t and 18 : 3δ3t, 9c, 12c) were found in the seed oils of Heteropappus hispidus and Asterothamnus centrali-asiaticus. The latter fatty acid, but not the trans-monoenes, was also found in one species of Artemisia. These unusual fatty acid isomers were characterized by capillary gas-liquid chromatographic (GLC) separations in combination with other chromatographic techniques (analytical thin layer chromatography, TLC and preparative argentation TLC), and infrared spectrocsopy (IR). Their identity was further confirmed by co-chromatography with other seed oils known to contain these trans-fatty acids. The fact that within the Compositae plant family there are apparently two or three distinct groups of genera containing δ3trans-fatty acids is discussed.
    Additional Material: 5 Ill.
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  • 200
    ISSN: 0935-6304
    Keywords: 2H/1H ratio analysis ; HRGC-P-IRMS ; stable isotopes ; benzaldehyde ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Isotope ratio monitoring gas chromatography-mass spectrometry of the 2H/1H ratio by pyrolysis isotope ratio mass spectrometry (P-IRMS) was used to analyze benzaldehyde originating from various sources. Based on the δ2HSMOW value of an authentic reference sample determined with an elemental analyzer (EA), the range of reproducibility and linearity was checked. Correct (EA related) and reproducible data were obtained for sample amounts 〉0.6 μg benzaldehyde (on column). In another series of experiments, the influence of sample preparation, i. e. simultaneous distillation-extraction (SDE) was found to be negligible. The following ranges of δ2HSMOW values were determined for benzaldehyde using five types of samples, i. e. (i) synthetic (δ2HSMOW -78 to -85‰, ex benzal chloride; +420 to +668‰, ex toluene) and ‘natural’ (including ‘ex-cassia’) references (δ2HSMOW -83 to -144‰); (ii) bitter almond oils (δ2HSMOW -113 to -148‰); (iii) fruits (δ2HSMOW -111 to -146‰); (iv) kernels (δ2HSMOW -115 to -188‰); and (v) leaves (δ2HSMOW -165 to -189‰).
    Additional Material: 1 Ill.
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