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  • Articles: DFG German National Licenses  (104,339)
  • 1990-1994  (52,298)
  • 1970-1974  (27,169)
  • 1945-1949  (3,661)
  • 1915-1919  (4,147)
  • 1890-1899  (12,616)
  • 1860-1869  (4,448)
  • Chemistry  (104,195)
  • Analyse von Insecticiden, phosphorhaltig in Gewebe, tierisches
  • Best. von Verunreinigungen in Yttriumoxid
  • apoptosis
  • chemotherapy
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  • Articles: DFG German National Licenses  (104,339)
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Year
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  • 1
    ISSN: 1436-2813
    Keywords: portal vein ; liver micrometastasis ; chemotherapy ; 5-fluorouracil
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract To clarify the significance of prophylactic portal vein chemotherapy for hepatic metastases, the correlation between the timing of the portal infusion and the growth of liver micrometastases was examined in a rat model. Male Donryu rats weighing 160-180g were first inoculated intraportally with 5 X 106 ascites hepatoma AH60C cells, following which an intraportal infusion of 5-fluorouracil (5-FU) 20 mg/kg/day with heparin 100 U/kg/day was given over 5 days, commencing on day 0, 3, and 6, in groups A, B, and C, respectively. Compared with a control group of rats which received no treatment, a significant inhibition of tumor growth and prolongation of survival time were observed in groups A (P 〈 0.01) and B (P 〈 0.05); however, group C, in which the mean diameter of the micrometastases was 0.52 ±0.10 mm at the commencement of the portal infusion, showed no therapeutic response. These results suggest that prophylactic portal vein chemotherapy should be given to prevent the lodgement of tumor cells in the portal system and inhibit their initial proliferation, rather than to destroy established micrometastases.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1436-0691
    Keywords: hepatocellular carcinoma ; partial hepatectomy ; recurrence ; prevention ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract A major problem in treating hepatocellular carcinoma (HCC) is intrahepatic recurrence after partial hepatectomy, despite the relatively early detection now possible due to recent developments in non-invasive diagnostic modalities. The present study evaluated the usefulness of preventive therapy for intrahepatic recurrence of HCC. In order to suppress intrahepatic recurrence in HCC patients at high risk of recurrence after tumor removal, we performed preventive transarterial chemotherapy in 23 such patients. Doxorubicin, at a dose of 0.5 mg/kg body weight, was administered, via a catheter inserted at the junction of the common hepatic artery and the gastroduodenal artery, every 2 weeks for the first 2 months, and every month thereafter for at least 1 year. The control group consisted of 30 patients with similar risk of recurrence who underwent partial hepatectomy during the same period without receiving transarterial preventive therapy. The 1-, 2-, 3-, and 5-year cumulative cancer-free survival rates in patients who received transarterial preventive chemotherapy after partial hepatectomy were 87.0%, 47.1%, 21.2%, and 21.2%, respectively, compared to 53.3%, 30.0%, 20.0%, and 13.3%, respectively, in the control group (P〈0.05). The 1-, 2-, 3-, and 5-year cumulative overall survival rates were 95.7%, 81.2%, 58.4%, and 48.7%, respectively, in the preventive chemotherapy group, compared to 70.0%, 49.4%, 41.7%, and 19.5%, respectively, in the control group (P〈0.05). Thus, the present study demonstrates the limited but significant effect of preventive transarterial chemotherapy for the intrahepatic recurrence of HCC after partial hepatectomy.
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  • 3
    ISSN: 1436-2813
    Keywords: activated charcoal ; cisplatin ; drug delivery system ; esophageal cancer ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract In this study, 1500AA, an activated charcoal with a strong affinity for the lymphatic system, was examined for its ability to deliver chemotherapy to metastatic lymph nodes. First, the anticancer effect on metastatic lymph nodes was assessed in an experiment using the mouse mammary tumor, MM48. Pathological examination of the inguinal lymph nodes revealed a metastatic rate of 50% in the group given cisplatin (CDDP)-saline, but 20% in the group given CDDP-charcoal. Next, in a canine model, CDDP dissolved in normal saline was administered directly into the mediastinum, and CDDP was given with fine particles of activated charcoal in the same manner in the other group. The concentration of CDDP in the lymph nodes and the plasma rapidly increased to peak in 10 min in the CDDP-saline group, whereas it increased slowly to peak in 20–30 min in the CDDP-charcoal group. Moreover, the CDDP-charcoal group was found to have a much higher concentration of CDDP in the lymph nodes than the CDDP-saline group.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Molecular and cellular biochemistry 135 (1994), S. 89-98 
    ISSN: 1573-4919
    Keywords: calcium ; cell death ; nuclei ; apoptosis ; gene expression
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The last decade has seen the rapid development of research investigating the molecular mechanisms whereby hormones, peptide growth factors and cytokines regulate cell metabolism, differentiation and proliferation. One general signalling mechanism used to transfer the information delivered by agonists into appropriate intracellular compartments involves the rapid Ca2+ redistribution throughout the cell, which results in transient elevations of the cytosolic free Ca2+ concentration. Ca2+ signals are required for a number of cellular processes including the activation of nuclear processes such as gene transcription and cell cycle events. The latter require that appropriate Ca2+ signals elicited in response to agonists be transduced across the nuclear envelope. It has generally been assumed that small molecules, metabolites and ions could freely diffuse across the nuclear envelope. Nevertheless several findings during the past few years have suggested that nuclear pore permeability can be regulated and that ion transport systems and ion-selective channels may exist on the nuclear membranes and regulate intranuclear processes. Intranuclear Ca2+ fluctuations can affect chromatin organization, induce gene expression and also activate cleavage of nuclear DNA by nucleases during programmed cell death or apoptosis. The possible mechanisms involved in nuclear Ca2+ transport and the control of nuclear Ca2+-dependent enzymes in apoptosis is discussed below.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Astrophysics and space science 216 (1994), S. 153-154 
    ISSN: 1572-946X
    Keywords: Chemistry ; Molecular Hydrogen ; Cloud Models
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Observations of the CO J=1-0 line are commonly used as a tracer for molecular material in clouds. The ratio of the H2 column density to the integrated intensity of this line,X, is often taken to be constant, despite theoretical and observational uncertainty. We have tried to identify how this ratio depends on cloud parameters, testing a simple theoretical argument suggesting its invariance with respect to density. The apparent constancy can be understood if clouds are clumpy on scales of Av ≈ 1-2 mag.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1573-4935
    Keywords: pancreatic B-cells ; streptozotocin ; apoptosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Treatment of cultured pancreatic B-cells (HIT-T15 and RINm5F) with the diabetogenic drug Streptozotocin resulted in a significant increase in the number of cells that became detached from the substrate during a subsequent culture period. Examination of the detached cells by fluorescence microscopy after staining with acridine orange or by electron microscopy revealed evidence of chromatin condensation and margination. Isolation and fractionation of DNA from these cells revealed a pattern of oligonucleosomal fragmentation that was not evident in untreated cells. All of these features are characteristic of entry of the cells into apoptosis and the results suggest that the diabetogenic action of Streptozotocin involves induction of apoptosis in pancreatic B-cells.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Investigational new drugs 12 (1994), S. 49-52 
    ISSN: 1573-0646
    Keywords: metastatic colorectal cancer ; chemotherapy ; GM-CSF
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract The response rate of patients with metastatic colorectal cancer to the 4-drug combination [5-Fluorouracil (5-FU), dacarbazine, vincristine and bis-chloronitrosourea given 5 weekly (FIVB)] was better than the response rate to 5-FU. The dose limiting toxicity of the FIVB was myelosuppression. The present study investigates the effect of FIVB given with GM-CSF so that drug cycles could be given every 4 weeks. Thirty-five ambulatory patients with measurable metastatic colorectal cancer were treated with FIVB plus GM-CSF 4 weekly. All patients were evaluable for toxicity. Among the 163 cycles given only 4 were delayed because of leucopenia and 8 cycles were delayed because of gastrointestinal (GI) toxicity. A 50% dose reduction was given to 10 patients who had Grade 2 and 3 GI toxicity. Four of the 35 patients developed thromboembolic complications, 2 of which were lethal. Two patients were not evaluable for response as they were removed from study early because of toxicity. There were 2 complete responses and 6 partial responses. The median time to treatment failure was 3.8 months and median survival time 9.9 months. The addition of GM-CSF to FIVB decreased the expected leucopenia allowing drug treatment to be given 4 weekly to most patients. GI toxicity was dose limiting. Despite the increased dose intensity that could be delivered (to two thirds of patients), response rates were not definitely increased, no survival benefit was seen and important thromboembolic complications occurred.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Investigational new drugs 12 (1994), S. 133-136 
    ISSN: 1573-0646
    Keywords: colorectal carcinoma ; chemotherapy ; alkylating agent
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Background Relatively few studies have examined the activity of alkylating agents in the treatment of advanced colorectal adenocarcinoma. Recent reports have suggested possible therapeutic activity for high-dose intravenous melphalan administered with autologous bone marrow transplantation (BMT) support. We conducted a phase II study to determine the efficacy of administering intravenous melphalan at doses that do not require BMT support in patients with advanced colorectal adenocarcinoma. Patients and methods Fifteen patients with histologically proven, bidimensionally measurable disease were treated. The starting dose of melphalan was 30 mg/m2, with dose escalation permitted. Results No objective responses were observed. Toxic effects were primarily reversible granulocytopenia and thrombocytopenia. There were no treatmentassociated deaths. Conclusion Melphalan's lack of efficacy at the doses administered does not disprove the steep chemotherapy dose-response relationship postulated for many solid tumors. However, we feel that it is unlikely that repetitive courses of high dose melphalan with autologous BMT support will be a practical approach to the management of advanced colorectal adenocarcinoma.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 1573-0646
    Keywords: pancreatic cancer ; AMAP ; 773U82 ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Pancreatic cancer is the fifth leading cause in cancer related death among adults in the United States. Thirtythousand new cases of pancreatic cancer are diagnosed each year, most are metastatic at diagnosis and no effective systemic therapy is available. 773U82 mesylate is one of a series of compounds (arylmethylaminopropanediols-AMAPS) which was synthesized at the Wellcome Research Laboratories. AMAPS bind to DNA, show evidence of topoisomerase 2 inhibition and are active in a variety of murine and human preclinical screens. Based on these data a phase II trial of 773U82 mesylate administered at 800 mg/ m2 daily × 3 at a 4 h infusion repeated every three weeks was carried out. Patients eligible for these trials had histologic proof of adenocarcinoma, good performance status, and normal organ function. This was a multi-institutional trial. Nineteen patients were entered; 15 patients were fully eligible and 4 were ineligible, but were evaluated. Thirteen patients were fully evaluable for response and no response was seen. Median time to progressive disease among eligible patients was 56 days. Toxicity of 773U82 mesylate was myelosuppression which was not prohibitive. 773U82 mesylate is not active in pancreatic cancer.
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  • 10
    ISSN: 1573-0646
    Keywords: breast cancer ; dipyridamole ; mitoxantrone ; 5-FU ; leukovorin ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Based upon the hypothesis that dipyridamole would potentiate the cytotoxicity of mitoxantrone and the combination of 5-fluorouracil (5-FU) and leukovorin, we performed a phase I/II trial of the combination of dipyridamole, 5-FU, leukovorin, and mitoxantrone in patients with metastatic breast cancer. The dose of dipyridamole was fixed at 175 mg/m2 by mouth every 6 h (700 mg/m2/day), based upon a previous phase I trial of oral dipyridamole with 5-FU and leukovorin. Dipyridamole therapy began 24 h prior to the first dose of chemotherapy and continued until 24 h after the last dose of chemotherapy for each course of treatment. At the initial dose level, leukovorin 200 mg/m2 was given intravenously immediately prior to 5-FU 375 mg/ m2 intravenously on days 1–5. Mitoxantrone 6 mg/m2 was given as a single dose on day 3. Unacceptable toxicity was observed at this dose level, leading to successive dose decrements rather than dose increments. The maximum tolerated dose was leukovorin 200 mg/m2 days 1–2, 5-FU 375 mg/m2 days 1–2, mitoxantrone 6 mg/m2 on day 2, and dipyridamole 175 mg/m2 every 6 h on days 0–3. Two responses were produced in 15 patients. This regimen is not recommended for further investigation in the treatment of breast cancer.
    Type of Medium: Electronic Resource
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Cytotechnology 15 (1994), S. 117-128 
    ISSN: 1573-0778
    Keywords: Animal cell culture ; anoxia ; apoptosis ; cell death ; hybridoma ; hypoxia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract It is now well documented that apoptosis represents the prevalent mode of cell death in hybridoma cultures. Apoptotic or programmed cell death occurs spontaneously in late exponential phase of batch cultures. Until lately, no specific triggering factors had been identified. Recently, we observed that glutamine, cystine or glucose deprivation induced apoptosis in both hybridoma and myeloma cell lines whereas accumulation of toxic metabolites induced necrotic cell death in these cells. Other triggering factors such as oxygen deprivation might also be responsible for induction of apoptosis. In the present study, induction of cell death by exposure to anoxia was examined in batch culture of the SP2/0-derived hybridoma D5 clone. The mode of cell death was studied by morphological examination of acridine orange-ethidium bromide stained cells in a 1.5 L bioreactor culture grown under anoxic conditions for 75 hours. Under such conditions, viable cell density levelled off rapidly and remained constant for 25 hours. After 45 hours of anoxia, cell viability had decreased to 30% and the dead cell population was found to be 90% apoptotic. In terms of cellular metabolism, anoxia resulted in an increase in the utilization rates of glucose and arginine, and in a decrease in the utilization rate of glutamine. The lactate production rate and the yield of lactate on glucose increased significantly while the MAb production rate decreased. These results demonstrate that glycolysis becomes the main source of energy under anoxic conditions. Cells incubated for 10 hours or less under anoxic conditions were able to recuperate almost immediately and displayed normal growth rates when reincubated in oxic conditions whereas cells incubated for 22 hours or more displayed reduced growth rates. Nonetheless, even after 22 h or 29 h of anoxia, cells reincubated in oxic conditions showed no further progression into apoptosis. Therefore, upon removal of the triggering signal, induction of apoptosis ceased.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neuro-oncology 20 (1994), S. 111-120 
    ISSN: 1573-7373
    Keywords: glioma ; chemotherapy ; radiotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Although primary brain tumors represent an important cause of cancer related mortality in the United States, advances in the treatment of these tumors has been slow and has generally lagged behind that of most systemic tumors. One of the major reasons for this is the paucity of well conducted, prospective radiation and chemotherapy trials. For the brain tumor trials that have been conducted, small patient numbers, heterogeneous patient populations, and non-uniformity of response criteria, have made the current clinical data base difficult to interpret. Data from several prospective, multi-institutional randomized trials have defined a role for radiation therapy in the treatment of malignant gliomas and on-going trials will help define refinements in technique. Although there does appear to be a place for the use of chemotherapy in the treatment of a subgroup of patients with malignant gliomas, its role for the majority of patients remains unclear. Only through better understanding of the biology of these tumors, more effective therapies, and the implementation of better clinical trial design can we hope to make significant progress in the treatment of malignant gliomas.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neuro-oncology 20 (1994), S. 155-163 
    ISSN: 1573-7373
    Keywords: chemotherapy ; high grade brain tumors
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Conventional treatment of malignant high grade gliomas includes maximal resection followed by external beam radiotherapy. The addition of adjuvant chemotherapy has provided little improvement in the median duration of survival for these patients, particularly those patients with glioblastoma multiforme. The failure of conventional dose chemotherapy to improve the outcome of patients with high grade brain tumors has led several investigators to utilize high dose chemotherapy in order to overcome the limited benefit seen with conventional dose therapy which is due to intrinsic drug resistance as well as the impermeability of blood brain barrier. The majority of published studies utilizing this approach suggest that the addition of high dose chemotherapy with bone marrow transplant is of marginal benefit. However, most of these trials include small numbers of patients with advanced, refractory disease. A few trials have been reported utilizing high dose therapy in an adjuvant setting and the data from these studies are somewhat more promising. This review will analyze these studies and also discuss possible modifications of this approach in order to improve this aggressive treatment for patients who otherwise would have a dismal prognosis.
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  • 14
    ISSN: 1573-7373
    Keywords: O6-alkylguanine-DNA alkyltransferase ; chloroethylnitrosourea ; malignant glioma ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Activity of the DNA repair protein O6-alkylguanine-DNA alkyltransferase (AGT) is an important determinant of responsiveness of tumor cells to chloroethylnitrosoureas (CENUs), representative chemotherapeutic agents for primary malignant gliomas. In order to assess the real states of this repair protein in human malignant gliomas, we assayed AGT activity in surgically extirpated 42 malignant glioma samples and studied the distribution of the activity under certain clinical conditions. There were wide variations in AGT activity between individuals. No significant difference in AGT activity on average was seen either between glioblastoma and anaplastic astrocytoma, nor between primary and recurrent tumors. Among 42 malignant gliomas, 7 samples (16.7%) had low AGT activity less than 0.1 pmoles/mg protein. In the case of glioblastoma, tumors possessing higher AGT activity tended to be less responsive to post-operation remission-induction therapy including CENUs. The result of the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) chemosensitivity assay by using the corresponding surgical specimens suggested a close relationship between cellular resistance to CENUs and AGT activity. It was found to be unlikely that a short term administration of CENUs had a significant effect on AGT activity of brain tumors in human body. We could detect a bit of definite evidences of the relevance of AGT to resistance to CENUs and need to conduct further investigations for other resistance factors.
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  • 15
    ISSN: 1573-7373
    Keywords: chemotherapy ; meningioma ; radiation-induced osteosarcoma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract A case of effective chemotherapy in postirradiation sarcoma is reported. A 30-year-old woman underwent a subtotal resection of a benign mixed meningioma followed by a course of radiotherapy. Five years later she developed a skull tumor which was resected. Histological study showed sarcomatous change corresponding most likely to a postirradiation osteosarcoma. Adjuvant chemotherapy (methotrexate, carboplatin, and VP16) was given. A progression occurred 8 months later and the patient was treated unsuccessfully with tamoxifen, LHRH, and later with high dose methotrexate and carboplatin. Six months later a lung metastasis was discovered and she received four cycles of IVP (ifosfamide, vepeside, cisplatin) alternating with IVA (ifosfamide, vepeside, adriamycin). Within 4 months the primary and lung tumours had decreased substantially without evidence of progression at follow-up 5 months later. We conclude that IVP/IVA regimen is a potentially useful therapy when an osteosarcoma of the skull is in progression.
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  • 16
    ISSN: 1573-7373
    Keywords: medulloblastoma ; brain neoplasm ; chemotherapy ; ACNU ; vincristine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract A favorable case of recurrent medulloblastoma, in which 19 years has elapsed with combination therapy due to surgery, radiation and chemotherapy since the initial operation, is reported. The case was a male of age 12 who was admitted due to medulloblastoma of the classical type. Tumor recurrences were observed 3 times within 7 years after the initial operation and radiation treatment. At the 3rd recurrence, a large tumor was found in the cerebellar vermis and left cerebellar hemisphere on CT with CSF dissemination and a high NSE level in the CSF (62 ng/ml). Only chemotherapy by intravenous administration of 2 courses of 120–150 mg ACNU (1.7–2.2 mg/kg) and 4 mg vincristine (0.06 mg/kg) with intrathecal administration of methotrexate was given at this time. The tumor image and gait disturbance with radicular pain disappeared completely and the NSE level in the CSF improved to within the normal range (5.4 ng/ml). The patient continues in complete remission, with a Karnovsky performance status of 100% at 4 years after the 3rd recurrence. We report full details of this case in which active treatments consisting mainly of chemotherapy proved to be effective for recurrent medulloblastoma, even though its prognosis is generally very unfavorable.
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  • 17
    ISSN: 1573-7373
    Keywords: high-grade astrocytoma ; chemotherapy ; children
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Purpose This study was undertaken to evaluate the radiographie response to two cycles of chemotherapy prior to irradiation in newly diagnosed children with high-grade astrocytomas.Patients and methods. One hundred and thirty children less than 21 years of age with newly-diagnosed highgrade astrocytoma were treated with the ‘eight-drugs-in-one-day’ chemotherapy regimen as part of a phase III multi-institutional Childrens Cancer Group (CCG) trial. Computerized Tomographic (CT) or Magnetic Resonance Image (MRI) scans, obtained after two cycles of chemotherapy had been administered, were compared with post-operative scans to determine treatment response. Scans were evaluated by institutional radiologists, and were reviewed centrally by a single neuroradiologist. Results Of 79 patients with evaluable post-operative residual tumor on CT or MRI scans, 26 (33%) were determined on institutional evaluation to have had an objective response. However, central review of scans documented responses on only 14/79 (18%). A significantly higher response rate on central review was observed for those children 36 months of age or less at study entry than for older children (33% v 11%; p 〈 0.001). However, a higher disease progression rate was also observed for those children 36 months of age or less than for older children (21% v 2.6%; p 〈 0.001). Conclusion In this study, the largest yet reported in newly-diagnosed children with high-grade astrocytomas, the chemotherapy regimen has activity in younger children. The differences in response rates reported by institutional and central review highlight the difficulties inherent in assessing response to brain tumor therapy. However, the study does demonstrate the consistent ability of radiologists to identify disease progression within the institutional and central reviews.
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  • 18
    ISSN: 1573-7373
    Keywords: ependymoma ; ependymal cells ; estramustine-binding protein ; immunohistochemistry ; estramustine ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The mainstays of primary treatment of ependymoma are aggressive surgery followed by radiotherapy. Although spreading occasionally occurs in the cerebrospinal pathways, chemotherapy is still not established and no ultimate drug has so far been found. Estramustine-phosphate (EMP), with a demonstrated effect on astrocytomain vitro, has been shown to penetrate the blood-tumor barrier and to accumulate in human brain tumor tissue including ependymoma. It has been proposed that the cytotoxic effect of EMP depends on the presence of a binding protein, estramustine-binding protein (EMBP). In the present paper we have, for the first time, immunohistochemically demonstrated an EMBP-like protein in a series of ependymomas. Immunoreactivity was found within the cytoplasm of the tumor cells with a tendency to increase with increasing malignancy of the tumor. In addition, the occurence of EMBP-like protein was demonstrated in human ependymal cells. In the rat brain, a weak immunoreactivity was detected in early fetal neuroepithelial cells while the staining intensity was increased in mature ependymal cells in late fetal, neonatal, and adult rat. Thus, immunoreactivity for an EMBP-like protein was demonstrated in ependymoma tissue, normal human ependyma and in the developing rat ependymal cells.
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  • 19
    ISSN: 1573-7373
    Keywords: glioblastoma ; brain tumor ; radiation therapy ; chemotherapy ; ACNU
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We analyzed our treatment results of 71 operated patients with cerebral glioblastoma treated by conventional external radiation therapy (mean dose 60.2 Gy) combined with radiosensitizing agents. More than 50% reduction of tumor volume was obtained in 20 patients (28.2%). A response rate of at least 40% was obtained in patients treated with combined ACNU-vincristine-nicardipine, ACNU-5FU-hydroxyurea, or cisplatin alone. The combination of ACNU and vincristine with or without nicardipine resulted in significantly longer survival. The median survival in this group was 101.1 weeks and the two-year survival rate was 45.9%; these results were significantly better than those achieved with other ACNU combinations or other combinations without ACNU. In the analysis of survival, factors correlated to longer survival were a patient age of younger than 45 years, wide resection of the tumor, a good postoperative performance status (KS ≥70%), a radiation dose of 68–72 Gy, small postoperative tumor remnants (〈 20 cm3), no visible tumor after radiation therapy, and the administration of adjuvant chemotherapy. Maximum resection of the tumor and localized irradiation with a dose of 70 Gy combined with ACNU and vincristine appears to be the most effective treatment at present.
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  • 20
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neuro-oncology 20 (1994), S. 103-109 
    ISSN: 1573-7373
    Keywords: rat brain tumor ; radiotherapy ; chemotherapy ; interaction ; drug delivery
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The rat 9L gliosarcoma brain tumor model has been used for more than thirty years to investigate a variety of potential therapeutic agents, combinations, schedules, and approaches that might be applicable to the management of high-grade malignant brain tumors in man. When tumor cells are implanted intracerebrally, a solid tumor grows until its mass results in the death of the animal, typically between 20 and 30 days post-inoculation. Radiation therapy (either single or fractionated doses) is effective at prolonging survival in a dose-dependent manner. Numerous cancer chemotherapeutic agents, by a variety of doses, schedules, and routes of delivery, have demonstrated therapeutic efficacy in the 9L model. The combination of radiation and agents such as AZQ, BCNU, bleomycin, and cis-platinum has resulted in prolongation of survival that is significantly better than either agent used alone, without exceeding the tolerance of critical normal tissues. These pre-clinical data suggest that combining standard fractionated radiation therapy with appropriate concomitant cytotoxic chemotherapeutic agents might benefit patients with high-grade brain tumors.
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  • 21
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neuro-oncology 20 (1994), S. 177-185 
    ISSN: 1573-7373
    Keywords: brain lymphoma ; chemotherapy ; survival ; prognosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
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  • 22
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neuro-oncology 20 (1994), S. 121-139 
    ISSN: 1573-7373
    Keywords: tissue concentrations ; brain tumors ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract There is general agreement that most chemotherapy agents achieve only relatively low concentrations in the normal central nervous system, that the blood-brain barrier is variably disrupted in malignant brain tumors, and that the concentration of chemotherapy drugs in the brain adjacent to tumor is intermediate between concentrations achieved in brain tumors vs normal brain. However, there is substantial controversy regarding the role of the blood-brain barrier in resistance to chemotherapy of intracerebral tumors. Many chemotherapy agents achieve concentrations in brain tumors that are comparable to those in extracerebral tumors, and drugs that cross the intact blood-brain barrier only poorly may be active against intracerebral tumors. Furthermore, the hypothesis that the brain is a pharmacological sanctuary where metastases may grow while tumor is responding in other parts of the body may be flawed: there are only 2 or 3 types of malignancies (out of all those that are sensitive to chemotherapy) in which the risk of isolated central nervous system relapse is moderately high, and even in these 2 or 3, effective central nervous system prophylaxis has minimal or no impact on overall survival. Furthermore, drugs that cross the BBB do not appear to be more effective than other drugs at reducing the risk of brain metastases, and brain metastases at the time of diagnosis do not necessarily convey a worse prognosis than metastases to various other sites. While average drug concentrations in brain adjacent to tumor are lower than those within brain tumors, very small numbers of tumor cells may be capable of inducing local leakiness in blood vessels, and there is little information on drug concentrations achieved in individual tumor cells within the brain adjacent to tumor. Furthermore, any limitation of uptake of drugs into brain tumors could be at least partially due to increased tissue pressure within tumors rather than being due to blood-brain barrier phenomena. This distinction could be important, since strategies that one might use to increase drug delivery to brain tumors might differ depending on whether the reduced delivery were due to barrier phenomena vs blood flow phenomena. The role of the blood-brain barrier in resistance of intracerebral tumors to chemotherapy remains unclear: while it may well play some role (and perhaps even a major one), self-fulfilling prophecies and unintentional bias in data selection and interpretation may have previously made it appear more important than it actually is. The feeling by many investigators that the blood-brain barrier is a major factor in brain tumor resistance to chemotherapy may at times have unnecessarily delayed and limited the exploration of new chemotherapy drugs and strategies in the treatment of human brain tumors. While antineoplastic drug pharmacology is important in the treatment of all malignant tumors, intrinsic drug cytotoxicity may well be a much more important factor in treatment outcome than is any limitation of drug uptake by the blood-brain barrier.
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  • 23
    ISSN: 1573-7373
    Keywords: extent of surgical resection ; tumor location ; glioblastoma multiforme ; radiation therapy ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Between 1988 and 1991, eighty-six patients with glioblastoma multiforme were evaluated in order to define the influence of extent of surgery and tumor location on treatment outcome. Patients underwent surgery followed by postoperative hyperfractionated radiotherapy and chemotherapy delivered according to one of two consecutive protocols. Surgery consisted of biopsy in 25 (29%) patients and subtotal or gross total tumor resection in 61 (71%) patients. Frontally located tumors were noted in 26 (30%) patients and other tumor locations were noted in 60 (70%) patients. Patients having more radical surgery had longer median survival time (MST) and higher 1- and 2-year survival rates than those with biopsy only (56 vs 29 weeks, respectively; 62 % and 23 % vs 16% and 0%, respectively; p=0.00000). Patients having frontally located tumors had longer MST and higher 1- and 2-year survival rates than those with other tumor locations (101 vs 47 weeks, respectively; 76% and 44% vs 37% and 2.5%, respectively; p=0.00001). Multivariate analysis confirmed that extent of surgery and tumor location were independent prognostic factors in patients with glioblastoma multiforme. Regarding progression-free survival, patients having more radical surgery had longer median time to tumor progression (MTP) than those with biopsy only (33 weeks vs 21 weeks, respectively). Also, progression-free survival at 1 year was higher in radically resected group than in biopsy only group (20% vs 0%, respectively; p=0.00000). Patients with frontally located tumors had longer MTP (42 weeks) and higher progression-free survival at 1 year (42%) than those with other tumor location (28 weeks and 1.7%, respectively; p=0.00002). Multivariate analysis confirmed that the extent of surgery and tumor location are independent prognosticators in patients with glioblastoma multiforme treated with combined modality approach using progression-free survival as an endpoint.
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  • 24
    ISSN: 1573-739X
    Keywords: Antimalarials ; Artemisia annua L ; Artemisinin ; Biosynthesis ; Chemistry ; Clinical trials ; Pharmacology ; Phytochemistry ; Sesquiterpenes ; Toxicology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Artemisinin, a sesquiterpene lactone endoperoxide isolated fromArtemisia annua L., and a number of its semisynthetic derivatives have shown to possess antimalarial properties. They are all eflective againstPlasmodium parasites that are resistant to the newest and commonly used antimalarial drugs. This article gives a survey of the literature dealing with artemisinin-relaled antimalarial issues that have appeared from the end of 1989 up to the beginning of 1994. A broad range of medical and pharmaceutical disciplines is covered, including phytochemical aspects like the selection of high-producing plants, analytical procedures, and plant biotechnology. Furthermore, the organic synthesis of artemisinin derivatives is discussed, as well as their mechanism of action and antimalarial activity, metabolism and pharmacokinetics, clinical studies, sideeffects and toxicology, and biological activities other than antimalarial activity.
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  • 25
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    Springer
    Veterinary research communications 18 (1994), S. 397-415 
    ISSN: 1573-7446
    Keywords: apoptosis ; avian ; chicken ; erythroblastosis ; leukosis ; oncogene ; virus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The various diseases that follow experimental infection with the acute and non-acute avian oncoviruses are discussed with special reference to the pathogenesis of avian erythroblastosis. One view, based onin vitro studies, sees erythroblastosis as the product of a failure in the differentiation of virus-infected stem cells to mature erythrocytes, as a result of cell ‘transformation’. The results of somein vivo studies, however, point to a resemblance of the disease to a haemolytic anaemia, where cellular death is an important component. It seems probable that the disease is the result of transformation of cells of the erythroblastic series followed by the death of many of these cells due to influences that have not yet been determined. Determination of the causes of this cellular death may prove to be as important for our understanding of the problem of leukaemia as the work that has already been accomplished in explaining the causes of cell transformation. It is also suggested that the tendency ofgs amino acid sequences of the avian leukosis viruses and mouse leukaemia viruses to form fusion proteins with a variety of proto-oncogenes may be part of a wider phenomenon, and that these sequences may fuse with other proteins, altering their properties. More work is required on the possibility that there is an undiscovered immunological component in the progression of the L/S diseases.
    Type of Medium: Electronic Resource
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  • 26
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    Springer
    Colloid & polymer science 272 (1994), S. 487-492 
    ISSN: 1435-1536
    Keywords: Electrophoretic mobility ; apoptosis ; HL-60RG cells
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract We measured the electrophoretic mobilities of HL-60RG cells and their apoptotic cells triggered by Actinomycin D as a function of the ionic strength of the suspending medium at pH 7.4. Both types of cells showed negative mobilities. The apoptotic HL-60RG cells exhibited larger mobility values in magnitude than intact HL-60RG cells in the whole range of the electrolyte concentration measured. The obtained data were analyzed via a mobility expression for “soft particles’, that is, colloidal particles with ionpenetrable surface layers. The observed mobility difference between the intact and apoptotic HL-60RG cells was found to be due mainly to the difference in friction exerted by the cell surface layers on the liquid flow around the cells between these two types of cells rather than the difference in charge density in their surface layers. A possible explanation for this mobility change by apoptosis is given.
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  • 27
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    Springer
    Breast cancer research and treatment 29 (1994), S. 127-138 
    ISSN: 1573-7217
    Keywords: EGF receptor ; monoclonal antibodies ; clinical trials ; humanized antibodies ; chemotherapy ; imaging
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The epidermal growth factor (EGF) receptor and its ligands have an important regulatory role in breast carcinoma. We have produced a series of monoclonal antibodies (MAbs) directed against the external portion of the EGF receptor. These MAbs prevent the binding of the ligands to the receptor, block ligand-induced activation of the receptor, and can inhibit the growth of breast cancer cells both in tissue culture and in human tumor xenografts in nude mice. We have also shown that anti-EGF receptor antibodies greatly enhance the antitumor effects of chemotherapeutic agents active in breast cancer. Phase I clinical trials with single doses of MAb conducted in patients with tumors over-expressing EGF receptors demonstrated favorable pharmacokinetics, good tumor imaging, and a lack of toxicity. A human:murine chimeric antibody has been produced with comparable affinity and antitumor activity that will enable us to administer repeated doses of MAb either alone or in combination with chemotherapy. Our pre-clinical data support the concept that the EGF receptor may be an optimal target for treatment with receptor blocking antibodies, either alone or in combination with chemotherapy.
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  • 28
    ISSN: 1573-7217
    Keywords: breast cancer ; doxorubicin ; chemotherapy ; ifosfamide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Ifosfamide has single agent activity in advanced breast cancer and may potentiate the activity of doxorubicin. The combination of ifosfamide 5 g/m2 and doxorubicin 40 mg/m2 every 3 weeks for 4 cycles was used to treat 77 patients with advanced breast cancer. Fifty three patients had not received prior chemotherapy. All patients had one or more poor prognostic features, including tumor expression of epidermal growth factor receptor in 11/12 tested. The overall response rate was 74% (95% confidence intervals 62%-83%). The median survival was 9.4 months. The principal toxicities were febrile neutropenia and ifosfamide encephalopathy each in 6% of patients. A high percentage of the projected dose intensity was administered. This is a highly active combination with acceptable toxicity in advanced breast cancer, although the long term survival remains poor. Further exploration of ifosfamide in combination chemotherapy for advanced breast cancer is warranted.
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  • 29
    ISSN: 1573-7276
    Keywords: cerebral metastasis ; chemotherapy ; sanctuary site ; testicular cancer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Isolated central nervous system relapse in patients treated successfully with cisplatin-based chemotherapy for testicular cancer has been described infrequently. In a retrospective analysis we identified this complication in six of 417 patients. Five of the six patients had advanced pulmonary dissemination at onset of chemotherapy, and post-chemotherapy surgery did not reveal viable tumour tissue in any of these cases. All six patients developed a single cerebral metastasis during complete remission a median four months after discontinuation of chemotherapy. Five patients were treated with surgery and subsequent radio-therapy, one patient with irradiation alone. Three patients are alive relapse-free 19, 62 and 86 months after diagnosis of cerebral relapse. One patient was alive with cerebral disease for 12 months without evidence of systemic recurrence. Our data demonstrate that the brain may act as a sanctuary site in chemotherapy-treated testicular cancer. A review of the literature shows that an isolated cerebral relapse is an extremely rare complication, but carries a relatively favourable prognosis.
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  • 30
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    Cancer and metastasis reviews 13 (1994), S. 309-315 
    ISSN: 1573-7233
    Keywords: prostaglandins ; prostaglandin D2 ; prostaglandin E2 ; prostaglandin J2 ; ovarian cancer ; cell cycle ; G1 arrest ; myc oncogene ; apoptosis ; immune systems ; interleukin-2 ; cisplatin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Pleiotropic actions of antitumor prostaglandins (PGs) on tumor cells are reviewed including our preclinical results focused on human ovarian cancer. Regarding inhibition of cell proliferation, antitumor PGs exerts its action as a G1 blocking agent. The cyclopentenone PGs inhibit myc oncogene expression while inhibiting the cell cycle progression and results in apoptotic cell death and growth inhibition. Cyclopentenone PGs inhibit growth of various tumors transplanted to mice or nude mice and show adjuvant effects to cis-diamminedichloroplatinum(II) (CDDP). In order to elucidate a role of antitimor PGs in immune systems, relevance of effects on tumor growth with those on the immune systems are also discussed with our results.
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  • 31
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    Digestive diseases and sciences 39 (1994), S. 2467-2475 
    ISSN: 1573-2568
    Keywords: apoptosis ; ionizing radiation ; photodynamic therapy ; lymphoma ; hepatoma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The aim of this study was to determine the relative role of apoptosis in photodynamically-induced cytotoxicity or radiation-induced cytotoxicity for hepatoma and lymphoma cells. Human hepatoma cells and mouse lymphoma cells were treated with either photodynamic therapy (PDT) or ionizing radiation. Dosimetry studies of immediate cell death following photodynamic therapy in the hepatoma cell line demonstrated second-order kinetics, similar to that seen in the lymphoma cells. No immediate cell death was noted in the hepatoma or lymphoma cells following ionizing radiation, but experiments measuring delayed cell death demonstrated a dose-dependent response. Maximum DNA ladder formation occurred 2 hr after PDT and 24 hr after ionizing radiation in the lymphoma cells, which was consistent with the time courses of cell death for these treatments. The hepatoma cell line did not demonstrate DNA ladder formation despite dosages of PDT or ionizing radiation sufficient to cause high levels of cytotoxicity.
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  • 32
    ISSN: 1573-6830
    Keywords: JunB ; c-jun ; JunD ; neuronal differentiation ; JunB phosphorylation ; neuronal plasticity ; circadian rhythm ; apoptosis ; antisense
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary 1. To investigate the role of the Jun transcription factors in neuronal differentiation, programmed neuronal cell death, and neuronal plasticity, we used phosphorothioate oligodeoxynucleotides (S-ODN) to inhibit selectively the expression of c-Jun, JunB, and JunD. 2. We have shown previously that in contrast to c-Jun, the JunB and JunD transcription factors are negative regulators of cell growth in various cell lines. Here we confirm this finding in primary human fibroblasts. 3. c-Jun and JunB are counterplayers not only with respect to proliferation, but also in cell differentiation. Since JunB expression is essential for neuronal differentiation, we analyzed possible posttranslational modifications of JunB after induction of PC-12 cell differentiation by nerve growth factor (NGF). 4. JunB was strongly phosphorylated after induction of PC-12 cell differentiation with NGF but not after stimulation of cell proliferation with serum. Thus, while cell proliferation is associated with c-Jun phosphorylation, cell differentiation is correlated with JunB phosphorylation. This supports the finding that c-Jun and JunB play antagonistic roles in both proliferation and differentiation. 5. The JunB transcription factor together with the c-Fos transcription factor is also inducedin vivo in the suprachiasmatic nucleus (SCN) of rat brain after a light stimulus that induces resetting of the circadian clock. 6. Using antisense oligonucleotides injected into the third ventricle, we selectively cosuppressed the two transcription factorsin vivo as shown by immunohistochemistry. Expression of c-Jun, JunD, and FosB was not affected. Inhibition of JunB and c-Fos expression prevented the light-induced phase shift of the circadian rhythm. In contrast, rats injected with a randomized control oligonucleotide showed the same phase shift as untreated animals. 7. In primary rat hippocampal cultures, anti-c-jun S-ODN selectively inhibited neuronal cell death and promoted neuronal survival. This indicates a causal role of c-Jun in programmed neuronal cell death. 8. These findings demonstrate the essential role of inducible transcription factors in the reprogramming of cells to a different functional state. Jun transcription factors play an essential role not only in fundamental processes such as cell proliferation, differentiation, and programmed neuronal cell death, but also in such complex processes as plastic adaptations in the mature brain. The inhibition of neuronal cell death by anti-c-jun S-ODN shows the great therapeutic potential of selective antisense oligonucleotides.
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  • 33
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 57-65 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Positive und negative Photostrukturen wurden in einem Polyimid (PI) aus 4,4′-Biphthalsäureanhydrid (BPA) und 4,4′-Diamino-3,3′-dimethyldiphenylmethan (DADMDPM), PI(BPA/DADMDPM) erzeugt, nachdem dieses mit Michlers Keton (MK) bzw. Benzophenon (BP) dotiert und einer ultravioletten Strahlung von 400 ± 50 nm ausgesetzt und naß entwickelt wurde. Das Prinzip der positiven Abbildung basiert auf dem Photokupplungseffekt von MK mit PI, der die Löslichkeit des Polyimids erhöht und so die Entwicklung eines Positivmusters ermöglicht. Die Erzeugung negativer Muster wird durch intermakromolekulare Wasserstoffbrücken zwischen der Carbonylgruppe des Imid-Rings und der Hydroxygruppe, die bei der photoinduzierten Kupplung von Benzophenon mit dem Polyimid gebildet wird, bewirkt. Die lithographische Auswertung zeigt, daß der mit MK dotierte, positive Polyimidfilm nicht in der Lage ist, brauchbare Muster zu erzeugen, da die UV-Wellenlängen von MK absorbiert werden, wodurch die Photokupplung in den tieferen Schichten des Films verhindert wird. Andererseits können in dem 0,6 μm dicken, mit Benzophenon dotierten Polyimidfilm sogar 2 μm schmale Linien aufgelöst werden.
    Notes: Positive and negative photostructures are formed after the polyimide (PI) of 4,4′-biphthalic anhydride (BPA) and 4,4′-diamino-3,3′-dimethyldiphenylmethane (DADMDPM), PI(BPA/DADMDPM) is doped with Michler′s ketone (MK) and benzophenone (BP), respectively, and is subjected to UV light (400 ± 50 nm) irradiation and solvent development. The principle of positive feature formation is based on the photocoupling of MK with PI, which increases PI solubility and thus enables a positive pattern to be developed. The phenomenon of negative photopatterning results from intermacromolecular H-bonding between the carbonyl group of the imide ring and the hydroxy group which is formed in the photoinduced coupling reaction between BP and PI. Lithographic evaluation shows that the MK-doped positive-acting PI film cannot form useful patterns because UV wavelengths are strongly absorbed by MK, which limits the depth of photocoupling in the film. On the other hand, 2-μm-wide lines can be resolved in the BP-doped negative-acting 0.6-μm-thick PI film.
    Additional Material: 5 Ill.
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  • 34
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 101-113 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polyhydrazid/Polyamid-Blends (PEHZ12/PA6) wurden durch Niedrigtemperatur-Polykondensation von 4,4′-Dichlorformyl-α,ω-diphenoxydodecan und Terephthaloyldihydrazid (TDH) zu Poly(etheraroylhydrazid) in Gegenwart von Polyamid 6 synthetisiert. Die DSC-Analysen lassen vermuten, daß die zwei Polymerkomponenten nicht wechselwirken. Bei der Extraktion des PA6-Anteils der Blends mit Ameisensäure zeigt die Charakterisierung des PEHZ12-Extraktionsrückstands aber, daß zumindest bei bestimmten Zusammensetzungen Wechselwirkungen zwischen den Komponenten auftreten. Modellreaktionen erlauben die Annahme, daß die PEHZ12-Polymerisation zwischen den Amino-Endgruppen des PA6 und den wachsenden PEHZ12-Polymerketten abläuft.
    Notes: Poly(etheraroylhydrazide) is synthesized in the presence of PA6 by means of low-temperature condensation polymerization of 4,4′-dichloroformyl-α,ω-diphenoxydodecane with terephthaloyl dihydrazide (TDH) in order to prepare polyhydrazide/poly-amide 6 (PEHZ12/PA6) blends. The thermal analysis of the blends by DSC seems to indicate that the two polymers are not interacting. Nevertheless, when the blends are subjected to an extraction process with formic acid in order to remove the PA6, the characterization of the residual PEHZ12 reveales that some interactions do occur between the constituent polymers, at least for selected compositions. Model experiments permit to hypothesize that the polymerization of PEHZ12 proceeds with a chemical interaction between amino end groups of PA6 and growing PEHZ12 chains.
    Additional Material: 7 Ill.
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  • 35
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 179-196 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The crystallization behavior of PBT as well as PC is changed in the controlled-processed blend due to intermolecular interactions between the different macromolecules in molten state.If the kinetics of the crystallization process prevents a crystallization-induced separation, the partial miscibility of the amorphous phases, measured by the glass transition temperatures, will lead to a decrease of the crystallinity of PBT. The crystallinity, normalized to the concentration of PBT in the blend, is independent from the concentration of PC at low coolling rates.At high cooling rates, PBT is crystallizing stepwise in the blend PBT/PC 40/60 wt.-%. The crystallization temperature in the anisothermic crystallization process is increased at low contents of PC due to a changed nucleation mechanism. The half-time of crystallization is increasing in blends with an increasing PC-content in isothermic crystallization experiments.The normally amorphous PC crystallizes considerably fast in presence of PBT in PC-rich blends. The crystallization or change in the state of order of PC was measured in situ by X-ray diffraction. Calorimetric experiments confirm this result and allow a quantitative estimation of the PC-crystallinity, which amounts to some 20% in the blend PBT/PC 5/95 wt.-%.
    Notes: Das Kristallisationsverhalten sowohl von PBT als auch von PC ist im definiert verarbeiteten Blend infolge intermolekularer Wechselwirkungen zwischen den unterschiedlichen Molekülen in der Schmelze verändert.Die über die Glasübergangstemperaturen gemessene teilweise Mischbarkeit der amorphen Phasen führt bei PBT zu einer Erniedrigung des Kristallinitätsgrades, wenn die kinetischen Bedingungen des Kristallisationsprozesses keine kristallisationsbedingte Entmischung zulassen. Der auf den PBT-Anteil normierte Kristallinitätsgrad ist bei kleinen Abkühlgeschwindigkeiten vom PC-Anteil unabhängüg.In der Mischung PBT/PC 40/60 Gew.-% kommt es bei hohen Kühlraten zu einer fraktionierten Kristallisation. Die Kristallisationstemperatur bei anisothermer Kristallisation ist bei geringen PC-Gehalten durch Änderung des Keimbildungsmechanismus erhöht. Bei isothermer Kristallisation steigt mit zunehmendem PC-Anteil die Kristallisationshalbwertszeit des PBT an.Das normalerweise amorphe PC kann in Gegenwart von PBT in den PC-reichen Mischungen besonders schnell kristallisieren, wobei der Kristallisations- bzw. Ordnungsprozeß des PC in situ mittels der Röntgenbeugung gemessen wurde. Kalorimetrische Untersuchungen bestätigen dieses Ergebnis und erlauben eine quantitative Abschätzung des PC-Kristallinitätsgrades zu ca. 20% im Blend PBT/PC 5/95 Gew.-%.
    Additional Material: 12 Ill.
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  • 36
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 214 (1994), S. 197-210 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Elementaranalytische sowie NMR-, IR- und UV-spektroskopische Untersuchungen zeigen, daß die Photolyse von Halogenphenolnovolaken zur Substitution der Halogenatome durch Wasserstoff, der Bildung chinoider Gruppen und intermolekularen Vernetzung führt. Die Geschwindigkeit der Halogeneliminierung hängt von der Art des Halogens ab. Sie steigt in der Reihenfolge F 〈 Cl 〈 Br 〈 I. Die Chloreliminierung aus der 4-Position ist gegenüber der aus der 2- und 3-Position begünstigt. Außerdem verläuft die Abspaltung para-ständiger Chloratome aus Dimeren schneller als aus Trioder Tetrameren. ESR-Messungen bei 77 K sowie die Laserblitzphotolyse bei 296 K deuten auf die intermediäre Bildung von Phenoxyl- und Arylradikalen. Lithographische Tests belegen die hohe UV-Empfindlichkeit von Resisten auf der Basis von Halogenphenolnovolaken. Im Vergleich zu nichthalogenhaltigen Novolakresisten wird eine 6 - 10fache (System: 4-Chlorphenolnovolak/4,4′-Bisazidobiphenyl (5%)) bzw. eine ca. 25fache (System: 4-Chlorphenol-/m-Cresolnovolak/Hexamethoxymethylmelamin (5%)) Steigerung der Empfindlichkeit erreicht. Zur Interpretation wird ein Mechanismus postuliert, demzufolge die durch Halogenabspaltung hervorgerufene Sekundärradikalbildung zu einer zusätzlichen Vernetzung beiträgt. In den melaminhaltigen Resisten katalysiert der gebildete Halogenwasserstoff (Hal· + RH → H-Hal + R·) außerdem die Reaktion der Melaminverbindung mit der Novolakmatrix.
    Notes: The photolysis of halogenophenol novolacs is determined by the substitution of halogens by hydrogen and the formation of quinoid groups and intermolecular crosslinks. This is concluded from elemental analysis, NMR, IR and optical absorption measurements. The rate of halogen release depends on the chemical nature of the halogen. It increases in the order F 〈 Cl 〈 Br 〈 I. Chlorine elimination from 4-position is favored over that from 2- and 3-position. Moreover, dimers release chlorine from 4-position much more readily than trimers and tetramers. ESR measurements at 77 K and flash photolysis studies at 296 K yielded evidence for the intermediate existence of phenoxyl and aryl radicals. Lithographic tests demonstrated the high UV-sensitivity of resist formulations based on halogen-containing novolacs. The increase in sensitivity relative to that of formulations based on nonhalogenated novolacs is 6 to 10fold system: 4-chlorophenol novolac/4,4′-bisazidobiphenyl (5%) and ca. 25fold system: 4-chlorophenol/m-cresol novolac/hexamethoxymethylmelamine (5%). A postulated reactions mechanism concerning the sensitivity increase takes into account that halogen elimination results in the formation of additional radicals that accelerate the rate of crosslinking. Moreover, hydrogen halide generated by hydrogen abstraction of halogen radicals (Hal· + RH → H-Hal + R·) provides for the acid required to catalyze the reaction of the melamine compound with the novolac matrix.
    Additional Material: 6 Ill.
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  • 37
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    Angewandte Makromolekulare Chemie 215 (1994), S. 11-24 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Calciumcarbonate unterschiedlicher Teilchenform (sphäarisch, kubisch und nadelfäormig) wurden mit Polypropylen (PP) in einer Zwei-Walzen-Mäuhle gemischt und anschließend zu Platten gepreßt. Der Einflußder Teilchenform auf das Kristallisationsverhalten der PP/CaCO3-Composite, d.h. Kristallisationspeaktemperatur (Tmax), Kristallisationsverlauf usw., wurde mittels Differentialkalorimetrie untersucht. Der Wert von Tmax häangt von der Größe der Gesamtoberfläache der CaCO3-Teilchen ab; Tmax ist bei nadelfäormigen Teilchen gräoßer als bei kubischen oder sphäarischen und hauangt in allen Fäallen der nicht-isothermen Kristallisation von der Abkäuhlgeschwindigkeit und der vorher erreichten maximalen Temperatur ab.
    Notes: Calcium carbonate of various particle shape (spheric, cubic, needle-shaped type) and polypropylene (PP) were mixed on a two roll mill and the mixture was pressed into plates. The effect of particle shape on the crystallization behavior of PP/CaCO3 composites, such as crystallization peak temperature (TMAX), crystallized pattern, etc., was investigated with differential scanning calorimetry measurements. The value of TMAX is explained by the total surface area of added CaCO3 particles; TMAX of needle-shaped series is larger than that of cubic or spheric ones. TMAX of various shaped CaCO3-filled PP totally depends on the cooling rate and maximum temperature in the non-isothermal crystallization, respectively.
    Additional Material: 9 Ill.
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  • 38
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    Angewandte Makromolekulare Chemie 215 (1994), S. 107-119 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Polyaddition von Polyethylenglykol (PEG) Oligoglycidylethern (Mn (PEG): 396,587, 1437 und 3554) mit asymmetrischen Diaminen, wie N,N-Dimethylund N,N-Diethyl-1,3-diaminopropan, wurden wasserläosliche kationische Polymere erhalten. Die Eigenschaften der kationischen Polymeren sind vom urspräunglichen PEG-Molekulargewicht und der Diaminreaktivitäat abhäangig. PEG mit Mn = 396 zeigt das beste Verhalten. In verdäunnten wäassrigen Läosungen und in wäassrigen 2M NaCl-Läosungen der Polymeren wurde das Polyelektrolytverhalten veranschaulicht. Die Gegenwart der PEG Kette bestimmt das Polyelektrolytverhalten in den 2M NaCl Läosungen.
    Notes: Water-soluble cationic polymers were obtained by polyaddition of poly(ethylene glycol) (PEG) diglycidylethers (M̄n of PEG were 396, 587, 1437 and 3554, resp.) with asymmetrical diamines such as N,N-dimethyl-1,3-diaminopropane and N,N-diethyl-1,3-diaminopropane. The cationic polymer properties depend on the PEG initial molecular weight and on the diamine reactivity too. PEG with M̄n = 396 had the best behaviour in these reactions. The polyelectrolyte feature of cationic polymers was emphasized both in dilute aqueous solutions and in 2M aqueous NaCl solutions. The polyelectrolyte behaviour in 2M aqueous NaCl solution is determined by the PEG chain presence.
    Additional Material: 4 Ill.
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  • 39
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 139-145 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Reaktion von o-Kresol mit Formaldehyd wurde unter Verwendung verschiedener tertiäarer Amine als Katalysatoren untersucht. Der Einfluß der Reaktionsparameter Basizitäat, Temperatur, Reaktionszeit und Formaldehydkonzentration wird diskutiert. Für die bevorzugte Bildung von 2,4-Bis(hydroxymethyl)-6-methylphenol wurden optimierte Synthesebedingungen erarbeitet. Die Bildung von Zwei-bzw. Mehrkernprodukten konnte nicht ausgeschlossen werden.
    Notes: The reaction between o-cresol and formaldehyde was investigated using various tertiary amines as catalysts. The influence of the reaction parameters basicity, temperature, reaction time and concentration of formaldehyde was discussed. To yield preferentially 2,4-bis(hydroxymethyl)-6-methylphenol the conditions of synthesis were optimized. The formation of bi- and polynuclear products cannot be avoided.
    Additional Material: 4 Ill.
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  • 40
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 215 (1994), S. 189-200 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Scherviskositäat fläussigkristalliner Ethylcellulose, die mit Cellulosepulver unterschiedlicher Partikelgräoße gefäullt war, wurde bei konstantem Schergefäalle mit einem Kegel-Platte-Viskosimeter bestimmt. Der Einfluß des Cellulosepulvergehalts, des Läange/Breite-Verhäaltnisses der Pulverteilchen und der Temperatur auf das viskose Verhalten und die Phasenäubergäange wird diskutiert. Der Zusatz von Cellulosepulver erhäoht die Viskositäat und verringert die Aktivierungsenergie des Fließens(Ea), ohne jedoch die Phasenäubergäange zu beeinflussen. Die Viskositäat und die Aktivierungsenergie sind abhäangig vom Läange/Breite-Verhäaltnis der Pulverteilchen; mit zunehmender Gräoße dieses Verhäaltnisses wird die Viskositäatszunahme beschleunigt und die Aktivierungsenergie des Fließens erhäoht, wäahrend die Aktivierungsenergie mit steigendem Pulvergehalt abnimmt. Die Phasenumwandlungen sind unabhäangig von der Partikelform. Der Einfluß des Pulvergehalts auf Viskositäat und Aktivierungsenergie ist abhäangig von der Art der fläussigen Phase; in der anisotropen Phase ist der Einfluß geringer als in der isotropen Phase. Dies scheint von der Ausrichtung der Pulverteilchen und der stäabchenfäormigen Molekäule herzuräuhren.
    Notes: Steady-state shear viscosity for the liquid crystalline ethyl cellulose solution filled with cellulose powders was determined using a cone-plate-type viscometer and the effects of cellulose powder content, powder aspect ratio and temperature on the viscometric behavior and phase transformation were discussed. The addition of powder increased the viscosity and decreased the activation energy (Ea) for flow, but did not affect the phase transformation. The viscosity and Ea depended on the aspect ratio; with greater aspect ratio, the viscosity enhancement was accelerated and Ea as well as the decrease in Ea with powder content increased. The phase transformation did not depend on the aspect ratio, the dependences of viscosity and of Ea on powder content depended on the solution phase; the dependences for the anisotropic phase were smaller than those for the isotropic one. The findings appeared to originate from the alignments of powders and rod-like molecules.
    Additional Material: 4 Ill.
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  • 41
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The UV-degradation of an unstabilized and two HALS stabilized polyethylene (PE) films is described. The degradations are characterized by measuring the oxygen uptake, the formation of CO and CO2, the FT-IR spectra, the mechanical properties, the stabilizer concentration and the oxygen content of the film.The oxygen uptake of the unstabilized PE film led to the expected changes in the IR spectra and embrittlement of the film, while the oxygen uptake by the HALS stabilized films caused only minor changes. The differences between the results for the unstabilized and the HALS stabilized polymers are explained assuming that the initiation of the photodegradation of PE is due to charge transfer complexes.
    Additional Material: 6 Ill.
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  • 42
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Principal chemical pathways characteristic of active participation of radical scavenging polymer stabilizers (phenols, aromatic, hydroaromatic and hindered aliphatic amines) are outlined. Pathways resulting in a partial depletion or distortion of activity of stabilizers, in formation of polymer discolouring products, or in interactions in bifunctional stabilizers are involved.
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  • 43
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Irradiations (λ≥300 nm) of poly(butyleneterphtalate) films were carried out in both vacum and air. Photoproducts were investigated by FTIR spectroscopy, chemical derivatization reactions and physical treatments. The repartition of photoproducts in the polymer was shown to be heterogeneous. A scheme accounting for the main routes of PBT photolysis was found on the basis of photoproducts identification. Most of oxidation products were analogous to vacum photolysis species; the mechanism of photooxidation proposed implied both pure photolytical processes and a photo-induced oxidation route.
    Additional Material: 8 Ill.
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  • 44
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of polymer density, processing conditions (quenching of annealing), degree of crystallinity, size of crystallite and mobility of polymer chains on the photo-and radiation-induced degradation and the polymer stability have been studied by UV, FTIR spectroscopic, viscosity and mechanical property measurements. Four kinds of annealed or quenched polyethylene (PE) films varying densities were used to the studies. Polystyrene (PSt) films were used to investigate the effect of chain mobility on polymer degradation. The following results were obtained. 1.In linear low density (LLD) PE, greater amounts of crosslinking (irradiated in vacuum) and chain scission (irradiated in air) were noticed than in mediun density (MD) PE and high density (HD) PE samples.2.Polyene formation is favored in the case of the irradiation in vacuum for LLDPE.3.Polymer stability evaluated by mechanical property such as elongation at break (%) is superior in LLDPE to MDPE and HDPE for annealed and quenched samples.4.Segmental motion of polymer chain also affects the polymer stability
    Additional Material: 19 Ill.
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  • 45
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 217 (1994), S. 43-49 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The study is on two component blends of high density polyethylenes, having normal and ultra-high molecular weight. The polyethylenes were homogenized by two routes: in powder state or by rolling in melt, then pressed at temperatures in the range from 140°C to 220°C. Comparative studies showed that the way of homogenizing of the components does practically not affect the main mechanical properties of the blends when pressed at temperatures ≥ 160°C. Of special interest are the characteristics of those systems where ultra-high molecular weight polyethylene is the matrix component.
    Notes: Untersucht wurden binäre Mischungen von Polyethylenen hoher Dichte rnit normaler und ultrahochmolekularer Molmasse, die auf zweierlei Weise - in Pulverform oder durch Walzen im Schmelzezustand - homogenisiert und bei Temperaturen zwischen 140 und 220°C gepreßt waren.Es wurde festgestellt, daß die Art der Homogenisierung der Komponenten praktisch keinen Einfluß auf die Eigenschaften bei Preßtemperaturen ≥ 160°C hat. Von besonderem Interesse sind die Eigenschaften der Systeme, in welchen das ultrahochmolekulare Polyethylen die Rolle der Matrixkomponente spielt.
    Additional Material: 4 Ill.
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  • 46
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 218 (1994), S. 81-109 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Verhalten eines neuartigen photoinitiierenden Systems, das die Polymerisation von pigmenthaltigen Schichten großer Dicke in einem Reaktionsschritt gestattet, wird dargestellt. Die verschiedenen Wechselwirkungen, die in einem pigmenthaltigen System auftreten, werden qualitativ beschrieben, und der Anteil der von einem Photoinitiator absorbierten Lichtintensität wird berechnet. Neben dem Absorptions- und Reflexionsverhalten von verschiedenen Pigmentklassen werden die optischen Eigenschaften verschiedener Strahlungsquellen untersucht, um die Strahlungsbereiche zu finden, die am besten mit den optischen Parametern der Pigmente korrespondieren. Weiterhin wird die Beschleunigung von Polymerisationen durch die photokatalytische Wirkung einiger Pigmente behandelt.
    Notes: Ce travail sur le rôe des pigments définit le comportement d'un nouveau systeme photosensible qui permet de polymériser des milieux épais et pigmentés selon un procédé en une seule étape. Les différentes interactions présentes en milieu pigmenté sont décrites de façon qualitative, et la part de l'intensité lumineuse absorbée par un photo-amorceur dans un systéme pigmenté est evaluée. Les propriétés optiques telles que l'absorption et la réflectance des différentes familles chimiques de pigments sont déterminées, et, en paralléle, les propriétés optiques des différentes sources d'irradiation sont étudiées de manière à répondre au mieux aux fenêtres de transmission des pigments. L'effet photocatalytique de certains pigments est mentionné, ceci afin d'amkliorer la réaction de polymérisation.
    Additional Material: 18 Ill.
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  • 47
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 218 (1994), S. 153-162 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Herstellung von cis-1,4-Polybutadien erfolgte mittels Polymerisation von 1,3-Butadien mit einem Katalysatorsystem, das in einer zweistufigen Reaktion gebildet wird: (1) BF3 · O(C2H5)2 und Al(C2H5)3, (2) Ni(OOC8H15)2 und Al(C2H5)3, genannt in-situ-Katalysatorsystem.Die Molmassenverteilungen (MMD) der erhaltenen Polymeren sind mit der Größenausschlußchromatographie (SEC) untersucht worden. Sie lassen sich mit Summen aus Schulz-Flory-Funktionen (SFF) beschreiben. Veränderte Katalysatorformierungs- und Polymerisationsbedingungen beeinflussen die Parameter der SFF. Veränderte Peakflächen und Molmassenmittelwerte der Einzelpeaks zeigen, daß die Polymerisation über mehrere Arten aktiver Zentren verläuft.
    Notes: Cis-1,4-polybutadiene was produced by polymerization of 1,3-butadiene using a catalyst system formed by a two-step formation, Namely (1) BF3 . O(C2H5)2 and Al(C2H5)3, (2) Ni(OOC8H15)2 and Al(C2H5)3 named in-situ-catalyst.The molar mass distributions (MMD) of the polybutadienes are investigated by means of size exclusion chromatography (SEC). The MMD's were fitted by a sum of Schulz-Flory-Functions (SFF). Changed catalyst formation and polymerization conditions influenced the parameters of the SFF. Changed areas and changed molar mass averages indicate a polymerization with more than one peak maximum and kind of active species and lead to a better understanding of the polymerization.
    Additional Material: 9 Ill.
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  • 48
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 1-10 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Umsetzung von Chromacrylat mit Bisphenol A und einem Überschuß Epichlorhydrin wurden neuartige Epoxid-Harze hergestellt. Epoxy-Äquivalentgewicht, Gehalt an Hydroxygruppen und hydrolysierbarem Chlor sowie die Viskosität wurden bestimmt, und die Harze wurden mittels IR- und 1H-NMR-Spektroskopie charakterisiert. Die thermischen Eigenschaften der bei 30°C für 24 h mit Ciba Geigy HY 850 (aliphatisches Amin) gehärteten Harze wurden gemessen. Die Harze besitzen eine gute thermische und chemische Stabilität und eine gute elektrische Leitfähigkeit. Die Reaktion verläuft nach erster Ordnung; die Aktivierungsenergie beträgt 47 kJ mol-1 bzw. 34 kJ mol-1 mit bzw. ohne Chromacrylat. Aus spektroskopischen Untersuchungen wird geschlossen, daß das Chrom mit Bisphenol A einen Komplex bildet, der die Epoxidierung beschleunigt.
    Notes: Novel epoxy resins containing chromium acrylate have been synthesized by reacting chromium acrylate with bisphenol-A and excess epichlorohydrin. The quantities such as epoxy equivalent weight, hydroxy content, hydrolyzable chlorine content and viscosity have been determined. The resins have been characterized by IR and 1H NMR spectroscopy. The cured resins were evaluated for thermal properties. The curing of resins was carried out with Ciba Geigy HY 850 (aliphatic amine adduct) at 30°C for 24 h. The cured resins have excellent thermal and chemical resistance, in addition to an excellent electrical conductivity. The reaction follows first order kinetics with an activation energy of 47 kJ mol-1 and 34 kJ mol-1 in the presence and absence of chromium acrylate, respectively. The chromium forms a complex with bisphenol-A, as indicated by spectroscopic studies, which increases epoxidation.
    Additional Material: 6 Ill.
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  • 49
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 67-76 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Interpenetrierende Polymernetzwerke (IPNs) aus Polystyrol und Polyurethan auf der Basis von hydroxyterminiertem Naturkautschuk mit unterschiedlichen NCO/OH-Verhältnissen wurden unter verschiedenen Reaktionsbedingungen hergestellt und zu widerstandsfähigen Filmen verarbeitet. Die IPNs wurden durch ihre physikalischen, mechanischen und morphologischen Eigenschaften wie Dichte, Shore-A-Härte, Vernetzungsdichte, Zugfestigkeit und Reißdehnung charakterisiert. Mit steigendem Polystyrolgehalt erhöhen sich auch Dichte, Shore-A-Härte und Zugfestigkeit, während die Reißdehnung abnimmt. Die Untersuchungen der Vernetzungsdichte lassen eine Phasenumkehr vermuten.
    Notes: Interpenetrating polymer networks (IPNs) of polyurethane based on hydroxyterminated natural rubber with varying NCO/OH ratios and polystyrene were synthesized under different experimental conditions. These IPNs were found to make tough films. The IPNs were characterized by their physical, mechanical and morphological properties like density, Shore-A hardness, crosslink density, tensile strength and elongation at break. The IPNs exhibited an increasing trend in density, Shore-A hardness and tensile strength with increasing polystyrene content, while elongation at break decreased with similar variation in polystyrene content. The crosslink density measurements indicated a possible phase inversion process.
    Additional Material: 7 Ill.
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  • 50
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 117-124 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß einer Plasmabehandlung von Ultrafiltrationsmembranen aus Polyethylen auf die Fouling- und Reinigungseigenschaften bei der Filtration von Rinderserumalbumin werden diskutiert. Bei 2,45 GHz erzeugtes Luft-Plasma steigert die Hydrophilie der Membranoberfläche von 0 auf 60%. Der Durchfluß bleibt bei 90 bis 99%. Mit Plasma behandelte Membranen sind leichter zu reinigen als unbehandelte; dennoch sind sie anfälliger für die Ablagerung von Rinderserumalbumin.
    Notes: The effect of plasma treatment of polyethylene ultrafiltration membranes on fouling and cleaning phenomena during filtration of bovine serum albumin solutions is discussed. Air-plasma of 2.45 GHz raises the membrane surface hydrophilicity from 0 up to 60%. The flux is maintained at 90-99%. Plasma-treated membranes are easier to clean than untreated polyethylene membranes. Despite that, the plasma-modified membranes are susceptible to more intensive deposition of albumin.
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  • 51
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 101-115 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Immobilisierung von Glucose-Oxidase in einer Poly(vinylalkohol) (PVAL)-Membran in Gegenwart von UV-Photoinitiatoren wurde untersucht. Enzym-Membranen wurden aus PVAL-Diazoharz- und PVAL-Photoinitiator-Systemen durch Vernetzung mit UV-Licht hergestellt. Mit diesen immobilisierten Glucose-Oxidase-Membranen wurde eine wirkungsvolle Enzymelektrode entwickelt, deren Eigenschaften untersucht wurden. Der Einfluß der Photoinitiatorkonzentration in Poly(vinylalkohol) und der UV-Bestrahlungsdauer auf den Grad der Unlöslichkeit sowie die Aktivitätsausbeute der Membran wurden mit Glucose als Substrat untersucht. Temperatur- und pH-Abhängigkeit der relativen Aktivität, Stabilität bei mehrmaligem Gebrauch, Lagerstabilität und Kalibrierungsdiagramme der Enzym-Membranen wurden ermittelt. Eine beim Erstgebrauch auftretende Instabilitätserscheinung der Membranen wurde ebenfalls untersucht.
    Notes: A study of the immobilization of glucose oxidase on a poly(vinyl alcohol) (PVAL) membrane in the presence of UV sensitizers was carried out. Enzyme membranes were prepared from PVAL-diazoresin and PVAL-sensitizer systems, crosslinked by means of UV irradiation. An effective enzyme electrode was developed by using the immobilized glucose oxidase membrane, and its characteristics were investigated. The effects of the concentration of sensitizers in poly(vinyl alcohol) and UV irradiation time on the degree of insolubility as well as the activity yield of the membrane were examined for the immobilized glucose oxidase using glucose as a substrate. Temperature and pH dependences of the relative activity, stability in repeated use, storage stability and calibration plots of the enzyme membranes were evaluated. The unstability phenomenon, found in the initial use of the immobilized glucose oxidase membrane, which was prepared from PVAL-sensitizer system, was also investigated.
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  • 52
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 219 (1994), S. 11-26 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Biopol, Biocellat and Mater-Bi, three biologically decomposable plastics have been tested for their use in medical industries. Biopol did not loose its stress and stiffness under sterilisation, and was also resistant against temperature and alcohol. Mater-Bi and Biocellat, the two other materials, did not satisfy the test applications. Water vapor sterilisation, temperature up to 60°C, at higher temperatures this material will embrittle.
    Notes: Für den Einsatz biologisch abbaubarer Kunststoffe in der pharmazeutischen Industrie und Medizintechnik wurden Produkte verschiedener Hersteller, wie Biopol, Biocellat und Mater-Bi untersucht. Dabei zeigte vor allem Biopol das notwendige Anforderungsprofil, d.h. die Anwendbarkeit aller Sterilisationsverfahren ohne Festigkeitsbzw. Steifigkeitsverluste sowie Temperatur- und Alkoholbeständigkeit. Dagegen wiesen die Werkstoffe Mater-Bi und Biocellat einige Schwachstellen auf. Bei Mater-Bi lagen diese bei der Wasserdampfsterilisation sowie bei der geringen thermischen und Medienbeständigkeit. Biocellat versprödet dagegen durch die erhöhte Temperatur bei der Dampfsterilisation, d.h. daß ein Einsatz über 60°C nicht möglich wäre.
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  • 53
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Alkylierung von Poly(5-vinyltetrazol) mit Dimethylsulfat und tert-Butylalkohol sowie Alkylhalogeniden RHal (R=CH3, C2H5, CH2—CH=CH2, n-C4H9 und t-C4H9) und die Kinetik dieser Reaktion wurden untersucht, um eine neue Herstellungsmethode für tetrazolhaltige Polymere mit wertvollen Eigenschaften zu entwickeln. Die vergleichenden Untersuchungen über die isomere Zusammensetzung und die spektroskopischen Daten von Poly(N-alkyl-5-vinyltetrazol)en, die durch die Alkylierung von Poly(5-vinyltetrazol) sowie durch die Copolymerisation der entsprechenden Monomeren hergestellt wurden, wurden mit IR-, 1H-NMR- und 13C-NMR-Spektroskopie durchgeführt. Der Alkylierungsumsatz beträgt bis zu 99,8%; dadurch können polymere Produkte erhalten werden, deren Zusammensetzung, Struktur und Eigenschaften denen der Homo- und Copolymeren sehr ähnlich sind.
    Notes: Alkylation of poly(5-vinyl tetrazole) with dimethyl sulfate and tert-butyl alcohol as well as with alkyl halides RHal (R=CH3, C2H5, CH2—CH=CH2, n-C4H9, t-C4H9) has been studied under various conditions in order to develop a new method of synthesis of tetrazole-containing polymers having a complex of valuable properties. The kinetic study of the process and comparison of isomeric compositions and spectroscopic characteristics (IR, 1H NMR and 13C NMR) of poly(N-alkyl-5-vinyl tetrazole)s synthesized by alkylation of poly(5-vinyl tetrazole) and of those prepared by (co)polymerization of the corresponding vinyl tetrazoles have been carried out. The alkylation is found to proceed to high conversion extents (up to 99.8%) and enables to obtain a wide variety of polymeric products having the composition, structure and properties very similar to those of homo- and copolymers.
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  • 54
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Farbstoffe mit nichtlinearen optischen Eigenschaften wurden in einer zweistufigen Synthese aus 2-Hydroxyethylmethacrylat (HEMA), 4-Carboxybenzaldehyd und verschiedenen Anilinderivaten hergestellt. Die Farbstoffe (aromatische Iminester von HEMA) wurden mit Styrol copolymerisiert, die erhaltenen Copolymere wurden mit DSC sowie IR-, 1H NMR- und UV-VIS-Spektroskopie charakterisiert, und ihre nichtlinearen Eigenschaften wurden untersucht. Es zeigte sich, daß die nichtlinearen Koeffizienten d31 und d33 vom Farbstoffgehalt der Copolymeren und der Art der elektronenspendenden Gruppen abhängig sind.
    Notes: Dyes for nonlinear optics have been synthesized in two steps from 2-hydroxyethyl methacrylate (HEMA), 4-carboxybenzaldehyde and various substituted anilines. The obtained dyes (aromatic imine esters of HEMA) have been copolymerized with styrene, the copolymers characterized by DSC as well as IR, 1H NMR and UV-VIS spectroscopy, and studied for their nonlinear properties. The d31 and d33 nonlinear coefficients proved to be dependent on the dye content of the copolymers and on the nature of electrondonating groups.
    Additional Material: 4 Ill.
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  • 55
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 220 (1994), S. 123-132 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß von Ca2+-bzw. Al3+-Ionen auf das Viskositätsverhalten (Salzverträglichkeit) wäßriger Lösungen von Natriumcarboxymethylcellulose (CMC) sowohl mit unterschiedlichem Polymerisationsgrad (DP) als auch mit unterschiedlichem Substitutionsgrad (DS) und verschiedenartiger Substitutentenverteilung wurde untersucht. Aus Viskositätsmessungen mit einem Rotationsviskosimeter bei einer Scherrate von 500 s-1 geht hervor, daß die relative Abnahme der Viskosität im Ergebnis des Zusatzes der mehrwertigen Metallkationen unabhängig vom DP (im Bereich von 160 bis 900) der CMC ist. Homogen hergestellte CMC-Proben 2 mit einem größeren Gehalt an 2,3,6-Tri-O-carboxymethylglucose-Einheiten in der Polymerkette weisen im Vergleich zu heterogen hergestellten CMCs 1 bei gleichem Gesamt-DS eine höhere Salzverträglichkeit auf.
    Notes: The influence of Ca2+-and Al3+-ions, respectively, upon the viscosity behaviour (so-called salt tolerance) of aqueous solutions of sodium carboxymethyl cellulose (CMC) with different degree of polymerization (DP) and, on the other hand, with both different degree of substitution (DS) and distribution of substituents, was investigated. Viscosimetry by means of a rotational rheometer at a shear rate of 500 s-1 shows that the relative drop in viscosity as a result of addition of the multivalent metal cations is independent of DP (ranging from 160 to 900) of the CMC samples. Homogeneously synthesized CMCs (2) with a higher content of 2,3,6-tri-O-carboxymethyl glucose units in the polymer chain possess a significantly higher salt tolerance than those (1) prepared under heterogeneous reaction conditions at comparable total DS values.
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  • 56
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    Angewandte Makromolekulare Chemie 222 (1994), S. 61-87 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Melamin-Formaldehyd-Harz-Formmassen (MF) wurden durch mechanisches Mischen mit Ethylen-Vinylacetat-Copolymeren (EVA) und teilverseiftem EVA modifiziert, wobei Etherbindungen zwischen dem hydrolysierten EVA und dem MF-Harz nachgewiesen werden konnten, die die mechanischen Eigenschaften von spritzgepreßten Formteilen im Vergleich zur Modifizierung mit EVA verbessern. Der Zusatz solcher Modifikatoren erhöht die Duktilität und verringert im Falle von EVA die Nachschwindung der überaus steifen MF-Matrix, solange der Modifikatoranteil gering bleibt. Dagegen werden die Steifigkeit und die Wärmeformbeständigkeit verschlechtert. Die durch solche unvernetzten Polymeren erreichbare Steigerung der Schlagzähigkeit bleibt allerdings unzureichend.
    Notes: Melamine-formaldehyde moulding compounds (MF) were modified by mechanical mixing with ethylene/vinyl acetate copolymers (EVA) and with partially hydrolysed EVA. Ether linkages between the hydrolysed material and the MF resin improve the mechanical properties of the transfer moulded parts containing the hydrolysed material compared to those made with EVA. The use of both modifying polymers improves the ductility and, in case of the partially hydrolysed material, the postshrinkage of the extremely rigid MF matrix, as long as the modification polymer content is kept low. On the contrary, Young's modulus and the heat deflection temperature are deteriorated. The improvement in impact strength by use of those uncrosslinked polymers is still insufficient.
    Additional Material: 17 Ill.
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  • 57
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    Angewandte Makromolekulare Chemie 222 (1994), S. 111-123 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Eine Reihe von Copolyesteramiden mit Molekulargewichten zwischen 1000 und 7000 (GPC, NMR) wurden aus Adipinsäure/1,6-Hexandiamin/∊-Caprolacton bzw. Nylon 6,6-Salz/∊-Caprolacton hergestellt. Die thermischen Eigenschaften der synthetisierten Polymeren (Glasübergangs-, Schmelz-, und Zersetzungstemperaturen, Schmelzenthalpien) wurden durch DSC- und TGA-Messungen bestimmt und in Bezug auf das Comonomerverhältnis in der Ausgangsmischung diskutiert. Die Übereinstimmung der Copolymerzusammensetzung mit dem Ausgangscomonomerverhältnis wurde mit FT-IR- und NMR-Spektroskopie untersucht. Die Bioabbaubarkeit der Copolyesteramide wurde durch enzymatische Hydrolyse geprüft.
    Notes: A series of copolyesteramides based on adipic acid/1,6-hexane diamine/∊-caprolactone and Nylon 6,6 salt/∊-caprolactone were synthesized. Their molecular weights, determined by gel permeation chromatography and NMR spectroscopy, were found to lie within the range from 1000 up to 7000. Their thermal properties (glass transitions, melting points and heats of melting, and decomposition temperatures) were recorded with diferential scanning calorimetry and thermogravimetry, respectively, and correlated to the comonomer feed composition. The FT-IR and NMR spectra were also recorded in order to confirm the composition of the copolyesteramides and to compare them with that of the comonomer feed. The biodegradability of the synthesized copolymers was tested by enzymatic hydrolysis.
    Additional Material: 4 Ill.
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  • 58
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    Angewandte Makromolekulare Chemie 222 (1994), S. 165-174 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch sulfonsäurekatalysierte Umsetzung von Abietinsäure und Paraformaldehyd bei hohen Temperaturen wurden neuartige Kondensationsprodukte erhalten. Als Nebenprodukte der Polykondensation werden eine Ketoverbindung sowie Wasser und Kohlendioxid gebildet. Die Carboxygruppen der Abietinsäure sind an der Kondensationsreaktion beteiligt. In Abwesenheit von Paraformaldehyd wurde das Abietinsäure/Sulfonsäurekatalysator-System untersucht, um zusätzliche Informationen über die Reaktion zu erhalten. Der Reaktionsverlauf hängt von der Temperatur und der chemischen Struktur des Katalysators ab. Ein möglicher Reaktionsmechanismus der Kondensation wird diskutiert.
    Notes: New condensation products have been synthesized by heating abietic acid and formaldehyde at high temperatures in the presence of sulfonic-type acid catalysts. The main polycondensation reaction is associated with a secondary one which leads to a ketonic compound, carbon dioxide and water. The carboxylic groups of abietic acid participate in this condensation reaction. The behaviour of the abietic acid-sulfonic acid catalyst system was studied in absence of formaldehyde to acquire additional information about the reaction. The process is defined by the reaction temperature and chemical nature of the catalyst. A possible mechanism of the condensation reaction is discussed on the basis of the obtained results.
    Additional Material: 2 Ill.
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  • 59
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    Angewandte Makromolekulare Chemie 223 (1994), S. 1-11 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: After a general classification of the cationic ring-opening polymerizations (CROP's) according to their polymerization mechanism, a number of examples of tailored polymers based on CROP are presented. The monomers used for the synthesis of these tailored structures are tetrahydrofuran (THF), N-tert-butyl aziridine (TBA), 2-methyl-1,3-oxazoline (MeOX) and 1,3-dioxolane (DXL).The polymer structures include different block and graft copolymers, macromonomers, star-shaped polymers, polymer networks and interpenetrating polymer networks (IPNs).
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  • 60
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In diesem Beitrag wird ein überblick über neuere Entwicklungen auf dem Gebiet der Synthese von Telechelen, Makromonomeren, Block- und Pfropfcopolymeren gegeben. Synthesestrategien aus den Bereichen der Polykondensation, der radikalischen, anionischen und kationischen Polymerisation, der Kettenspaltung sowie der Criss-Cross-Cycloaddition werden diskutiert.
    Notes: New developments in the synthesis of telechelics, macromonomers, block- and graftcopolymers are presented. Synthetic strategies for them are demonstrated with examples from different fields such as polycondensation, radical, anionic, and cationic polymerization, chain cleavage and criss-cross-cycloaddition.
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  • 61
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    Angewandte Makromolekulare Chemie 223 (1994), S. 69-79 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Alkanes with highly substituted carbon-carbon bonds can be cleaved in free radicals by homolytic dissociation under the influence of thermal energy. The energy of dissociation is mainly determined by the type and size of the respective substituents. For tetraarylbutane dinitriles the temperatures of decomposition are in the range of other technically used initiators. But nevertheless, these compounds are up to now rather seldom used to initiate free radical polymerizations. This is connected with the special mechanism of initiation: the formed highly substituted alkyl radicals are relatively stable and show only a rather low reactivity against the usually used monomers. Therefore, in the beginning of the polymerization the radical concentration is rather high which leads not only to addition to monomers but also to a pronounced primary radical termination. In some cases this termination process is reversible which results in an unusual polymerization kinetics. Depending on the type of monomer and the degree of reversibility of the primary radical termination, either a period of “dead-end” polymerization follows or the cleavage of the oligomers at the chain end results in a re-initiation process with a “normal” polymerization with increased rate. The reaction mechanism, kinetics and some possible applications of such initiating alkanes are reported.
    Additional Material: 3 Ill.
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  • 62
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    Angewandte Makromolekulare Chemie 223 (1994), S. 121-133 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Untersuchungen wesentlicher Aspekte der Polymerisation und der Eigenschaftsmodifikation auf Metallocen-Katalyse basierender Cycloolefin-Copolymere (COC) zeigen, daß mit dieser Monomer-Katalysator-Kombination eine neue Klasse transparenter Thermoplasten zugänglich gemacht wird. COC können mit Metallocenen in beliebiger zusammensetzung und mit kontrollierter Mikrostruktur hergestellt werden. Die somit erreichte und durch zusätzliche Modifikationen noch erweiterbare Breite des Eigenschaftsspektrums ermöglicht vielfältige Anwendungen dieser neuen Polymerklasse. Die wichtigsten Schlüsselfaktoren im rohstofflich-technologischen Bereich, die diese Struktur- und Eigenschaftsvielfalt ergeben, werden beispielhaft beschrieben.
    Notes: Investigation of the polymerization process and property modification of metallocene-based cycloolefin copolymers (COC) shows that this monomer-catalyst combination enables synthesis of a new class of transparent thermoplastic polymers. Metallocene catalysis offers much opportunity to vary the composition and microstructure of the copolymers. The breadth of the polymer spectrum which can be further widened by polymer modification enables many applications for this new class of thermoplastics. The key parameters that control structure and properties in the COC family are discussed in this paper.
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  • 63
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    Angewandte Makromolekulare Chemie 223 (1994), S. 165-175 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The present paper deals with the synthesis and modification of functionalized polymers characterized by a special molecular architecture. The reactivity of a functionalized polymer with comb-like structure can be controlled in a significant manner by the crystalline order of the side chains. In contrast, photocrosslinking of comblike polymers containing cinnamic components in the side chains influences the crystallization process. The air drying process of a modified polybutadiene system with comb-like structure was shown to depend sensitively on the side chain order. Enzymatic synthesis of new monomers and polymers is briefly reviewed. The complexing capability of cyclodextrines were used to synthesize polyrotaxanes. Finally, the synthesis of a chiral polymerizable dendrimer containing eight estergroups in the monomer unit is presented.
    Additional Material: 8 Ill.
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  • 64
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    Angewandte Makromolekulare Chemie 223 (1994), S. 203-216 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Intramolecularly crosslinked poly(organosiloxane) particles are prepared by means of emulsion polycondensation or emulsion polymerization of alkoxysilanes or cyclic organic siloxanes. Starting from these intramolecularly crosslinked poly(organosiloxane) particles, graft copolymers are obtained by free-radical emulsion polymerization of unsaturated olefinic monomers (e.g. acrylates, styrene) in the presence of (functionalized) organosiloxanes. Intramolecularly crosslinked poly(siloxane) particles and their graft copolymers are characterized by means of light scattering (in dispersion), electron microscopy and thermal analyses (DSC, DMTA).
    Additional Material: 4 Ill.
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  • 65
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    Angewandte Makromolekulare Chemie 214 (1994), S. 153-167 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Zusammenhang zwischen der Mischbarkeit und den physikalischen Eigenschaften von Polymerblends aus Poly(2,6-dimethyl-1,4-phenylenoxid) (PPO), die in unterschiedlichen Zusammensetzungen in einem Doppelschneckenextruder mit Polystyrol, schlagzähem Polystyrol oder Styrol-Butadien-Copolymeren hergestellt wurden, wird diskutiert. Die Verträglichkeit der Komponenten wurde mittels DSC und DMA, die Morphologie der Blends mittels SEM untersucht. Mit abnehmendem Polystyrolanteil wurde eine schlechtere Mischbarkeit bei den Blends beobachtet, deren Kerbschlagempfindlichkeit sich erhöhte. Die Untersuchungsergebnisse werden mit dem Micellmodell interpretiert.
    Notes: The relationship between the miscibility and the physical properties of polymer blends of poly(2,6-dimethyl-1,4-phenylene oxide) and polystyrene (PS), high-impact polystyrene (IPS) and poly(styrene-block-butadiene-block-styrene) (SBS), which are blended in different compositions by a twin-screw extruder is discussed. The three types of SBS that were used are SBS1, SBS2 and SBS3 having different styrene/butadiene ratios. Dynamic mechanical analysis and differential scanning calorimetry were used to study the miscibility. The morphology was examined by SEM. The miscibility of the blends decreases with decreasing PS content. The notch sensitivity is improved by blending. Finally, the micelle model was used to explain the testing phenomena.
    Additional Material: 8 Ill.
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  • 66
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Aliphatische Polyamide mit Poly(ethylenoxid)-Kettensegmenten unterschiedlicher Länge wurden durch Grenzflächenpolymerisation aus Succinylchlorid und Jeffamine ED-900 (O,O'-Bis(2-aminopropyl)poly(ethylenglykol) 800) bzw. Jeffamine ED-2001 (O,O'-Bis(2-aminopropyl)poly(ethylenglykol) 1900) zur Verwendung als Trägersubstanzen für Medikamente synthetisiert. Copolyamide mit kurzkettigen Diamin- und Jeffamine-Segmenten sowie Polyamide aus Cystin und Diamineinheiten wurden auf die gleiche Weise hergestellt. Die Polymerisationen wurden im zweiphasigen System Dichlormethan/Wasser bei Temperaturen um 0°C durchgeführt. Die Polymerprodukte wurden durch stufenweise Dialyse in wäßriger Phase bis zu einem Molekulargewicht von 25000 fraktioniert, nach Gefriertrocknung als wasserlösliche Harze oder Feststoffe erhalten und durch Mikroanalyse sowie 1H NMR-Spektroskopie charakterisiert. Die inhärenten Viskositäten liegen im Bereich von 10-20 ml/g. Die Eignung eines repräsentativen Zielmoleküls zur Bindung von Medikamenten wurde durch eine kovalente Verankerung einer als Medikamentmodell fungierenden Ferrocen-Verbindung untersucht. Dabei wurde ein wasserlösliches Polymer-Ferrocen-Konjugat erhalten.
    Notes: Aliphatic polyamides comprising poly(ethylene oxide) chain segments of various lengths, designed for use as drug carriers, are synthesized by interfacial polymerization of succinyl chloride with the two Jeffamine types ED-900 and ED-2001, formally described by the supplier as O,O'-bis(2-aminopropyl)poly(ethylene glycol) 800 and O,O'-bis(2-aminopropyl)poly(ethylene glycol) 1900. Copolyamides comprising both short-chain diamine and Jeffamine segments are similarly prepared, as are polyamides made up of cystine and diamine segments. The polymerizations are performed in a two-phase methylene chloride-water system at temperatures near or below 0°C. The product polymers, crudely fractionated by staged aqueous-phase dialysis at an ultimate molecular-mass cut-off of 25000, are collected after freeze-drying as water-soluble resins or solids and are characterized microanalytically and by 1H NMR spectroscopy. Inherent viscosities are in the range of 10-20 ml g-1. The drug-binding potential of a representative target polymer is probed by the covalent anchoring of a ferrocene compound used as a drug model, giving a water-soluble polymer-ferrocene conjugate.
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  • 67
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    Angewandte Makromolekulare Chemie 214 (1994), S. 211-216 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Über die Anwendung von Vinylesterharzen aus dem Diglycidylether von Bisphenol A sowie dessen Urethanderivat als Beschichtungsmaterial wird berichtet. Die mit den Harzen beschichteten Flußstahlplatten wurden auf Oberflächenglanz, Kratzfestigkeit und Chemikalienbeständigkeit untersucht. Harze mit Styrolanteil zeigen deutlich verbesserte Beschichtungseigenschaften.
    Notes: The present paper is concerned with the coating applications of a vinyl ester resin derived from diglycidyl ether of bisphenol-A and its urethane derivative. The mild steel panels coated with the synthesized resins were evaluated for their gloss on the surface, scratch hardness and chemical resistance. The incorporation of styrene in the resin systems improves the properties of coatings remarkably.
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  • 68
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Katalysatorsystem Zirkonocendichlorid/Methylalumoxan wurde auf Siliciumdioxid aufgebracht, um Katalysatoren fur die Suspensions- order Gasphasenpolymerisation von Ethylen herzustellen. Die häochste Aktivitäat wurde für eine sandwichartige, dreilagige Verankerung von Zirkonzentren auf der Träageroberfläache gefunden. Dieneuen Katalysatorsysteme besitzen eine im Vergleich zu den entsprechenden homogenen Katalysatoren geringere Aktivitäat. Die Immobilisierung der aktiven Katalysatorzentren führt zu einer deutlichen Erhäohung der Polymermolmassen. Dabei bleibt die enge Molekulargewichtsverteilung der Polymerprodukte nahezu erhalten. Solche auf Träager aufgebrachte Metallocen-Katalysatoren käonnten für die Herstellung von Polyethylenen mit kontrollierter Rheologie Anwendung finden.
    Notes: The system zirconocene dichloride/methylalumoxane was supported on silica in order to provide ethylene polymerization catalysts for suspension or gas phase processes. Highest activity was found for a sandwich-like, three layer anchoring of the zirconium centers on the support surface. The new catalyst systems show a decrease of activity compared to polymerization experiments in homogeneous phase. However, the molecular weights are increased and the weight distributions remain narrow by immobilization of the active catalyst sites. Those supported metallocene catalysts could find application for the synthesis of polyethylene materials with controlled rheology.
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  • 69
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    Angewandte Makromolekulare Chemie 215 (1994), S. 129-138 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Vernetzte Copolmere aus Butylacrylat (BA) und Ethylenglycol-dimethacrylat (EGDMA) wurden auf ihre Eignung als stationäare Phase für die Chromatographie untersucht. Es wurde festgestellt, daß gering vernetzte Copolymere (〈 30 Gew.-% EGDMA) nicht poräos sind, wäahrend Matrices mit mehr als 40 Gew.-% EGDMA eine konstante Porositäat aufweisen. Eine Erhäohung des Vernetzergehaltes beeinflußt hauptsäachlich die Hydrophobie der Oberfläache. Zwei Meßmethoden für diese Eigenschaft werden diskutiert: Die Absorption von Alkylalkoholen und von Aminosäauren. Für letztere wurde aus der Steigung der Beziehung zwischen der Sälenkapazitäat und dem Hydrophobie-Parameter der Aminosäauren ein Matrix-Hydrophobie-Index berechnet und dieser mit den bekannten Energien der Wechselwirkung von Alkylalkohol—CH2 Gruppen mit der Polymermatrix verglichen. Die Vorteile der Verwendung des Hydrophobie-Indexes bei der Bewertung von polymeren Sorbentien werden aufgezeigt.
    Notes: Copolymers of butyl acrylate (BA) crosslinked with ethylene glycol dimethacrylate (EGDMA) were evaluated as potential chromatographic packings. It was found that slightly crosslinked copolymers (up to 30 wt.-% EGDMA) did not provide porous material, while for matrices which exceeded 40 wt.-% of EGDMA the porous structure remained unchangeable. The increase of crosslinker content mostly affected the surface hydrophobicity. Two methods of measurement of this property were discussed: Sorption of alkyl alcohols and amino acids. Taking the latter for testing, a polymer matrix hydrophobicity index was calculated as the slope of dependence of column capacity vs. amino acid hydrophobicity parameter. The indices were verified against well-established interaction energies of —CH2— groups of alkyl alcohols and polymer surfaces. Some benefits of the use of the hydrophobicity index in evaluation of polymer sorbents were demonstrated.
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  • 70
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Kondensation von 3-Glycidyloxypropyltrimethoxysilan I mit Diphenylsilandiol II wurde untersucht. Abhängig von Lösungsmittel, Temperatur und Katalysator werden unterschiedliche Primärprodukte erhalten. Die Reaktion in Masse bei 120°C mit Titan(IV)-isopropylat als Katalysator liefert ein transparentes Harz A. Das eduktfreie Produkt wurde IR-, 1H- und 13C-NMR-spektroskopisch charakterisiert und chromatographisch mit GPC und HPLC untersucht. Die trimeren und tetrameren Siloxane bestehen aus Diphenylsilan- und 3-Glycidyloxypropylmethoxysilaneinheiten. Das Verhältnis von cyclischen zu linearen Molekülen beträgt 2:1. Höhermolekulare Verbindungen entstehen nur in geringen Mengen. Das Epoxysiloxangemisch löst sich in unterschiedlichen organischen Lösungsmitteln und ist mit kommerziell verfügbaren Epoxiden mischbar. Die Zeitabhs̈ngigkeit von Viskosität und Epoxidwert bei der Lagerung unter Normalbedingungen wurden gemessen und mit HPLC verfolgt . Die Lagerstabilität wurde durch eine zusätzliche thermische Behandlung verbessert.
    Notes: Condensation of 3-glycidyloxypropyltrimethoxysilane I with diphenylsilanediol II was investigated. Depending on solvent, temperature and catalyst, different products were obtained. Bulk reaction at 120°C using titanium(IV)-isopropylate as a catalyst provided the transparent resin A. A was characterised by IR, 1H- and 13C-NMR spectroscopy and contained no reactants. GPC and HPLC studies revealed that A consists of trimer and tetramer siloxanes of pertinent diphenylsilane and 3-glycidyloxypropylmethoxysilane moieties. The proportion of cyclic to linear molecules was evaluated 2:1. Only small amounts of high-molecular-weight compounds were observed. The epoxysiloxane product proved to be miscible with various organic solvents and with commercial epoxy resins. Time dependence of viscosity and epoxy content were recorded during ambient storage and monitored by HPLC. Pot-life was improved by a subsequent thermal procedure.
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  • 71
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    Angewandte Makromolekulare Chemie 218 (1994), S. 163-170 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Cis-1,4-Polybutadien wurde durch Polymerisation von 1,3-Butadien mit Katalysatorsystemen hergestellt, die Ni(OOC8H15)2 und Al(C2H5)3 sowie die Lewissäuren BF3 · O(C2H5)2 oder TiCl4 enthalten. Die Molmassenverteilungen (MMD) der erhaltenen Polybutadiene wurden mit der Größenausschlußchromatographie (SEC) untersucht. Sie lassen sich mit Summen aus Schulz-Flory-Funktionen (SFF) beschreiben. Da eine Art aktiver Zentren eine SFF ergibt, die durch Molmassenmittelwerte definiert ist, lassen sich verschiedene Molmassenverteilungen nach Bandentrennung auf gleiche und verschiedene Arten aktiver Zentren untersuchen. In den untersuchten Systemen lassen sich zwei vergleichbare und eine unterscheidbare Art aktiver Zentren zuordnen. Auf diese Weise wurde das Kettenwachstum in Abhängigkeit von den Komponenten und Katalysatorformierungsbedingungen untersucht.
    Notes: Cis-1,4-polybutadiene was produced by polymerization of 1,3-butadiene using a catalyst system containing Ni(OOC8H15)2 and Al(C2H5)3 and the Lewis acids BF3 · O(C2H5)2 or TiCl4. The molar mass distributions (MMD) of the polybutadienes are investigated by means of size exclusion chromatography (SEC). The MMD's were fitted by a sum of Schulz-Flory-Functions (SFF). Taking into account that one kind of active species gives one SFF defined by molar mass averages, one comparable active species in both systems and one different were found. This way it was tried to find a relationship between the grown up of the active species depending on components and reactions conditions.
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  • 72
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    Biopolymers 34 (1994), S. 11-20 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: αD-N-acetyl neuraminic acid (Neu5Ac, sialic acid) is a commonly occurring carbohydrate residue in various cell surface glycolipids and glycoproteins. This residue is linked terminally or internally to Gal residues via an α(2 → 3) or α(2 → 6) linkage. In the cell surface receptor, sialyl-LewisX, a terminal α(2 → 3) linkage is present. Previous studies from our laboratory have shown that in solution LewisX adopts a relatively rigid structure. In order to model the Neu5Ac residue, vacuum molecular dynamics of this monosaccharide were compared with simulations that explicitly include solvent water. The dynamical average of the monosaccharide conformation obtained from the two simulations was similar. Vacuum calculations for the disaccharide Neu5Ac α(2 → 3) Gal β-O-methyl show that a number of low energy minima are accessible to this disaccharide. Molecular dynamics simulations starting from the low energy minima show conformational transitions with a time scale of 10-50 ps among several of the minima while large barriers between other minima prevent transitions on the time scale studied. Simulations of this disaccharide in the presence of solvent show fewer conformational transitions, illustrating a dampening effect of the solvent that has been observed in some other studies. Our results are most consistent with an equilibrium among multiple conformations for the Neu5Ac α(2 → 3) Gal β linkage. © 1994 John Wiley & Sons, Inc.
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  • 73
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The properties of collagen are affected by the replacement of Pro by imino acid analogues. The structural effect of the low-level local substitution of L-azetidine-2-carboxylic acid (Aze) has been analyzed by computing the energy of CH3CO-(Gly-Pro-Pro)4-NHCH3 triple helices in which a single residue of one strand has been replaced by Aze. When Aze is in position Y of a (Gly-X-Y) unit, low-energy local deformations are introduced in the triple helix, i.e., it becomes more flexible. On the other hand, the flexibility of the triple helix is not increased with Aze in position X. The energy of the triple helix to coil transition is not changed significantly by this amount of substitution. In an earlier study, we have demonstrated that the regular substitution of Aze in every tripeptide distorts or destabilizes the triple helix to a large extent [A. Zagari, G. Némethy, & H. A. Scheraga (1990) Biopolymers, Vol. 30, pp. 967-974 ]. Thus, it appears that a high level of substitution is required to cause the observed chemical and biological effects of Aze on collagen. © 1994 John Wiley & Sons, Inc.
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  • 74
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    Biopolymers 34 (1994), S. 357-364 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A dielectric relaxation peak due to bound water of globule proteins in aqueous solution was observed at first by the use of a time domain reflectometry. This peak locates around 100 MHz as well as that of the aqueous DNA solution and the moist collagen, and has a relaxation strength in proportion to surface of the globule protein except for trypsin and pepsin of hydrolase. It is suggested that this peak is caused by orientation of bound water molecules on the protein surface. The number of bound water molecules estimated is in good agreement with that obtained by other method such as x-ray analysis. The solution exhibits another peak below 100 MHz, which is caused by the rotation of globule protein supplemented by migration of the counterion. Its relaxation time is completely proportional to the molecular weight of the protein. © 1994 John Wiley & Sons, Inc.
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  • 75
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    Biopolymers 34 (1994), S. 393-401 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enthalpies of interactions of porcine arterial elastin with alkali metal and alkali earth halides and sulphates were investigated by means of flow microcalorimetry and the stoichiometry measured using radiotracer techniques. In aqueous solutions, all alkali earth halides interacted exothermically at concentrations ranging from 0.01 to 2.5M. All the alkali metal halides, particularly NaCl, exhibited complex concentration-dependent interactions, exothermic at low concentrations and endothermic at high concentrations. Both the anion and cation contributed to the response, although the anion seemed to dominate. SO42- interacted most strongly of the anions tested. All interactions were reversible in the sense that repeat experiments gave identical results, but the enthalpy of “adsorption” was generally different from that of “desorption.” The enthalpy of interaction depended on the conformation of the elastin in a salt-specific manner. For example, CaCl2 and MgCl2 interacted similarly in water but very differently in 1 : 1 water : methanol. © 1994 John Wiley & Sons, Inc.
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  • 76
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    Biopolymers 34 (1994), S. 435-442 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photophysical behavior of protoporphyrin IX (P) and 1-naphthylacetic acid (N), covalently bound to ε-amino groups of poly (L-lysine) (PL), was investigated by steady-state and time-resolved fluorescence as a function of pH. Within the whole range of pH explored, i.e., 7-11, exciplex emission is minor and nearly pH independent. Fluorescence quantum yields, decay time measurements, and transient absorption spectra suggest that quenching of the excited naphthyl chromophore chiefly occurs by interconversion to the triplet state when the sample is randomly coiled and by intramolecular electron transfer (ET) from ground-state porphyrin when the polypeptide is in α-helical conformation. The kinetic law, based on a two-state model for the polymeric matrix, is presented. The specific rate constant of photoinduced ET is 3.1 · 107 s-1 (25°C), in excellent agreement with that obtained by taking simply into account the lifetimes of naphthalene fluorescence in α-helical PNPL and NPL (pH 11). The relaxation time of the helix-coil transition was found to be definitely shorter than 20 ns. © 1994 John Wiley & Sons, Inc.
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  • 77
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aggregation of filipin in aqueous medium and filipin-induced changes in cholesterol micelles have been studied using intensity and dynamic light scattering. The dependencies of filipin aggregate dimensions on concentration, solvent, and temperature were studied, and revealed that the aggregates do not have a well-defined geometry, i.e., a critical micelle concentration cannot be detected and stable structures are not formed. The aggregates are of size Rg ≈ 110 nm and Rh ≈ 63 nm, referring to the radius of gyration and hydrodynamic radius, respectively. In the concentration range studied (1 μM 〈 C 〈 30 μM), a low molecular weight species (monomer/dimer) is always present together with the aggregates. In ethanol/ water mixtures, large (Rg ≈ 500 nm), narrow distribution aggregates are formed in the water volume fraction range 0.45 〈 ΦH2O 〈 0.65. Aggregation also occurs on changing the temperature; In the range 7-37°C, smaller aggregates (10-30 nm) form and the process is only partially reversible.No pronounced effect of filipin on the structure of the cholesterol micelles was observed (a small increase in Rg and Rh is noted). These results rule out any “specificity” for the filipin interactions with cholesterol, which has been considered a key event in the filipin biochemical mode of action. A reevaluatiori Of this question is suggested and some alternatives are advanced. © 1994 John Wiley & Sons, Inc.
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    Biopolymers 34 (1994), S. 489-505 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polypeptide α-carbon backbones were modeled as freely rotating chains made up of spherical monomers. The monomers were assigned an abstract binary “hydrophobicity” property that could be either present or absent. Under the assumption that “hydrophobic” residues tend to cluster together, away from the polar solvent, three-dimensional conformations of random copolymers of “hydrophobic” and “hydrophilic” monomers were calculated by a novel algorithm based on distance geometry techniques. The simulated molecules were globular and compact, in shape, and possessed distinct hydrophobic cores, indicating that our method was capable of reproducing some of the important global features of real polypeptides. © 1994 John Wiley & Sons, Inc.
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  • 79
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    Biopolymers 34 (1994), S. 559-563 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 80
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The linear nonapeptide hormone bradykinin (Arg1-Pro2-Pro3-Gly4-Phe5-Ser6-Pro7-Phe8-Arg9) is involved, either directly or indirectly, in a wide variety of physiological processes, particularly pain and hyperanalgesia. Additional evidence suggests that bradykinin also plays a major role in inflammatory response, asthma, sepsis, and symptoms associated with the rhinoviral infection. It has long been speculated that a β-turn at the C-terminus of bradykinin plays a major role in the biological activity of the neuropeptide. The β-turn forming potential of bradykinin in three vastly different local chemical environments, DMSO, 9 : 1 dioxane/water, and in the presence of 7.4 mM lyso phosphatidylcholine micelles, was investigated using two-dimensional homonuclear nmr experiments coupled with simulated annealing calculations. The results of these investigations show that in all three systems residues 6-9 of the C-terminus adopt very similar β-turn like structures. These results suggest that the β-turn at the C-terminus of bradykinin is an important secondary structural feature for receptor recognition and binding. © 1994 John Wiley & Sons, Inc.
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  • 81
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using dynamic light scattering (DLS), we have measured the diffusion coefficient and internal motions of narrow topoisomer distributions of pUCl8 DNA (2687 base pairs) as a function of linking number. The topoisomer distributions were prepared by C-18 reversed phase high performance liquid chromatography separation of topoisomerase I/ethidium-generated topoisomer families. The measured diffusion coefficients agree well with those predicted by a Monte Carlo model for the generation of equilibrium ensembles of DNA topoisomers of defined linking number. The only parameters used in the model were the bending persistence length, torsional rigidity, and hydrodynamic radius of DNA known independently from other techniques. Two different values for the torsional rigidity, α = 4 · 10-12 and 8.8 · 10-12 dyn cm, were used. Intrachain interactions in the DNA were taken into account by using an “effective DNA radius,” which was varied between rDNA = 1-8 nm. The best agreement between the measured and calculated values was obtained for α = 4 · 10-12 dyn cm, rDNA = 4 nm. The internal motions of the DNA topoisomers were characterized by the amplitude of the fast relaxation of the DLS autocorrelation function. Our earlier result that supercoiling leads to a decrease in the amplitude of internal motion was confirmed. In addition, we see a characteristic maximum of the internal motion amplitude at a superhelix density of σ = -0.03. The maximum occurs in the same range as a structural transition in pUC8 dimers previously described by L. Song et al. (1990 J. Mol. Biol. 214, 307-326). © 1994 John Wiley & Sons, Inc.
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  • 82
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    Topics: Chemistry and Pharmacology
    Notes: The interaction of a series of 2-phenylquinoline derivatives with RNA was investigated by means of viscometric, pKa, spectroscopic, binding, Tm, and kinetic methods. Compounds 1,2, and 3 have a piperazyl substituent at the para, meta, or ortho position, respectively, while 4 has an unsubstituted phenyl ring. The pKa results suggest that 1 has three charges, 2 and 3 have more than two charges, and 4 has two charges at pH 6.2. Spectroscopic and Tm results indicate that 1 binds more strongly to RNA than 2-4. Kinetic and modeling results indicate that 1 is a threading intercalator while 2 and 4 are classical intercalators. All experimental results indicate that 3, which has a large twist between the phenyl and quinoline rings, binds weakly with RNA. © 1994 John Wiley & Sons, Inc.
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  • 83
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Urethane bonds, derived from the hydroxyl group of the tyrosine side chain, have been investigated as a new type of amide bond mimetic in the design of pseudopeptides. The structure of a representative cyclic pseudotetrapeptide that consists of an  -  Ala  -  Tyr(urethane) Ala  -  Tyr (urethane) sequence fused into a rigid ring has been studied in the solid state by x-ray crystallography and in solution by two-dimensional nmr techniques. The cyclic pseudotetrapeptide has an oblong shape. The backbone urethane bonds assume a trans-trans conformation. The carbonyl groups in the ring have an alternating pattern of down, up, down, up with respect to the average ring plane. Solution nmr studies give observed nuclear Overhauser effects and coupling constants largely in agreement with the crystal structure. However, in solution the observed structure is likely to be conformationally averaged, and in the averaged structure, the urethane bond is perpendicular to the plane of the aromatic ring of the tyrosine, while in the crystal it is close to this plane. These differences may be explained by intermolecular hydrogen-bonding interactions. Four aspects of the conformation of the cyclic pseudotetrapeptide were investigated in detail: the tyrosine residue with the attached side-chain urethane bond (the tyrosine-urethane unit), the conformation of the two urethane backbone linkages, the conformation of the two conventional peptide bonds within this unusual ring structure, and the tight turns within the cyclic pseudotetrapeptide. The conformation of the tight turns present in the cyclic pseudotetrapeptide is very similar to that of a β-bend of type II. Intermolecular hydrogen bonding, joining adjacent layers of the cyclic pseudotetrapeptide in the solid state, resemble a parallel β-pleated sheet. The presence of these structural motifs in the cyclic pseudotetrapeptide indicates that the tyrosine urethane unit may find applications in peptide and protein engineering. © 1994 John Wiley & Sons, Inc.
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  • 84
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    Biopolymers 34 (1994), S. 415-433 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have developed a model for the simulation of the structure and dynamics of covalently closed circular DNA. It is based on the generalization of the original Brownian dynamics algorithm [D. L. Ermak & J. A. McCammon (1978) Journal of Chemical Physics, Vol. 69, pp. 1352-1359; M. Fixman (1978) Journal of Chemical Physics, Vol. 69, pp. 1527-1537] developed for bead-chain models of linear DNA to a second order numerical integration [ A. Iniesta & J. Garcia de la Torre (1990) Journal of Chemical Physics.Vol. 92, pp. 2015-2018], which we extended here to accommodate the torsional potential. The topological constraints and torsional-bending coupling in superhelical DNA are explicitly taken into account in this work by adapting a model for torsional-bending motion of linear DNA developed by Allison et al. [S. A. Allison, R. Austin, & M. Hogan (1989) Journal of Chemical Physics, Vol. 90, pp. 3843-3854].The dynamics of closed DNAs of 1124 base pairs (380 nm in length) were simulated up to ≅ 40 μs for linking number differences ΔLk between 0 and -6. Each bead in the model corresponded to 37 base pairs.For -2 ≅ ΔLk -6, the writhing number appears to decay to a limiting negative value with a single exponential law, and the relaxation time of this decay, starting from a planar closed molecule, is 3-6 μs. For the trajectories studied here, the formation of the superhelix proceeds through an initial phase of 1-2 μs where a toroidal-like structure is formed, which then converts into an interwound structure starting from a random nucleation site. For one simulation at ΔLk = -6, a branched structure was observed that did not convert into the linear interwound form for the time course of the simulation (31 μs).A verification of the simulation was performed by computing the diffusion coefficient of the 1124 base pair circle through known hydrodynamic formulas or through the center of mass displacement, and comparing these theoretical values with diffusion coefficients previously measured by dynamic light scattering. © 1994 John Wiley & Sons, Inc.
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  • 85
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    Biopolymers 34 (1994), S. 443-445 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 86
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    Biopolymers 34 (1994), S. 337-346 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present a new method for measuring the widths and depths of the grooves formed within DNA helices. This method overcomes the limitations of simply measuring interstrand phosphate-phosphate distances and has the advantage of yielding continuous values for groove geometry along a DNA fragment. In the case of oligonucleotides, it also clearly indicates the zones in which grooves exist, bounded by two phosphodiester backbones. The methodology has been developed within the Curves algorithm for studying irregular DNA geometries and is based on the optimal, and generally curved, helical axis obtained by this analysis. © 1994 John Wiley & Sons, Inc.
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  • 87
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the component synthesis method (CSM) for analyzing the normal mode dynamics of macromolecules is reported. The procedure involves a reduction of the dimensions of the normal mode problems for large molecular systems and the accurate extraction of the low-frequency modes. A macromolecule is divided into small components based on a hierarchical clustering of the residues in the structure. Interactions between coupled components are treated by the method of static correlation. The normal modes of the components are obtained first, and a fraction of the low-frequency normal modes of the components under mutual correlations are then used as a reduced basis for solving for the normal modes of the whole molecule. Multiple components are introduced for large macromolecules so that the dimensions of the eigenvalue problems at the component level are small. The method is applied to the protein crambin. In test calculations in which the dimensions of the eigenvalue equations are reduced to 1/6 of their natural size, the errors in the normal mode frequencies calculated by the CSM procedure are only about 1-2% when compared with the exact values. The rms fluctuations of all atoms in crambin calculated by the CSM procedure are basically identical to the exact results. The CSM procedure is shown to be accurate for calculating the normal modes of large macromolecules with a significant reduction of the size of the problem. © 1994 John Wiley & Sons, Inc.
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  • 88
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    Biopolymers 34 (1994), S. 365-370 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Water loss during lyophilization of a 49.4 mg/mL solution of lysozyme in D2O was studied with ir spectroscopy using a low-temperature, single reflection, horizontal, attenuated, total reflectance accessory. Four regions of water loss were identified and assignable to different forms of bound water. The amide I band begins to shift to higher frequency while the amide II concurrently shifts to lower frequency and broadens after the first stage of water loss (sublimation) at -10°C. Additionally, the carboxylate band (at 1584 cm-1) shifts slightly to lower frequency. A second stage at 17°C is characterized by continued shifts in the carboxylate and amide II bands to low frequency, further broadening in the amide II and greater shift to high frequency in the amide I (ascribed to the removal of periphery water around the protein). At the third stage of water loss, the carboxylate band decreases substantially in relative absorbance (consistent with the removal of water from the carbonyl backbone). In the fourth and last stage, the carboxylate band nearly disappears and water loss is very slow. Based upon a final level of hydration of 0.037 h, the last stage corresponds to 25% completion of the removal of water associated with ionizable side chains. From start to finish, the amide I shifts 9 cm-1 to higher frequency. © 1994 John Wiley & Sons, Inc.
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  • 89
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using internal conformational degrees of freedom for biopolymers as natural variables, and introducing a Lagrangian dynamics approach, one can simulate time-dependent processes over a much longer time scale than in classical Newtonian molecular dynamics (MD) techniques. Two factors contribute to this: a substantial reduction in the number of degrees of freedom and a very large increase in the size of the time step. We present the Lagrangian equations of motion for repuckering transitions in model furanose (F), ribose (R), and 2′-deoxyribose (dR) ring systems using the pseudorotation phase angle as the single dynamic variable. As in most Lagrangian analyses, the effective masses for the R and dRmodels are dependent on conformation, and we test the behavior of this variable mass (VM) model. Since the variation in effective mass is small, the VM model is compared with a simplified constant mass (CM) model, which is shown to be an excellent approximation. The equations of motion for the CM and VM models are integrated with the leapfrog and the iterative leapfrog algorithms, respectively. The Lagrangian dynamics approach reduces the number of degrees of freedom from about 40 to 1, and allows the use of time steps on the order of 20 fs, about an order of magnitude greater than is used in conventional MD simulations. © 1994 John Wiley & Sons, Inc.
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  • 90
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    Biopolymers 34 (1994) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 91
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    Biopolymers 34 (1994), S. 481-488 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation of α-helical assembly by complexing biologically active peptides with de novo designed protein is described. The de novo designed protein described here is a cystinelinked 4-helix bundle protein constructed with 80 amino acid residues and forms a hydrophobic core region surrounded by 4 helices in an aqueous solution. The biologically active peptides, such as melittin and human growth hormone releasing factor, contain the sequences that are able to form amphiphilic helices. These peptides alone do not form the α-helix structure in a diluted solution with low ion strength. But on mixing with the designed helix bundle protein, the peptides are strongly bound to the protein with the induction of α-helical structure in the biologically active peptides. The content of induced α-helix is in accord with that estimated from the amphiphilic sequence. The results mean that a novel architecture composed of α-helices is formed. Fluorescent and temperature-scanning measurement revealed that the α-helical assembly is constructed with hydrophobic interaction. Also, it is shown by means of fluorescence depolarization that the assembly has a compact globular form corresponding to 1 : 1 complex. © 1994 John Wiley & Sons, Inc.
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  • 92
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The DNA interaction of derivatives of ellipticine with heterocyclic ring systems with three, four, or five rings and a dimethylaminoethyl side chain was studied. Optical spectroscopy of drug complexes with calf thymus DNA, poly [(dA-dT) · (dA-dT)], or poly [(dG-dC) · (dG-dC)] showed a 10 nm bathochromic shift of the light absorption bands of the pentacyclic and tetracyclic compounds upon binding to the nucleic acids, which indicates binding by intercalation. For the tricyclic compound a smaller shift of 1-3 nm was observed upon binding to the nucleic acids.Flow linear dichroism studies show that the geometry of all complexes is consistent with intercalation of the ring system, except for the DNA and poly [(dG-dC) · (dG-dC)] complexes of the tricyclic compound, where the average angle between the drug molecular plane and the DNA helix axis was found to be 65°.One-dimensional 1H-nmr spectroscopy was used to study complexes between d(CGCGATCGCG)2 and the tricyclic and pentacyclic compounds. The results on the pentacyclic compound show nonselective broadening due to intermediate chemical exchange of most oligonucleotide resonances upon drug binding. The imino proton resonances are in slow chemical exchange, and new resonances with upfield shifts approaching 1 ppm appear upon drug binding, which supports intercalative binding of the pentacyclic compound. The results on the tricyclic compound show more rapid binding kinetics and very selective broadening of resonances. The data suggest that the tricyclic compound is in an equilibrium between intercalation and minor groove binding, with a preference to bind close to the AT base pairs with the side chain residing in the minor groove. © 1994 John Wiley & Sons, Inc.
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  • 93
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    Biopolymers 34 (1994), S. 663-672 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A 16-residue amphiphilic oligopeptide (EAK16) with every other residue alanine and also containing glutamic acid and lysine (Ac-NH-AEAEAKAKAEAEAKAK-CONH2) is able to form an unusually stable β-sheet structure. The β-sheet structure is stable at very low concentrations in water and at high temperatures. Various pH changes at 1.5, 3, 7, and 11 had little effect on the stability of the β-sheet structure. The β-sheet structure was not altered significantly even in the presence of 0.1% SDS, 7 molar guanidine hydrochloride, or 8 molar urea. One of the structural characteristics of the EAK16 is its ionic self-complementarity in that ionic bonds and hydrogen bonds between Glu and Lys can form readily between two oligopeptide β-sheet structures. This structural feature is probably one of the factors that promotes its extreme stability. This is the first example of such an extended ionic self-complementarity in a protein structure. EAK16 and its related peptides may have applications as useful biomaterials. It also offers a good model for studying the mechanism of β-sheet formation. Because the oligopeptide can self-assemble to form a membranous structure, it may have relevance to origin of life research. © 1994 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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  • 94
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complex formation behaviors of an α-helical polypeptide containing pyridyl ligands in the side chains, poly (Nω-2-pyridylmethyl L-glutamine) (P2PG), were investigated by absorption and CD spectroscopy using Cu2+ ion as a guest molecule in 2,2,2-trifiuoroethanol solution. In the low Cu2+ ion concentration, P2PG exhibited the predominant formation of Cu2+ and two pyridyl side-chain complexes, involving a regular arrangement of the pyridyl side chains. On the other hand, the complexes were converted to Cu2+ and one pyridyl side-chain species with increasing Cu2+ ion concentration. The conversion was accompanied by the disappearance of the side-chain ordered structure without any changes in the backbone conformation. Moreover, the still remaining coordination sites of Cu2+ were capable of complexing monomer pyridine (Py) added as a second guest to form ternary complexes, P2PG-Cu2+-Py, following the reconstitution of the ordered structure on the periphery of the α-helix backbone. The unique characteristics of P2PG can be explained in terms of the restriction of the pyridyl side chains to form intramolecular chelate complexes, depending on the rigid α-helix conformation. © 1994 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
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  • 95
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 747-757 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bovine carbonmonoxy hemoglobin investigated with light scattering studies is found to dissociate from its native tetramer structure into dimers and monomers. The values of the hydrated tetramer radius, RT = 32.1 Å, and the fractional dissociation vs pH, have been obtained at different ionic strengths from the autocorrelation function of the scattered light.The results suggest that a relevant contribution to Hb dissociation is due to electrostatic effects and, by means of a model derived by Tanford, it has been possible to predict the behavior of dissociation. Among the findings of this approach, we recall the estimates of the electrostatic energy contributions to Hb dissociation, up to ≃ GRT, and the predicted charge of tetrameric Hb vs pH, which agrees very well with the experimental data. © 1994 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
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  • 96
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 799-804 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 97
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 783-797 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The secondary structure of xanthan in solutions of relatively low salt concentration and at room temperature has been investigated using static light scattering experiments. Additional evidence has been found for a dimeric structure at 25°C in 0.01M NaCl. From the experimental z-average mean square (ms) radius of gyration, a value for the persistence length p has been estimated, taking explicitly into account the polydispersity of the three samples used, which has been established by gel permeation chromatography (GPC) measurements. The experimental particle scattering functions of the three samples are consistent with theoretical estimates for polydisperse systems with the same value of p = 65 ± 10 nm and the molar mass per unit length for a dimeric structure.This secondary structure remains unaffected by the ionic strength in the 0.005-0.0lM range. Partial aggregation seems to occur at higher NaCl concentrations.Light scattering and GPC data show that heating the xanthan 0.01M NaCl solutions to about 70°C considerably reduces the Mw of the low molar mass sample (2.3 × 105-g·mol-1), contrary to what is observed for the high molar mass sample (1.8 × 106-g·mol-1). These experimental findings can be accounted for by a partial temperature-induced dissociation of the xanthan dimers according to an all-or-none mechanism. © 1994 John Wiley & Sons, Inc.
    Additional Material: 14 Ill.
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  • 98
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 34 (1994) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 99
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 34 (1994), S. 849-868 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A rigorous theory is developed for ethidium binding to linear and circular DNAs and for the ratios of topoisomers produced upon ligation of an equilibrium population of noncovalently closed circles in the presence of ethidium. Assuming an unwinding angle φE = 26° for intercalated ethidium, optimum values of the intrinsic binding constant, KE = 7.16 × 104 M-1, the intrinsic twist, l0 = 23.746 turns, and twist energy parameter, Et = 5250, are obtained by fitting the present theory to the data of Shore and Baldwin [(1993) Journal of Molecular Biology, Vol. 170, pp. 983-1007] for a 247 base pair DNA. A very good fit is achieved with these optimum values, but a poor fit results when the parameters estimated by Shore and Baldwin are employed in the same theory. Three assumptions employed in the analysis of Shore and Baldwin are found to be not strictly valid. Adoption of the present substantially larger Et value as representative of their short DNAs would allow the Et vs N data of Shore and Baldwin to conform to the shape predicted by Shimada Yamakawa [(1985) Journal of Molecular Biology, Vol. 184, pp. 319-329] and Frank-Kamenetskii et al. [(1985) Journal of Biomolecular Structure and Dynamics, Vol. 2, pp. 1005-1012], and would imply that all of their DNAs exist in a substantially stiffer than normal state. © 1994 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
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  • 100
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Commonly a key element enabling proteins to function is an amino acid residue or residues with functional side chains having shifted pKa values. This article reports the results on a set of protein-based polymers (model proteins) that exhibit hydrophobic folding and assembly transitions, and that have been designed for the purpose of achieving large hydrophobic-induced pKa shifts by selectively replacing Val residues by Phe residues. The high molecular weight polypentapeptides, actually poly (tricosapeptides) with six varied pentamers in fixed sequence, were designed and synthesized to have the same amino acid compositions but different proximities between a single aspartic acid residue and 5 Phe residues per 30 residues. With the 5 Phe residues distal from the Asp residue, the observed pKa shift was 2.9 when compared to the Val-containing reference. With the 5 Phe residues within 1 nm of the Asp residue, the pKa shift was 6.2. This represents a free energy of interaction of 8 kcal/moles. To our knowledge, this is the largest pKa shift documented for an Asp residue in a polypeptide- or protein-water system.Data are reviewed that do not support the usual electrostatic arguments for pKa shifts of charge-charge repulsion and/or unfavorable ion self-energies arising from displacement of water by hydrophobic moieties, but rather the data are interpreted to indicate the presence of an apolar-polar repulsive free energy of hydration, which results from a potentially highly cooperative competition between apolar and polar species for hydration. © 1994 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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