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  • Bone
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Diseases of the colon & rectum 42 (1999), S. 1225-1227 
    ISSN: 1530-0358
    Keywords: Colon cancer ; Adenocarcinoma ; Intramuscular metastasis ; Bone ; Heterotopic ossification ; Soft tissue tumor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract PURPOSE: This report presents a patient who developed severe buttock pain because of an ossified intramuscular metastasis from a sigmoid colon cancer. METHODS: This is a case report and review of the literature for intramuscular metastasis from colon cancer. RESULTS: Computed tomography and magnetic resonance imaging showed a soft-tissue mass with heavy calcification. Histologically, mature compact bone was observed with adenocarcinoma cells dispersed among the bony trabeculae. CONCLUSION: When an intramuscular mass is seen, even if it contains extensive calcification, metastasis from colon cancer should be included in differential diagnosis.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Skeletal radiology 28 (1999), S. 90-95 
    ISSN: 1432-2161
    Keywords: Key words DXA ; Bone ; Cadaver ; Biomechanics ; Metastases ; Fracture
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Objective. To determine whether the load-bearing capacity of human proximal femora with metastatic defects can be predicted from the bone mineral content. Design. The bone mineral content (BMC) of the total proximal femur was measured by dual-energy X-ray absorptiometry (DXA). The femurs were loaded so as to simulate stair ascent or external rotation. Patients. Simulated lytic defects were created using specialized cutting tools in the intertrochanteric region of 32 human cadaveric femora. Bone density measurements were made before and after creating defects. Results. A linear relation could be used to predict failure load from BMC or bone mineral density. The slope of the linear relation was greater for loads representing external rotation than for loads representing stair ascent. The linear relations suggest that the BMC measurements account for both the density of the host bone and the amount of bone removed by the defect. Conclusions. The data suggest that between 70% and 80% of the variation in failure load of human femora with lytic metastatic defects can be predicted from the BMC and that relations between BMC and failure load are sensitive to the type of loading. Combined with information on the loads associated with the activities of daily living, these data may be used to help identify patients in whom prophylactic stabilization might prevent a pathologic fracture.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Mund-, Kiefer- und Gesichtschirurgie 3 (1999), S. 140-145 
    ISSN: 1434-3940
    Keywords: Schlüsselwörter Konfokale Laser-Scanning-Mikroskopie ; Dunkelfeldmikroskopie ; Bisbenzimidmarkierung ; Knochen ; Strahlenfolgen ; Radiogener Osteozytentod ; Key words Confocal laser scanning microscopy ; Microscopy ; Bisbenzimide labelling ; Bone ; Radiation effects ; Osteocytes ; Osteoradionecrosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Early radiation effects on human bone may lead to osteoradionecrosis (ORN). Direct bone cellular lesions [28] as well as fibrous degeneration of blood vessels [21] are considered to be pathologically relevant. Only few data on initial subclinical radiation effects are available. Patients were grouped according to the dose of radiation and clinical findings. Group 1: sound human bone of lower jaw, mostly collected during orthodontic surgery (n = 10 patients); group 2: specimens of lower jaw from patients with ORN (n = 12 patients); group 3: specimens of lower jaw from patients with head and neck cancer who were preoperatively treated with 36 Gy radiation; group 4: specimens of lower jaw from patients with head and neck cancer (n = 9) who were treated with 60–70 Gy radiation. Specimens were studied by confocal laser scanning microscopy (CLSM), by conventional light microscopy (DL) and by flourescence darkfield microscopy (DFM) after bisbenzimide staining (H 33258) of the viable cellular nuclei. For the correlating study of identical areas in CLSM and DL the specimens were prepared according to the sawing and grinding technique [8]. All the radiated bony specimens, regardless of the dose of radiation, showed areas of extensive or total loss of vitality of the osteocytes. This finding was also evident after 36 Gy and a short interval between radiation and sample collection (group 3). Additionally, in CLSM micromorphologic lesions of the lamellate structure were seen. With these results we can confirm the loss of vitality of the osteocytes as an initial radiation effect as described earlier [10, 23, 28]. In addition to these findings, alteration of the lamellate microstructure was found in the early phase after radiation. The functional and mechanical significance of these findings should be the subject of further studies.
    Notes: Für die infizierte Osteoradionekrose (IORN) des Kiefers werden unterschiedliche pathogenetische Mechanismen initialer Strahlenfolgen im Knochen diskutiert: Wichtige Parameter sind dabei die direkte Zellschädigung der Osteozyten [28] und die Gefäßfibrosierung [21]. Bislang liegen wenige Kenntnisse zum Ausmaß der initialen, subklinischen Veränderungen vor. 4 Probengruppen wurden anhand verschiedener Patientenkollektive definiert: Gruppe 1: gesunde Unterkieferproben meist von orthodontischen Operationen (n = 10 Patienten); Gruppe 2: Unterkieferproben mit manifester IORN (n = 12 Patienten); Grruppe 3: Unterkieferproben nach 36 Gy präoperativer Radio(chemo)therapie (n = 9 Patienten); Gruppe 4: Unterkieferproben nach 60–70 Gy Bestrahlung ohne Hinweise auf IORN (n = 9 Patienten). Alle Proben wurden histotomographisch mit konfokaler Laser-Scanning-Mikroskopie (CLSM), durchlichtmikroskopisch (DL) und dunkelfeldmikroskopisch (DFM) nach Fluoreszenzmarkierung des intakten Zellkerns (Bisbenzimid H 33258) untersucht. Korrelierende Histologien identischer Probenareale erfolgten an Trenndünnschliffen [8]. Als Ergebnisse wurden gefunden: 1. Alle unterschiedlich bestrahlte Knochenproben zeigten Areale mit weitgehendem bis vollständigem Verlust vitaler Osteozyten. Diese Strahlenfolge trat auch schon nach 36 Gy und kurzem Intervall bis zur Operation (Gruppe 3) auf. 2. Im CLSM zeigten sich zusätzlich mikromorphologische Veränderungen der lamellären Struktur, die zwischen den Probengruppen progredient waren. Hieraus können folgende Schlußfolgerungen gezogen werden: 1. Der vorbeschriebene Vitalitätsverlust der Osteozyten [10, 23, 28] konnte als sehr frühe, initiale, radiogene Läsion bestätigt werden. 2. Zusätzlich zeigten sich Veränderungen der lamellären Mikroarchitektur des Knochens als frühe und im Gruppenvergleich progrediente Strahlenläsion. Die mikromechanisch funktionelle Bedeutung dieser Veränderung muß in weiterführenden Untersuchungen eruiert werden.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    European journal of orthopaedic surgery & traumatology 9 (1999), S. 251-254 
    ISSN: 1432-1068
    Keywords: Bone ; Scintigraphy ; symptomatic ; Knee ; Arthroplasty ; Os ; Scintigraphie ; Genou ; Arthroplastie ; Symptomatique
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Objectif: Evaluation de la scintigraphie osseuse dans l'arthroplastie totale de genou douloureux. Lieu: Hôpital universitaire, Maastricht et Hôpital Maasland, Sittard. Projet: Investigation clinique retrospective. Méthode: Les dossiers cliniques de 27 patients ayant subi une scintigraphie de l'os, ont été étudiés afin d'analyser les plaintes et la façon de décider le diagnostic. Ces patients avaient des symptômes persistants après l'arthroplastie totale du genou. En plus ont été étudiées les radiographies conventionelles et les scanographies isotopes, sans connaître les dossiers cliniques. Sur la base de ces données nous avons évalué les cas dans lesquels la scanographie isotope du genou a contribué de façon décisive au traitement future. Résultats: La scanographie isotope ne contribue pas à la planification du traitement, si l'examen physique ou les radiographies conventionelles n'ont pas apporté de diagnostic clinique. Il s'agissait ici de 37 % des patients de cette série. Dans les cas où le diagnostic clinique était fait, la scanographie isotope a influencé la décision de diagnostic de 65 % des patients. Cependant, pour les autres patients avec diagnostic clinique (35 %), ce ne fut pas le cas. Conclusion : La répresentation radionucléide est de valeur limitée dans le diagnostic d'une arthroplastie symptomatique totale du genou. Elle peut supporter ou rejeter un diagnostic clinique mais entraînera rarement un changement de traitement, dans l'absence de constatations anormales pendant les examens physiques ou radiologiques.
    Notes: Summary Objective: Determination of the value of bone scanning in symptomatic total knee arthroplasties. Setting Academic Hospital Maastricht and Maasland Hospital Sittard. Design: Retrospective clinical investigation. Method: The clinical reports of 27 patients, who underwent a bone scintigraphic study, were investigated for complaints and analysis of diagnostic decision making. These patients had persistent symptoms after total knee arthroplasty. In addition, conventional radiographs and the isotope scans were studied without knowledge of the clinical records. Based on these data we evaluated in which cases isotope scanning of the knee had contributed decisively to the further treatment. Results: Isotope scanning did not contribute to the treatment planning if physical examination or conventional radiographs had not led to a clinical diagnosis. This comprised 37% of the patients in our series. If a clinical diagnosis was present, isotope scanning did influence decision making in 65% of the patients. However in the remaining patients with a clinical diagnosis (35%) this was not the case. Conclusion: Radionuclide imaging is of limited value in the diagnostic process of symptomatic total knee arthroplasty. It may support or reject a clinical diagnosis, but in the absence of abnormal findings at physical examinations or radiologic studies, it seldom will induce a change in treatment
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    European journal of orthopaedic surgery & traumatology 9 (1999), S. 161-165 
    ISSN: 1432-1068
    Keywords: Bone ; Bone substitutes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Biocompatible calcium phosphate ceramics has been used for several years in orthopeadic surgery. We have been using two new synthetic biphasic calcium phosphate ceramics (BCP) since September 1996 for bone defect filling in any orthopaedic or trauma operation where autograft use was not possible or even wanted. The first, Eurocer 400® has 300 to 500 micron wide macropores with a totally interconnected porosity. This salt seed like product can be used in bone defect filling, when solidity is not a major concern. The second, Eurocer 200® has not totally interconnected 200 micron large pores. Its main characteristic is a mechanical resistance up to 30 Mpa. We use it in any case of weight-bearing surgery. Different sizes and presentation forms are available and will be chosen according to the recipient site shape. We report one hundred and fifty cases with a six to thirty month follow-up. In one third of the patients hip revision surgery was addressed. Another third concerned recent trauma or sequelae cases,.whereas the last third involved cold orthopaedic procedures. General principles are the need of a living and non-infected site after thorough debridement if necessary. Osteocompatibility of calcium phosphate ceramic is confirmed by our results. We report no mechanical failure. In all cases X-rays show a progressive integration, with new bone formation. Our substitutes have been histologically studied in nine cases, four to fifteen months after implantation. New bone formation around and in the substitute is impressive. Indeed, their good mechanical properties without loss of biological quality is the most relevant feature of these BCPs, leading to a wider indication field; therefore we have now abandoned the use of any bony auto, allo or xenograft.
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  • 6
    ISSN: 1433-7347
    Keywords: Key words Anterior cruciate ; ligament reconstruction ; Bone ; tunnel enlargement ; Hamstring ; tendons ; Magnetic resonance ; imaging ; Radiographic evaluation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Sports Science
    Notes: Abstract The aim of this study was to describe the contrast-enhanced magnetic resonance imaging (MRI) appearance of bone tunnel enlargement detected on radiography after anterior cruciate ligament (ACL) reconstruction with semitendinosus and gracilis tendon endobutton (STG-endobutton) fixation technique. Fourteen patients with a STG-endobutton ACL reconstruction were examined 3 months (n = 1), 1 year (n = 1) and 2 years (n = 12) postoperatively. An age- and sex-matched group with a bone–patellar tendon–bone (BTB) autograft ACL reconstruction with similar follow-up was taken as control. Data on clinical examination, laxity and isokinetic muscle torque measurements, anteroposterior and lateral view radiography were obtained, and knee scores (Lysholm and Tegner) were collected. Contrast-enhanced MRI was performed in the STG-endobutton group with a 1.5-T imager. There were no statistical differences between the groups with respect to clinical findings, stability tests, or knee scores. In the STG-endobutton group the average femoral and tibial bone tunnel diameter detected on anteroposterior view radiography had increased at 2-year follow-up by 33% and 23%, respectively. On MRI the ligamentous graft itself was not enhanced by the contrast medium whereas periligamentous tissue within and around the STG graft bundles showed mild contrast enhancement. In conclusion, the MRI results suggest that enhancing periligamentous tissue accumulated in and around the STG graft associated with the tunnel expansion. In spite of the significant bone tunnel enlargement observed on the follow-up radiography the STG-endobutton knees were stable and the patients satisfied.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 1432-5233
    Keywords: Key words Non-enzymatic glycosylation ; Advanced glycation endproducts ; Receptor for advanced glycation endproducts ; Diabetes mellitus ; Osteoblasts ; Bone ; Osteopenia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Advanced glycation endproducts have been implicated in the development of diabetic complications. In addition, these products could also mediate certain bone alterations such as diabetic osteopenia. Several receptors specific for advanced glycation endproduct-modified proteins have been characterized in different cell types, contributing to the recognition and degradation of senescent proteins. In the present report, we investigated the possible presence of advanced glycation endproduct-binding proteins on osteoblast-like cells. Both UMR106 and MC3T3E1 cell lines express specific advanced glycation endproduct-binding sites, with an affinity constant between 0.4 and 1.7 · 106 M−1, depending on the stage of osteoblastic differentiation; and with a receptor capacity of 1.5–2.0 · 107 sites/cell. Osteoblast-like cells were also found to participate both in the uptake and degradation of advanced glycation endproduct-modified bovine serum albumin at 37°C. Radiolabelled ligand blotting studies confirmed the presence of several membrane binding proteins, with apparent molecular masses of 50, 45–40, 30, 25 and 18 kDa; the major bands corresponded to 30 and 25 kDa proteins. This study provides evidence of the presence of advanced glycation endproduct-specific binding sites, and for their regulation with the stage of differentiation, in two osteoblast-like cells in culture.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    European journal of trauma 25 (1999), S. 230-236 
    ISSN: 1615-3146
    Keywords: Aneurysmatische Knochenzyste ; Knochentumor ; Hand ; Aneurysmal bone cyst ; Bone ; Hand
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Abstract The aneurysmal bone cyst localizised at the longfingers of the hand is an extremely rare clinical entity, particularly considering the age and the distinct aggressiveness in our case. In this specific case of a 53-year-old male the differentialdiagnosis as well as problems of the aneurysmal bone cyst with affection of the phalangeal bone will be discussed. Furthermore the various possibilities of therapy will be focussed on. At first the patient was treated with curettage followed by bone grafting. Already 5 months later a local recurrence appeared. The proximal phalangeal bone and the metacarpophalangeal joint V were almost distroyed. Aiming at preservation of a high funcionality of the hand we amputated the 5th finger in the metacarpophalangeal joint.
    Notes: Zusammenfassung Die aneurysmatische Knochenzyste mit Lokalisation an der Hand, insbesondere an den Phalangen, ist ein extrem seltenes Krankheitsbild. Auch das Alter des Patienten und die ausgeprägte Aggressivität unseres Falles sind bemerkenswert. Anhand der Krankengeschichte eines 53jährigen Mannes mit Befall der Grundphalanx des fünften Fingers der rechten Hand werden die Problemstellung bzw. Differentialdiagnose verdeutlicht und die verschiedenen Therapiemöglichkeiten besprochen. In unserem Fall wurde zunächst eine Kürettage mit anschließender Spongiosaaufftüllung durchgeführt. Bereits nach fünf Monaten kam es zu einem aggressiven Rezidiv mit Zerstörung der gesamten Grundphalanx und des Grundgelenks, so daß wir uns schließlich unter Berücksichtigung der bestmöglichen Funktion der Hand für eine Amputation des Kleinfingers entschieden haben.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Reproduktionsmedizin 15 (1999), S. 405-409 
    ISSN: 1434-808X
    Keywords: Schlüsselwörter Estrogenrezeptoren ; Knochen ; Arteriosklerose ; Endometrium ; Zentralnervensystem ; Key words Estrogen receptors ; Bone ; Arteriosclerosis ; Endometrium ; Central nervous system
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Summary Almost each cell in the body is estrogen-receptive. The strength of estrogen influence on organs or organ systems, however, may vary. Thus, estrogen withdrawal may have more or less severe pathophysiological consequences. Recently, the existence of two estrogen receptors has been established (estrogen receptor α and β = ERα and ERβ and several splice variants of these two basic receptor types have been desribed). This, together with our increasing knowledge about tissue-specific enhancer and repressor genes now allows a better understanding of the organ-specific effects of estrogens. In view of gynecological endocrinology, hormone replacement therapy with estrogens is beneficial for most organs in the body (bone, cardiovascular system, CNS). However, pure estrogen therapy may have deleterious effects in the endometrium of the uterus because it may initiate the development of uterine cancer. In the uterus of most species studied so far, no ERβ but only the classical ERα gene has been described. Hence, drug companies have now intensively begun to search for ERβ-specific estrogens. The first, relatively specific, non-steroidal product that addresses primarily the ERβ is the drug raloxifen, which has been recently introduced clinically. However, also some natural phyto-estrogens appear to be ERβ-specific.
    Notes: Zusammenfassung Fast jede Körperzelle ist estrogenrezeptiv. Es gibt allerdings Organe und Organsysteme, die besonders unter dem Einfluß von Estrogenen stehen und die sich bei Estrogenmangel krankhaft verändern können. Die vielfältigen Wirkungen von Estrogenen konnten nicht vollständig verstanden werden, solange die Existenz von nur einem Estrogenrezeptor quasi ein Dogma war. Erst die Klonierung eines zweiten (Estrogenrezeptor β = ERβ) sowie das bessere Verständnis von gewebespezifischen Enhancer- und Repressor-Genen konnten die vielfältigen und z. T. organspezifischen Wirkungen der Estrogene aufklären. Aus der Sicht der gynäkologischen Endokrinologie ist die Hormonersatztherapie mit Estrogenen für fast alle Organe des Körpers (Knochen, Herz-Kreislauf-System, Zentralnervensystem) segensreich. Eine nicht gestagenbegleitete Estrogentherapie kann allerdings verheerende Folgen am Endometrium mit Entwicklung eines Corpus-Karzinoms haben. Da der Uterus praktisch kein ERβ sondern nur den klassischen ERα exprimiert, hat eine intensive Suche nach ERβ-spezifischen Estrogenen begonnen. Ein erstes, halbwegs spezifisches nicht-steroidales Produkt scheint das kürzlich in die Klinik eingeführte Raloxifen zu sein, aber auch einige Phytoestrogene scheinen ERβ-spezifisch zu wirken.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    International journal of legal medicine 112 (1999), S. 195-197 
    ISSN: 1437-1596
    Keywords: Key words Trauma ; Calcification ; Bone ; Embolism ; Autopsy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Law
    Notes: Abstract Embolism of bone marrow to the lungs is a quite frequent finding after trauma but transport and deposition of solid bone is rarely seen, which may simply be because pulmonary calcifications are not recognized as bone fragments. We report on three patients with embolism of bone spicules to small lung arteries of about 0.5 mm in diameter which were plentiful in two of the patients on postmortem examination. However, the true nature of the emboli was only recognizable after decalcification of lung tissues. It appears that trauma occurring in a septic bone lesion has the greatest chance to provoke bone embolism. The bone spicules do not usually occlude vessel lumina and thus do not severely disturb the blood circulation in the lungs. The bone fragments become covered by endothelium and can remain recognizable for months or even years.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Annals of biomedical engineering 27 (1999), S. 508-516 
    ISSN: 1573-9686
    Keywords: Angiogenesis ; Artery ; Bone ; Creeping substitution ; Leukocytes ; Osteocytes ; Reperfusion injury ; Trauma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Technology
    Notes: Abstract An in vivo model has been developed for chronic observation of the effects of ischemia on cortical bone remodeling and perfused vascularity. Diaphragm occluders were implanted around the right common iliac artery of four rabbits and inflated to produce 10 h of ischemia to the limb. Microcirculation was monitored with intravital microscopy of injected fluorescent microspheres and FITC-Dextran 70 through a bone window, the tibial bone chamber implant (BCI). Bone resorption and apposition in the BCI were indicated with mineralization dyes. Between 2 and 12 h following release of the occluder, secondary ischemia/no-reflow and other evidence of reperfusion injury were observed. Vessel damage was suggested by abnormally high leakage of FITC-D70 from the few vessels perfused during secondary ischemia. In the weeks following occluder release perfused vasculature increased beyond pre-occlusion levels. Net bone resorption reached a maximum when vascularity passed normal levels. In order to further validate the arterial occlusion model for osteonecrosis, techniques for (1) confirming bone death and (2) detecting increased leukocyte adherence to endothelial cells were added. The dead cell stain Ethidium homodimer-1 was used to tag dead osteocytes immediately after occlusion and produced a measure designated “osteonecrosis index.” To detect leukocytes adhering to vessel walls, carboxyfluorescein diacetate, succinimidyl ester was injected at occluder release. An increase in the number of adherent leukocytes was detected. © 1999 Biomedical Engineering Society. PAC99: 8764Rr, 8717-d, 8719Tt
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Mund-, Kiefer- und Gesichtschirurgie 2 (1998), S. 141-145 
    ISSN: 1434-3940
    Keywords: Schlüsselwörter Konfokale Laser-Scanning-Mikroskopie ; Knochen ; Histotomographie ; Key words Confocal laser scanning microscopy ; Bone ; Histotomography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Objectives: Fixation (formalin), decalcification (sections) or mechanical treatment (grinding) all bear the risk of artifacts occurring during hard-tissue histology. Because studies on the etiology of pathological changes mostly focus on subclinical lesions, artifacts can simulate early changes or even be superimposed on existing changes. The objective of this study was to determine how artifacts can be reduced. Material and methods: In confocal laser scanning microscopy (CLSM) a focused laser beam scans the surface of the specimens and penetrates into the tissue. The intensity of the remitted light is recorded. The confocal effect is due to an extremely small aperture (pinhole), excluding light from out-of-focus planes of the sample. By stepwise movement of the object table, a tomographic series of tomographic images is obtained. Sound cortical bone samples of the lower jaw (n = 20) were studied by light microscopy and by CLSM, visualizing identical areas of a ground sectioned sample after H & E staining. Additionally, embedded and fresh blocks of tissue of the same bone sample were studied histotomographically in the CLSM. Results: (1) Light microscopic micromorphology of cortical bone can be visualized adequately in the CLSM; (2) many structures that can be visualized by light microscopy only after special staining (e.g., osteozyte processes) can be visualized by the CLSM using sample blocks without pretreatment. Conclusion: (1) Nondestructive subsurface histotomography by CLSM totally excludes mechanical artifacts; (2) physicochemical artifacts can be handled more easily because fresh samples can be studied; (3) pseudo-three-dimensional imaging allows histological interpretation of the tissue that is equivalent to macroscopic tomographic techniques (CT, MRT).
    Notes: Durch Fixierung (Formalin), Entkalkung (Schnitte) oder mechanische Bearbeitung (Schliffe) besteht bei der Hartgewebshistologie das Risiko physikalisch-chemischer oder mechanischer Artefakte. Da Studien zur Ätiopathogenese pathologischer Veränderungen meist auf subklinische Läsionen zielen, besteht die Gefahr, daß Artefakte frühe Veränderungen vortäuschen oder vorhandene überdecken. Es wird der Frage einer artefaktminimierten Histologie nachgegangen. Bei der konfokalen Laser-Scanning-Mikroskopie (CLSM) rastert ein monochromatischer Laserstrahl über die Probenoberfläche und dringt in das Gewebe ein. Die Intensität der remittierten Strahlung wird in einem Detektor gemessen. Durch eine konfokale Blende (pinhole) erreicht nur Laserlicht aus einer extrem dünnen In-Fokus-Ebene den Detektor, so daß schrittweises Bewegen des Objekttischs eine tomographische Serie von Einzelbildern visualisiert. Gesunde kortikale Knochenproben des Unterkiefers (n = 20) wurden durchlichtmikroskopisch und im CLSM untersucht: Dabei wurden identische Probenareale an Dünnschliffen nach HE-Färbung visualisiert. Außerdem wurden eingebettete und frische Gewebeblöcke derselben Knochenproben im CLSM histotomographiert. Als Ergebnisse wurden gefunden: 1. Lichtmikroskopische Mikromorphologie kortikalen Knochens ist im CLSM valide visualisierbar. 2. Viele lichtmikroskopisch erst nach Spezialfärbungen darstellbare Strukturen (z.B. Osteozytenfortsätze) können im CLSM an Probenblöcken ohne Vorbereitung mikroskopiert werden. Hieraus können folgende Schlußfolgerungen gezogen werden: 1. Die zerstörungsfreie Histotomographie des CLSM unter der Probenoberfläche vermeidet mechanische Artefakte völlig. 2. Physikalisch-chemische Artefakte werden kontrollierbar, da auch frische Proben mikroskopiert werden können. 3. Die pseudo-dreidimensionale Darstellung erlaubt eine histologische Gewebeinterpretation, die makroskopischen Schichtbildverfahren (CT, MRT) vergleichbar ist.
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  • 13
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    Springer
    Mund-, Kiefer- und Gesichtschirurgie 2 (1998), S. S37 
    ISSN: 1434-3940
    Keywords: Schlüsselwörter Kalzium ; Phosphat ; Hydroxylapatit ; Zement ; Knochenersatz ; Augmentation ; Key words Calcium ; Phosphate ; Hydroxyapatite ; Cement ; Bone ; Augmentation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Summary A new stoechiometric mixture of 27% dicalcium-phosphate (DCPA) and 73% tetra-calcium-phosphate (TTCP) can be prepared with water intraoperatively to a paste that subsequently sets to a structurally stabile implant composed of hydroxyapatite (HA). Primary setting time is about 20 min; pH during setting ranges from 6.5 to 8.5. There is no relevant curing heat or expansion or contraction. Compressive strength is about 50 MPa, tensile strength about 8 MPa. Over a period of about 4 h in physiological milieu, the cement converts to hydroxyapatite. This product is no longer redissolvable in normal body fluid. This cement can be used for non-load-bearing applications especially in craniofacial bone surgery. Cranial defects due to tumour or trauma as well as deficits in the facial skeleton may be reconstructed using this new biomaterial. In nine of ten patients we used the hydroxyapatite cement successfully for reconstructions in the craniofacial area. Fluid control of the operation field and implant site is extremely important and sometimes difficult to achieve. Further applications could be all non-load-bearing augmentations such as filling of blocked paranasal sinuses, of dentoalveolar cysts and defects following dental apectomy or fixation of implanted hearing-aid electrodes. The perspectives for the hydroxyapatite cement include its application as a carrier for osteogenic protein preparations, especially because of its isothermic reaction and intrinsic osteoconductive characteristics.
    Notes: Zusammenfassung Ein neuer Kalziumphosphatzement besteht aus 73% Tetrakalziumphosphat und 27% Kalziumhydrogenphosphat. Er bindet bei Körpertemperaturen nach Zugabe von Wasser innerhalb von 20 min ab. Innerhalb von 4 h wird der Zement zu Hydroxylapatitkristallen umgesetzt und damit wasserunlöslich. Der Abbindeprozeß verläuft nahezu isotherm im pH-Bereich von 6,5–8,5 ohne Schrumpfung. Die Druckfestigkeit liegt im ausgehärteten Zustand oberhalb von 50 MPa, die Zugfestigkeit bei mehr als 8 Mpa. Der Zement ist für alle nicht lasttragenden Knochenaugmentationen und Knochenersatzanwendungen insbesondere am Gesichtsschädel geeignet. Bei 9 von 10 Patienten benutzten wir den Zement erfolgreich für Rekonstruktionen im kraniofazialen Bereich. Beim klinischen Einsatz muß besonders auf sorgfältige Trockenlegung des Operations- und Implantationsfelds geachtet werden. Weitere Anwendungsmöglichkeiten sind das Auffüllen von ausgeräumten und verblockten Schädelhöhlen, die Fixation von implantierten Hörelektroden in der Hals-Nasen-Ohren-Heilkunde sowie das Auffüllen von Zysten und Wurzelspitzenresektionsdefekten in der dentoalveolären Chirurgie. Besondere Perspektiven bietet der Hydroxylapatitzement wegen seiner isothermen Abbindereaktion und seiner intrinsischen osteokonduktiven Eigenschaften als Trägermaterial für osteogene Proteinkomplexe.
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  • 14
    ISSN: 1432-2161
    Keywords: Key words Hemangiopericytoma ; Brain ; Bone ; Metastasis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Two cases of osseous hemangiopericytoma are presented that were initially diagnosed as primary in origin, but later reclassified as metastases, after a history of resection for an intracranial tumor was discovered. An intracranial source should be excluded before an isolated osseous tumor is determined to be a primary hemangiopericytoma.
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  • 15
    ISSN: 1423-0127
    Keywords: Muscular dystrophy ; Central nuclei ; Avian muscle ; Inflammation ; Dwarfism ; Lymphocyte ; Mechanochemical transducer ; Bone ; Steroid ; Fiber splitting
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Muscular dystrophy has long been believed to be characterized by degeneration and abortive regeneration of muscle fibers (the muscle degeneration theory), but unfortunately its pathogenesis is still unclear and an effective treatment has yet to be developed. As a challenge to the theory, we have proposed an alternative muscle-defective-growth theory and a further bone muscle growth imbalance hypothesis supposing possible defects in bone-growth-dependent muscle growth based on our findings in hereditary dystrophic dy mice (C57BL/6Jdy/dy). This review presents some new insights into the pathogenesis of the disease along with our hypothesis, focusing on the physiological meaning of centronucleation, one of the major pathological changes commonly observed in dystrophic muscles of man and experimental animals.
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Experimental biology online 3 (1998), S. 1-15 
    ISSN: 1430-3418
    Keywords: Bone ; Cell behaviour ; Chondrocyte ; Endothelia ; Epitenon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The motile behaviour, growth and reactions of osteoblasts, chondrocytes, epitenal cells and endothelia to culture on extended concave surfaces inside tubes is reported. Time-lapse video observations show that these cells can be successfully grown in quartz tubes for up to 21days. The cells would attach to the concave surfaces even when the radius of curvature was as low as 25 μm. The cells attached to the walls were not oriented. As culturing progressed the chondrocytes, osteoblasts and epitenon cells tended to detach from the walls of the tubes, forming long cords of cells attached to the walls at a few points only. Endothelial cells did not detach. These cords showed extensive lamellipodial activity at their points of attachment to the tube wall. The cells in these cords do not show contact inhibition of movement.
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  • 17
    ISSN: 1432-198X
    Keywords: Key words: Neonatal Bartter syndrome ; Bone ; Cal- cium ; Heparin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract. The neonatal Bartter syndrome (NBS) is associated with a complex disorder of mineral metabolism in children, including hypercalciuria, nephrocalcinosis, and diminished bone mineral density. Although cyclooxygenase inhibition usually brings about improvement in these findings, there is a variable component which is resistant to such therapy in many children. The factor mediating this disorder has not been identified. Blood and urine from 12 children with NBS were examined. When compared with samples from normal children and adults, all (NBS) sera reduced bone calcium uptake in a bone disc bioassay. This effect persisted in the presence of parathyroid hormone (PTH) antibody and PTH receptor blockade, indicating that neither PTH nor PTH related peptide was responsible. It was eliminated by indomethacin, suggesting that prostanoid generation was essential. Protamine was also inhibitory, as was the addition of ecteola, an anion binder. Activity could be recovered from ecteola by elution with hypertonic buffer. Urine samples from children with NBS had the same calcitropic effect. The agent was removed by ecteola and recovered by hypertonic elution. Activity was eliminated by protamine and by heparinase, but not by trypsin digestion. Size exclusion centrifugation showed that the activity was associated with a material between 10 and 30 kilodaltons. Finally, urine ecteola eluates from NBS patients raised serum concentrations of calcium after intraperitoneal injection in rats. These data suggest that children with NBS have a calcitropic substance in their serum and urine which is not found in normal individuals. The substance is heparin like, and mediates its effects through prostanoid production. These studies provide additional evidence against a direct renal cause of the urinary calcium disturbance characteristic of the disorder.
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  • 18
    Electronic Resource
    Electronic Resource
    Springer
    European spine journal 7 (1998), S. 257-259 
    ISSN: 1432-0932
    Keywords: Key words Angiomatosis ; Bone ; Osteolysis ; Cervical spine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The case of a 21/2-year-old boy with diffuse cystic angiomatosis of bone is presented. No evidence of visceral involvement was recorded. The clinical, radiographic and histologic findings during the course of the disease process are discussed. At the age of 15 years the patient died of neurologic alterations developed due to massive osteolysis and collapse of the cervical spine, and severe dyspnoea, secondary to persistent bilateral pleural effusions.
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  • 19
    Electronic Resource
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    Springer
    Skeletal radiology 27 (1998), S. 346-349 
    ISSN: 1432-2161
    Keywords: Key words Neurofibromatosis ; Malignant peripheral nerve sheath tumor ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Malignant peripheral nerve sheath tumors (MPNSTs) are uncommon sarcomas that almost always arise in soft tissue. They can develop in pre-existing neurofibromas or schwannomas, de novo from peripheral nerves, or following radiation therapy. Primary intraosseous MPNST is rare and has been reported most frequently in the mandible. Of the reported cases involving the long bones, none has been associated with neurofibromatosis type 1 (NF-1). We report a case of MPNST arising in the femur in a patient with NF-1.
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  • 20
    ISSN: 1432-2277
    Keywords: Key words Knee joint ; Vascularized graft ; Bone ; Transplantation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Four transplantations of an allogeneic vascularized human knee joint were performed at the Trauma Center Murnau between April 1996 and July 1997. The indication for the procedure was the total loss of the knee joint including the extensor apparatus due to severe trauma. These were the first transplants of this type. Management of patients started with closure of soft-tissue defects. After successful completion, stabilization was achieved with femoral and tibial nails plus a temporary arthroplasty. AB0 compatibility and a negative cross-match were the main criteria for selecting patients for transplantation. Interlocking compression nails were used for osteosynthesis. Vascular anastomoses between graft and recipient vessels were established by the end-to-side technique. Immunosuppression was started as a quadruple induction therapy for 3 days, then reduced to a two-drug maintenance therapy with cyclosporine and azathioprine. Six months posttransplantation the osteotomies were bridged by callus and the patients became completely mobile. Radiographic and histological examinations revealed vital graft tissue.
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  • 21
    ISSN: 1432-0878
    Keywords: Key words Osteoclasts ; Osteoblasts ; Osteocytes ; Bone ; Substance P (SP) ; Neurokinin-1 receptor (NK1-R) ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  Substance P (SP) is a neuropeptide that is released from axons of sensory neurons and causes signal transduction through the activation of the neurokinin-1 receptor (NK1-R). The present study demonstrates the distribution of SP-like-immunoreactive (SP-LI) axons and the localization of NK1-Rs in rat bone tissue using the avidin-biotin-peroxidase complex method. Axons with SP-LI were commonly found near the trabecular bone in the temporal bone marrow, but they were only sparsely distributed in the mandible, femur, and tibia. Immunoreactivity for NK1-Rs was found on the plasma membrane and in the cytoplasm of the osteoclasts. In the osteoblasts and osteocytes, a small number of weak, punctate immunoreactive products of NK1-Rs were distributed close to the plasma membrane. At the electron-microscopic level, immunoreactivity for NK1-R was distributed mainly in the whole cytoplasm, except for the clear zone of the osteoclasts, and in pit-like structures along the plasma membrane. The NK1-R-immunoreactive structures in the cytoplasm were divided into two types of organelles, consisting of vesicular and vacuolar structures (probably transport vesicles and early endosomes). In the osteoblasts and osteocytes, the number of NK1-R-positive vesicular structures was fewer than in the osteoclasts. These results thus suggest that SP secreted by the sensory axons could directly modulate bone metabolism via NK1-Rs.
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  • 22
    ISSN: 1432-0878
    Keywords: Key words Osteoclast ; Bone ; Bone resorption ; Alveolar bone ; Rat (Wistar)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  Glutaraldehyde-formaldehyde fixed undecalcified alveolar bone from 7-day-old rats was prepared for light and electron microscopy. Colloidal lanthanum was used as an ultrastructural tracer, and both random and semi-serial sections were examined. Lanthanum penetrated the infoldings of the ruffled border and some nearby vacuoles and vesicles. The majority of vacuoles and vesicles were lanthanum-free. Some osteoclast profiles contained a large vacuole with a cell enclosed in its interior. The enclosed cell exhibited an irregular nucleus containing condensed peripheral chromatin, intact cytoplasmic organelles, conspicuous rough endoplasmic reticulum and large blebs on the cell surface. These features are characteristic of osteoblasts or bone-lining cells or immature osteocytes which may be undergoing apoptosis or necrosis. The observation of remnants of cellular structures within internalized osteoclast vacuoles, together with the above results, suggests that osteoclasts engulf and probably degrade dying osteoblasts/bone-lining cells or immature osteocytes.
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  • 23
    Electronic Resource
    Electronic Resource
    Springer
    Clinical rheumatology 17 (1998), S. 47-51 
    ISSN: 1434-9949
    Keywords: Bone ; Fatigue ; Stress fracture ; Stress reaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Stress fractures are being increasingly reported as a common cause of morbidity in both healthy populations and those withunderlying diseases involving abnormal bone. An insight into the types and pathogenesis of stress fractures is necessary to considering the diagnosis, management and prevention of such conditions. The classification, aetiology and aspects of management are discussed.
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  • 24
    ISSN: 1434-5196
    Keywords: Key words Identification ; Forensic osteology ; DNA typing ; PCR ; Brain ; Bone ; Schlüsselwörter Identifikation ; Forensische ; Osteologie ; DNA-Typisierung ; PCR ; Gehirn ; Knochen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Law
    Description / Table of Contents: Zusammenfassung Ein weitgehend skelettierter Kleinkind-Schädel konnte mittels forensisch-anthropologischer Befunderhebung klassifiziert und mittels erfolgreicher DNA-PCR-Typisierung am Hirnbrei, nicht jedoch am Schädelknochen identifiziert werden. Die vorgestellte Kasuistik belegt eindrücklich, daß eine sorgfältige forensisch-anthropologische Befunderhebung eine wesentliche Grundlage für die molekularbiologische Identifizierung an Skeletteilen bildet und daß auch an fortgeschritten fäulnisverändertem Gehirn bei feuchtem Lagerungsmilieu eine DNA-PCR-Typisierung erfolgreich sein kann.
    Notes: Abstract The skull of a small child, which was largely devoid of soft tissue, was classified according to forensic/anthropological findings and could be identified on the basis of DNA typing by PCR using residual brain tissue, but not bone. This case illustrates the fact that careful forensic/anthropological investigation is an important basis for molecular biological identification from skeletal remains and that DNA typing by PCR may even be possible on brain tissue that has been exposed to damp conditions and is an advanced state of decomposition.
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  • 25
    ISSN: 0006-3525
    Keywords: folding type-specific secondary structure propensities ; amino acids ; α-helical proteins ; β sheet proteins ; α/β proteins ; α+β proteins ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Folding type-specific secondary structure propensities of 20 naturally occurring amino acids have been derived from α-helical, β-sheet, α/β, and α+β proteins of known structures. These data show that each residue type of amino acids has intrinsic propensities in different regions of secondary structures for different folding types of proteins. Each of the folding types shows markedly different rank ordering, indicating folding type-specific effects on the secondary structure propensities of amino acids. Rigorous statistical tests have been made to validate the folding type-specific effects. It should be noted that α and β proteins have relatively small α-helices and β-strands forming propensities respectively compared with those of α+β and α/β proteins. This may suggest that, with more complex architectures than α and β proteins, α+β and α/β proteins require larger propensities to distinguish from interacting α-helices and β-strands. Our finding of folding type-specific secondary structure propensities suggests that sequence space accessible to each folding type may have differing features. Differing sequence space features might be constrained by topological requirement for each of the folding types. Almost all strong β-sheet forming residues are hydrophobic in character regardless of folding types, thus suggesting the hydrophobicities of side chains as a key determinant of β-sheet structures. In contrast, conformational entropy of side chains is a major determinant of the helical propensities of amino acids, although other interactions such as hydrophobicities and charged interactions cannot be neglected. These results will be helpful to protein design, class-based secondary structure prediction, and protein folding. © 1998 John Wiley & Sons, Inc. Biopoly 45: 35-49, 1998
    Additional Material: 6 Ill.
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  • 26
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 45 (1998), S. 69-83 
    ISSN: 0006-3525
    Keywords: DNA branched junctions ; branch migration ; superhelical torque ; control of DNA structure ; endonuclease VII ; nanomechanical device ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: DNA branched junctions are analogues of Holliday junction recombination intermediates. Partially mobile junctions contain a limited amount of homology flanking the branch point. A partially mobile DNA branched junction has been incorporated into a synthetic double-stranded circular DNA molecule. The junction is flanked by four homologous nucleotide pairs, so that there are five possible locations for the branch point. Two opposite arms of the branched junction are joined to form the circular molecule, which contains 262 nucleotides to the base of the junction. This molecule represents a system whereby torque applied to the circular molecule can have an impact on the junction, by relocating its branch point. Ligation of the molecule produces two topoisomers; about 87% of the product is a relaxed molecule, and the rest is a molecule with one positive supercoil. The position of the branch point is assayed by cleaving the molecule with endonuclease VII. We find that the major site of the branch point in the relaxed topoisomer is at the maximally extruded position in the relaxed molecule. Upon the addition of ethidium, the major site of the branch point migrates to the minimally extruded position. © 1998 John Wiley & Sons, Inc. Biopoly 45: 69-83, 1998
    Additional Material: 9 Ill.
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  • 27
    ISSN: 0006-3525
    Keywords: conformation ; aggregation ; κ-carrageenan ; flow field-flow fractionation ; multiangle light scattering ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relatively novel combination of flow field-flow fractionation (FFF) and multiangle light scattering (MALS) was employed to study a nondegraded κ-carrageenan in different 0.1M salt solutions. The applicability of the technique was tested, and the effects of salt type and salt composition on the molar mass and radius of gyration were studied. A conformational ordering was induced at room temperature by switching the solvent from 0.1M NaCl (coil form) to 0.1M NaI (helix form). An approximate doubling of the average molar mass and an increase in radius of gyration was then observed, in agreement with results obtained previously using size exclusion chromatography-MALS. This increase in size was attributed to conformational ordering and to the formation of double helices. Severe aggregation was observed above 40% CsI in the 0.1M mixed salt solution of CsI and NaI. This was ascribed to the association of helices into large aggregates. For these large associates, having molar masses of several millions, a reversal of the elution order in flow FFF was detected. © 1998 John Wiley & Sons, Inc. Biopoly 45: 85-96 1998
    Additional Material: 10 Ill.
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  • 28
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 45 (1998), S. 119-133 
    ISSN: 0006-3525
    Keywords: conformations of D-alanyl-D-alanine ; β-lactam ; structural overlay ; AMBER force field ; AM1 ; ab initio ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this article a conformational analysis of the D-alanyl-D-alanine dipeptide, both charged and neutral, has been carried out. The preferred conformations were determined by means of ab initio and semiempirical quantum, together with empirical force field calculations. The AMBER* force field and the 6-31 + G** and 6-31G** ab initio levels give rise to a coincident minimum energy structure, which, on the other hand, differs from that determined by AM1, 3-21 + G, and 3-21G. The solvent effect on the different charged and neutral conformations have been considered through the AMSOL semiempirical method. A quantification regarding the structural similarities between the different dipeptide conformations and the ampicillin has been performed. The results show that the best overlay is attained by the minimum structure energy obtained by using the 6-31 + G** methodology, which presents a planar amidic nitrogen. © 1998 John Wiley & Sons, Inc. Biopoly 45: 119-133, 1998
    Additional Material: 5 Ill.
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  • 29
    ISSN: 0006-3525
    Keywords: chemical oxidation ; cellulose ; conformational transition ; capillary viscosity ; microcalorimetry ; calcium ions ; gels ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational behavior of different molecular weight fractions of a synthetic C6-oxidized derivative of cellulose were investigated by means of capillary viscometry, CD, and microcalorimetric measurements. Experiments were carried out in the presence of either monovalent or divalent counterions.The experimental data indicated that C6-oxidized cellulose can assume an ordered extended conformation at low ionic strength, induced by the intrachain repulsions of negative charges. This conformation was suggested to be very similar to the fully extended structure of cellulose. In addition to this, upon increasing the ionic strength, a conformational transition of the order-to-disorder type occurred. In fact, the screening of the electrostatic repulsions introduced a number of conformational kinks into the cellulosic backbone, which enabled the polymer to assume a more coiled conformation hence producing less viscous aqueous solutions. © 1998 John Wiley & Sons, Inc. Biopoly 45: 157-163, 1998
    Additional Material: 6 Ill.
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  • 30
    ISSN: 0006-3525
    Keywords: conformational stability ; biological polyelectrolytes ; enthalpy ; entropy ; conformational transitions ; carrageenan ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new method is proposed for the determination of the enthalpy and entropy changes of nonionic origin upon conformational transition of linear biopolyelectrolytes in solution. For all transition midpoints, defined by given temperature and ionic strength, the total free energy change of the system is zero, which means that the nonionic contribution to the free energy change is equal in value and opposite in sign to the polyelectrolytic one. The counterion condensation theory of linear polyelectrolytes provides for the appropriate analytical expression to be used in such calculations. Linear plots of the proper functions of the calculated free energy changes vs the proper functions of temperature allows for the determination of the enthalpic and entropic terms of the nonionic free energy change of transition.The method has been applied to the extensive available data of the ion-induced conformational change of κ-carrageenan, a linear sulfated galactan extracted from seaweeds. The method has proved very successful, with the results showing a remarkable convergency of the enthalpy values for different monovalent counterions. On the other hand, the above approach has made it possible to explain the known effect of counterion specificity on the transition by a small difference in the nonionic entropic contributions. © 1998 John Wiley & Sons, Inc. Biopoly 45: 203-216, 1998
    Additional Material: 5 Ill.
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  • 31
    ISSN: 0006-3525
    Keywords: uv resonance Raman spectroscopy ; Raman cross section ; hypochromism ; DNA ; deoxynucleoside ; protein ; aromatic amino acid ; virus assembly ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ultraviolet resonance Raman (UVRR) spectra of H2O and D2O solutions of the nucleoside (dA, dG, dC, dT) and aromatic amino acid (Phe, Trp, Tyr) constituents of DNA viruses have been obtained with laser excitation wavelengths of 257, 244, 238, and 229 nm. Using the 981 cm-1 marker of Na2SO4 as an internal standard, Raman frequencies and scattering cross sections were evaluated for all prominent UVRR bands at each excitation wavelength. The results show that UVRR cross sections of both the nucleosides and amino acids are strongly dependent on excitation wavelength and constitute sensitive and selective probes of the residues. The results provide a library of UVRR marker bands for structural analysis of DNA viruses and other nucleoprotein assemblies. © 1998 John Wiley & Sons, Inc. Biopoly 45: 247-256, 1998
    Additional Material: 4 Ill.
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  • 32
    ISSN: 0006-3525
    Keywords: hemoglobin ; hexagonal bilayer ; Lumbricus ; electron microscopy ; three-dimensional reconstruction ; small-angle x-ray scattering ; three-dimensional models ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The quaternary structure of Lumbricus terrestris hemoglobin was investigated by small-angle x-ray scattering (SAXS). Based on the SAXS data from several independent experiments, a three-dimensional (3D) consensus model was established to simulate the solution structure of this complex protein at low resolution (about 3 nm) and to yield the particle dimensions. The model is built up from a large number of small spheres of different weights, a result of the two-step procedure used to calculate the SAXS model. It accounts for the arrangement of 12 subunits in a hexagonal bilayer structure and for an additional central unit of cylinder-like shape. This model provides an excellent fit of the experimental scattering curve of the protein up to h = 1 nm-1 and a nearly perfect fit of the experimental distance distribution function p(r) in the whole range. Scattering curves and p(r) functions were also calculated for low-resolution models based on 3D reconstructions obtained by cryoelectron microscopy (EM). The calculated functions of these models also provide a very good fit of the experimental scattering curve (even at h 〉 1 nm-1) and p(r) function, if hydration is taken into account and the original model coordinates are slightly rescaled. The comparison of models reveals that both the SAXS-based and the EM-based model lead to a similar simulation of the protein structure and to similar particle dimensions. The essential differences between the models concern the hexagonal bilayer arrangement (eclipsed in the SAXS model, one layer slightly rotated in the EM model), and the mass distribution, mainly on the surface and in the central part of the protein complex. © John Wiley & Sons, Inc. Biopoly 45: 289-298, 1998
    Additional Material: 4 Ill.
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  • 33
    ISSN: 0006-3525
    Keywords: conformational changes ; vicinal glycosylation ; branched α-l-Rhap(1-2)[β-d-Galp(1-3)]-β-d-Glc1-OMe trisaccharide ; parent disaccharides ; hydrogen bond ; isotope effect ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformations of the α-l-Rhap(1-2)-β-d-Glc1-OMe and β-d-Galp(1-3)-β-d-Glc1-OMe disaccharides and the branched title trisaccharide were examined in DMSO-d6 solution by 1H-nmr. The distance mapping procedure was based on rotating frame nuclear Overhauser effect (NOE) constraints involving C- and O-linked protons, and hydrogen-bond constraints manifested by the splitting of the OH nmr signals for partially deuteriated samples. An “isotopomer-selected NOE” method for the unequivocal identification of mutually hydrogen-bonded hydroxyl groups was suggested. The length of hydrogen bonds thus detected is considered the only one motionally nonaveraged nmr-derived constraint. Molecular mechanics and molecular dynamics methods were used to model the conformational properties of the studied oligosaccharides. Complex conformational search, relying on a regular Φ,Ψ-grid based scanning of the conformational space of the selected glycosidic linkage, combined with simultaneous modeling of different allowed orientations of the pendant groups and the third, neighboring sugar residue, has been carried out. Energy minimizations were performed for each member of the Φ,Ψ grid generated set of conformations. Conformational clustering has been done to group the minimized conformations into families with similar values of glycosidic torsion angles. Several stable syn and anti conformations were found for the 1→2 and 1→3 bonds in the studied disaccharides. Vicinal glycosylation affected strongly the occupancy of conformational states in both branches of the title trisaccharide. The preferred conformational family of the trisaccharide (with average Φ,Ψ values of 38°, 17° for the 1→2 and 48°, 1° for the 1→3 bond, respectively) was shown by nmr to be stabilized by intramolecular hydrogen bonding between the nonbonded Rha and Gal residues. © 1998 John Wiley & Sons, Inc. Biopoly 46: 417-432, 1998
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  • 34
    Electronic Resource
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    New York : Wiley-Blackwell
    Biopolymers 46 (1998), S. 489-492 
    ISSN: 0006-3525
    Keywords: refractive index increment ; proteins ; solvent ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The refractive index increment of a protein solution is a property not only of the protein, but also of the solvent. This is demonstrated theoretically and confirmed experimentally using analytical interferometry. © 1998 John Wiley & Sons, Inc. Biopoly 46: 489-492, 1998
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  • 35
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    New York : Wiley-Blackwell
    Biopolymers 47 (1998), S. 1-1 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
    Type of Medium: Electronic Resource
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  • 36
    ISSN: 0006-3525
    Keywords: hepatitis A ; synthetic peptides ; CD ; liposomes ; computational study ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The present study was undertaken to examine the structural features that may be important to explain the immunogenicity of the (110-121) peptide sequence (FWRGDLVFDFQV) of VP3 capsid protein of hepatitis A virus. A conformational analysis of the preferred conformations by CD and molecular mechanics was carried out. Present results suggest that the interaction with liposomes as biomembrane model induces and stabilizes the amphipathic β-structure of the peptide.To study the contribution of amino acid replacements at the RGD tripeptide as well as the influence of the peptide chain length on peptide conformation, solid-phase peptide synthesis of several peptide analogs was carried out and the peptide conformation was studied using CD spectroscopy. The results show that the RGD sequence is necessary to induce the β-structure in the presence of liposomes. © 1998 John Wiley & Sons, Inc. Biopoly 45: 479-492, 1998
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  • 37
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    Biopolymers 46 (1998), S. 31-37 
    ISSN: 0006-3525
    Keywords: DNA liquid crystals ; DNA fragments ; screened Coulomb interactions ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The critical volume fractions pertaining to the formation of DNA liquid crystals were obtained from polarization microscopy, 31P-nmr, and phase separation experiments. The DNA length (approximately one to two times the persistence length 50 nm), ionic strength, and counterion variety dependencies are reported. The cholesteric-isotropic transition is interpreted in terms of the coexistence equations, which are derived from the solution free energy including orientational entropy and excluded volume effects. With the wormlike chain as reference system, the electrostatic contribution to the free energy is evaluated as a thermodynamic perturbation in the second virial approximation with a Debye-Hückel potential of mean force. The hard core contribution has been evaluated with scaled particle theory and/or a simple generalization of the Carnahan-Starling equation of state for hard spheres. For sufficiently high ionic strengths, the agreement is almost quantitative. At lower amounts of added salt deviations are observed, which are tentatively attributed to counterion screening effects. The contour length dependence agrees with a DNA persistence length 50 nm. © 1998 John Wiley & Sons, Inc. Biopoly 46: 31-37, 1998
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  • 38
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    Biopolymers 46 (1998), S. 245-252 
    ISSN: 0006-3525
    Keywords: gelatin ; gelation ; atomic force microscopy ; interfacial rheology ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Gelation of gelatin under various conditions has been followed by atomic force microscopy (AFM) with the objective of understanding more fully the structure formed during the gelation process. AFM images were obtained of the structures formed from both the bulk sol and in surface films during the onset of gelation. While gelation occurred in the bulk sol, the extent of helix formation was monitored by measurements of optical rotation, and the molecular aggregation was imaged by AFM. Interfacial gelatin films formed at the air-water interface were also studied. Measurements of surface tension and surface rheology were made periodically and Langmuir-Blodgett films were drawn from the interface to allow AFM imaging of the structure of the interfacial layer as a function of time. Structural studies reveal that at low levels of helical content the gelatin molecules assemble into aggregates containing short segments of dimensions comparable to those expected for gelatin triple helices. With time larger fibrous structures appear whose dimensions suggest that they are bundles of triple helices. As gelation proceeds, the number density of fibers increases at the expense of the smaller aggregates, eventually assembling into a fibrous network. The gel structure appears to be sensitive to the thermal history, and this is particularly important in determining the structure and properties of the interfacial films. © 1998 John Wiley & Sons, Inc. Biopoly 46: 245-252, 1998
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  • 39
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    Biopolymers 48 (1998), S. 65-81 
    ISSN: 0006-3525
    Keywords: nucleotide analogue interference mapping ; phosphorothioate ; group I intron ; interference suppression ; RNA ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this review I will outline several chemogenetic approaches used to determine the chemical basis of large ribozyme function and structure. The term chemogenetics was first used to describe site-specific functional group modification experiments in the analysis of DNA-protein interactions. Within the past few years equivalent experiments have been performed on large catalytic RNAs using both single-site substitution and interference mapping techniques with nucleotide analogues. While functional group mutagenesis is an important aspect of a chemogenetic approach, chemical correlates to genetic revertants and suppressors must also be realized for the genetic analogy to be intellectually valid and experimentally useful. Several examples of functional group revertants and suppressors have now been obtained within the Tetrahymena group I ribozyme. These experiments define an ensemble of tertiary hydrogen bonds that have made it possible to construct a detailed model of the ribozyme catalytic core. The model includes a functionally important monovalent metal ion binding site, a wobble-wobble receptor motif for helix-helix packing interactions, and a minor groove triple helix. © 1998 John Wiley & Sons, Inc. Biopoly 48: 65-81, 1998
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  • 40
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    Biopolymers 48 (1998), S. 83-96 
    ISSN: 0006-3525
    Keywords: nucleic acid ; disulfide cross-link ; structure ; dynamics ; stability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this review I discuss straightforward and general methods to modify nucleic acid structure with disulfide cross-links. A motivating factor in developing this chemistry was the notion that disulfide bonds would be excellent tools to probe the structure, dynamics, thermodynamics, folding, and function of DNA and RNA, much in the way that cystine cross-links have been used to study proteins. The chemistry described has been used to synthesize disulfide cross-linked hairpins and duplexes, higher order structures like triplexes, nonground-state conformations, and tRNAs. Since the cross-links form quantitatively by mild air oxidation and do not perturb either secondary or tertiary structure, this modification should prove quite useful for the study of nucleic acids. © 1998 John Wiley & Sons, Inc. Biopoly 48: 83-96, 1998
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  • 41
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    Biopolymers 48 (1998), S. 113-135 
    ISSN: 0006-3525
    Keywords: divalent cations ; magnesium ; RNA ; ion binding ; RNA folding ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Divalent cations, like magnesium, are crucial for the structural integrity and biological activity of RNA. In this article, we present a picture of how magnesium stabilizes a particular folded form of RNA. The overall stabilization of RNA by Mg2+ is given by the free energy of transferring RNA from a reference univalent salt solution to a mixed salt solution. This term has favorable energetic contributions from two distinct modes of binding: diffuse binding and site binding. In diffuse binding, fully hydrated Mg ions interact with the RNA via nonspecific long-range electrostatic interactions. In site binding, dehydrated Mg2+ interacts with anionic ligands specifically arranged by the RNA fold to act as coordinating ligands for the metal ion. Each of these modes has a strong coulombic contribution to binding; however, site binding is also characterized by substantial changes in ion solvation and other nonelectrostatic contributions. We will show how these energetic differences can be exploited to experimentally distinguish between these two classes of ions using analyses of binding polynomials. We survey a number of specific systems in which Mg2+-RNA interactions have been studied. In well-characterized systems such as certain tRNAs and some rRNA fragments these studies show that site-bound ions can play an important role in RNA stability. However, the crucial role of diffusely bound ions is also evident. We emphasize that diffuse binding can only be described rigorously by a model that accounts for long-range electrostatic forces. To fully understand the role of magnesium ions in RNA stability, theoretical models describing electrostatic forces in systems with complicated structures must be developed. © 1999 John Wiley & Sons, Inc. Biopoly 48: 113-135, 1998
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  • 42
    ISSN: 0006-3525
    Keywords: 1H-nmr ; molecular modeling ; peptaibol ; peptide-lipid interaction ; sodium dodecyl sulfate micelles ; trichorzianin TA VII ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Trichorzianin TA VII, Ac0 U1 A2 A3 U4 J5 Q6 U7 U8 U9 S10 L11 U12 P13 V14 U15 I16 Q17 Q18 Fol19, is a nonadecapeptide member of the peptaibol antibiotics biosynthesized by Trichoderma soil fungi, which is characterized by a high proportion of the α,α-dialkylated amino acids, α-aminoisobutyric acid (Aib, U) and isovaline (Iva, J), an acetylated N-terminus and a C-terminal phenylalaninol (Pheol, Fol). The main interest in such peptides stems from their ability to interact with phospholipid bilayers and form voltage-dependent transmembrane channels in planar lipid bilayers. In order to provide insights into the lipid-peptide interaction promoting the voltage gating, the conformational study of TA VII in the presence of perdeuterated sodium dodecyl sulfate (SDS-d25) micelles has been carried out. 1H sequential assignments have been performed with the use of two-dimensional homo- and -heteronuclear nmr techniques including double quantum filtered correlated spectroscopy, homonuclear Hartmann-Hahn, nuclear Overhauser effect spectroscopy, 1H-13C heteronuclear single quantum correlation, and heteronuclear multiple bond correlation. Conformational parameters, such as 3JNHCαH coupling constants, temperature coefficients of amide protons (Δδ/ΔTNH) and quantitative nuclear Overhauser enhancement data, lead to detailed structural information. Ninety-eight three-dimensional structures consistent with the nmr data were generated from 231 interproton distances and six Φ dihedral angle restraints, using restrained molecular dynamics and energy minimization calculations. The average rms deviation between the 98 refined structures and the energy-minimized average structure is 0.59 Å for the backbone atoms. The structure of trichorzianin TA VII associated with SDS micelles, as determined by these methods, is characterized by two right-handed helical segments involving residues 1-8 and 11-19, linked by a β-turn that leads to an angle about 90°-100° between the two helix axes; residues 18 and 19 at the end of the C-terminal helix exhibit multiple conformations. © 1998 John Wiley & Sons, Inc. Biopoly 46: 75-88, 1998
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  • 43
    ISSN: 0006-3525
    Keywords: 9-hydroxyellipticine ; DNA ; CD ; linear dichroism ; resonance light scattering ; intercalation ; drug-drug interactions ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding of 9-hydroxyellipticine to calf thymus DNA, poly[d(A-T)]2, and poly-[d(G-C)]2 has been studied in detail by means of CD, linear dichroism, resonance light scattering, and molecular dynamics. The transition moment polarizations of 9-hydroxyelliptiycine were determined in polyvinyl alcohol stretched film. Spectroscopic solution studies of the DNA/drug complex are combined with theoretical CD calculations using the final 50 ps of a series of molecular dynamics simulations as input. The spectroscopic data shows 9-hydroxyellipticine to adopt two main binding modes, one intercalative and the other a stacked binding mode involving the formation of drug oligomers in the DNA major groove. Analysis of the intercalated binding mode in poly[d(A-T)]2 suggests the 9-hydroxyellipticine hydroxyl group lies in the minor groove and hydrogen bonds to water with the pyridine ring protruding into the major groove. The stacked binding mode was examined using resonance light scattering and it was concluded that the drug was forming small oligomer stacks rather than extended aggregates. Reduced linear dichroism measurements suggested a binding geometry that precluded a minor groove binding mode where the plane of the drug makes a 45° angle with the plane of the bases. Thus it was concluded that the drug stacks in the major groove. No obvious differences in the mode of binding of 9-hydroxyellipticine were observed between different DNA sequences; however, the stacked binding mode appeared to be more favorable for calf thymus DNA and poly[d(G-C)]2 than for poly[d(A-T)]2, an observation that could be explained by the slightly greater steric hindrance of the poly[d(A-T)]2 major groove. A strong concentration dependence was observed for the two binding modes where intercalation is favored at very low drug load, with stacking interactions becoming more prominent as the drug concentration is increased. Even at DNA : drug mixing ratios of 70:1 the stacked binding mode was still important for GC-rich DNAs. © 1998 John Wiley & Sons, Inc. Biopoly 46: 127-143, 1998
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  • 44
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    Biopolymers 46 (1998), S. 169-179 
    ISSN: 0006-3525
    Keywords: macromolecular carriers ; drug targeting and delivery ; branched chain synthetic polypeptides ; membrane-synthetic polypeptide interaction ; lipid monolayers/bilayers ; polymer therapeutics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The surface properties at the air/water interface and the interaction of branched chain polymeric polypeptides with a general formula poly[Lys-(DL-Alam-X1)], where X = Π (AK), Ser (SAK), or Glu (EAK), with phospholipids were investigated. Polylysine derivatives with polycationic (SAK, AK) or amphoteric (EAK) were capable to spread and form stable monomolecular layers. The stability of monolayers at the air/water interface was dependent on the side-chain terminal amino acid residue of polymers and can be described by SAK 〈 AK 〈 EAK order. The area per amino acid residue values calculated from compression isotherms were in the same range as compared to those of linear poly-α-amino acids and proteins. Moreover, these polymers interact with phospholipid monomolecular layers composed of dipalmitoyl phosphatidyl choline (DPPC) or DPPC/PG (PG: phosphatidyl glycerol; 95/5, mol/mol). Data obtained from compression isotherms of phospholipids spread on aqueous polymer solutions at different initial surface pressure indicated that insertion into lipid monolayers for SAK or AK is more pronounced than for EAK. The interaction between branched polypeptides and phospholipid membranes was further investigated using lipid bilayers with DPPC/PG and fluorescent probes located either at the polar surface [1-(4-trimethylammonium-phenyl)-6-phenyl-1,3,5-hexatriene (TMA-DPH) sodium anilino naphthalene sulfonate (ANS)] or within the hydrophobic core (DPH) of the liposome. Changes in fluorescence intensity and in polarization were observed when TMA-DPH or ANS, but not DPH were used. Comparative data also indicate that all three polymers interact only with the outer surface of the bilayer, but even the most marked penetration of polycationic polypeptide (SAK) did not result in alteration of the ordered state of the alkyl chains in the bilayer. Taken together, data obtained from mono- or bilayer experiments suggest that the interaction between branched polymers and phospholipids are highly dependent on the charge properties (Ser vs Glu) and on the identity (Ser vs Ala) of side-chain terminating amino acids. The binding of polymers to the model membranes could be mainly driven by electrostatic forces, but the significant role of hydrophilic properties in case of SAK cannot be excluded. © 1998 John Wiley & Sons, Inc. Biopoly 46: 169-179, 1998
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  • 45
    ISSN: 0006-3525
    Keywords: Cα,α-dialkylated glycines ; molecular dynamics ; geometry and conformation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relationship between the local backbone conformation and bond angles at Cα of symmetrically substituted Cα,α-dialkylated glycines (Cα,α-dimethylglycine or α-aminoisobutyric acid, Aib; Cα,α-diethylglycine, Deg; Cα,α-di-n-propylglycine, Dpg) has been investigated by molecular dynamics (MD) simulation adopting flat bottom harmonic potentials, instead of the usual harmonic restraints, for the Cα bond angles. The MD simulations show that the Cα bond angles are related to the local backbone conformation, irrespectively of the side-chain length of Aib, Deg, and Dpg residues. Moreover, the N-Cα-C′ (τ) angle is the most sensitive conformational parameter and, in the folded form, is always larger and more flexible than in the extended one. © 1998 John Wiley & Sons, Inc. Biopoly 46: 239-244, 1998
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  • 46
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    Biopolymers 46 (1998), S. 319-327 
    ISSN: 0006-3525
    Keywords: methionine ligation ; parathyroid hormones ; biomimetic ligation ; S-methylation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In biological systems, both proteolysis and aminolysis of amide bonds produce activated intermediates through acyl transfer reactions either inter- or intramolecularly. Protein splicing is an illustrative example that proceeds through a series of catalyzed acyl transfer reactions and culminates at an O- or S-acyl intermediate. This intermediate leads to an uncatalyzed acyl migration to form an amide bond in the spliced product. A ligation method mimicking the uncatalyzed final steps in protein splicing has been developed utilizing the acyl transfer amide-bond feature for the blockwise coupling of unprotected, free peptide segments at methionine (Met). The latent thiol moiety of Met can be exploited using homocysteine at the α-amino terminal position of a free peptide for transthioesterification with another free peptide containing an α-thioester to give an S-acyl intermediate. A subsequent, proximity-driven S- to N-acyl migration of this acyl intermediate spontaneously rearranges to form a homocysteinyl amide bond. S-methylation with excess p-nitrobenezensulfonate yields Met at the ligation site. The methionine ligation is selective and orthogonal, and is usually completed within 4 h when performed at slightly basic pH and under strongly reductive conditions. No side reactions due to acylation were observed with any other α-amines of both peptide segments as seen in the synthesis of parathyroid hormone peptides. Furthermore, cyclic peptide can also be obtained through the same strategy by placing both homocysteine at the amino terminus and the thioester at the carboxyl terminus in an unprotected peptide precursor. These biomimetic ligation strategies hold promise for engineering novel peptides and proteins. © 1998 John Wiley & Sons, Inc. Biopoly 46: 319-327, 1998
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  • 47
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    Biopolymers 46 (1998), S. 359-373 
    ISSN: 0006-3525
    Keywords: boundary element method ; DNA electrophoresis ; electrophoretic mobility of DNA ; free solution electrophoretic mobility of DNA ; ion relaxation, DNA electrophoresis ; modeling electrophoresis of polyions ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Boundary element methods are used to model the free solution electrophoretic mobility of short DNA fragments. The Stern surfaces of the DNA fragments are modeled as plated cylinders that reproduce translational and rotational diffusion constants. The solvent-accessible and ion-accessible surfaces are taken to be coincident with the Stern surface. The mobilities are computed by solving simultaneously the coupled Navier-Stokes, Poisson, and ion-transport equations. The equilibrium electrostatics are treated at the level of the full Poisson-Boltzmann equation and ion relaxation is included. For polyions as highly charged as short DNA fragments, ion relaxation is substantial. At .11 M KCl, the simulated mobilities of a 20 base pair DNA fragment are in excellent agreement with experiment. At .04 M Tris acetate, pH = 8.0, the simulated mobilities are about 10-15% higher than experimental values and this discrepancy is attributed to the relatively large size of the Tris counterion. The length dependence of the mobility at .11 M KCl is also investigated. Earlier mobility studies on lysozyme are reexamined in view of the present findings. In addition to electrophoretic mobilities, the effective polyion charge measured in steady state electrophoresis and its relationship to the preferential interaction parameter γgG is briefly considered. © 1998 John Wiley & Sons, Inc. Biopoly 46: 359-373, 1998
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  • 48
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    Biopolymers 45 (1998), S. 341-346 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
    Additional Material: 5 Ill.
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  • 49
    ISSN: 0006-3525
    Keywords: diffusional encounter ; Brownian dynamics ; average Boltzmann factor ; acetylcholinesterase ; Poisson-Boltzmann ; electrostatics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The utility of the average Boltzmann factor around the active site of an enzyme as the predictor of the electrostatic enhancement of the substrate binding rate is tested on a set of data on wild-type acetylcholinesterase and 18 charge mutants recently obtained by Brownian dynamics simulations. A good correlation between the average Boltzmann factors and the substrate binding rate constants is found. The effects of single charge mutations on both the Boltzmann factor and the substrate binding rate constant are modest, i.e., 〈5 fold increase or decrease. This is consistent with the experimental results of Shafferman et al. but does not support their suggestion that the overall rate of the catalytic reaction is not limited by the diffusional encounter of acetylcholinesterase and its substrate. © 1998 John Wiley & Sons, Inc. Biopoly 45: 355-360, 1998
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  • 50
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    Biopolymers 45 (1998), S. 469-478 
    ISSN: 0006-3525
    Keywords: molecular dynamics ; hydrated proteins ; crystal structures ; density distributions ; globular proteins ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using molecular dynamics simulations of fully hydrated proteins and analysis of crystal structures contained in the Protein Data Bank, we develop a transferable set of perpendicular radial distribution functions for water molecules around globular proteins. These universal functions may be used to reconstruct the unique three-dimensional solvent density distribution around every individual protein with a modest error. We discuss potential applications of this solvent treatment in protein x-ray crystallographic refinements and in theoretical modeling. We also present a fast, grid-based algorithm for construction of the perpendicular solvent density distributions. © 1998 John Wiley & Sons, Inc. Biopoly 45: 469-478, 1998
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  • 51
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    Biopolymers 47 (1998), S. 23-29 
    ISSN: 0006-3525
    Keywords: independently folded polypeptide motifs ; miniproteins ; natural target domains ; BBA motif ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper we present a redesign strategy for the development of uniquely folded polypeptide motifs of less than 40 residues. These mini proteins are based on natural target domains, including the zinc finger domains (BBA motif) Nomenclature corresponds to the defined elements of secondary structure, beginning at the N-terminus of the peptide. Roman lettering refers to a specific motif while Greek characters correspond to the elements of secondary structure within that motif. and the disulfide-rich snake and scorpion toxins (BBB motif). These motifs are designed to act as the molecular framework for the construction of novel functional polypeptides. We will explore the structural determinants of the folded BBA motif, inspired by the zinc finger peptides, in relation to the redesign process. © 1998 John Wiley & Sons, Inc. Biopoly 47: 23-29, 1998
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  • 52
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    Biopolymers 47 (1998), S. 75-81 
    ISSN: 0006-3525
    Keywords: ion channel ; synthetic peptide ; de novo design ; template-assembled synthetic proteins ; supramolecular assembly ; membrane protein ; planer lipid bilayers ; amphiphilic peptide ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To create ion channel function by synthetic peptides is a challenge in the de novo design of artificial membrane proteins. Amphiphilic α-helical motifs of ∼ 20 amino acid residues to span lipid bilayers are most often used for the creation of peptide ion channels. Template molecules to tether helical peptides have been employed to obtain more organized pore structures. Approaches to form molecular assembly of peptides in the membranes by hydrogen bonding have been also investigated. We have developed approaches to assemble helices with individual amino acid sequences to construct artificial helical proteins. Using one of these approaches, four helices corresponding to the voltage sensor segments (S4 in repeat I-IV) of the sodium channel were assembled on a peptide template to give a protein having ion channel activity with rectification. © 1998 John Wiley & Sons, Inc. Biopoly 47: 75-81, 1998
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  • 53
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    Biopolymers 47 (1998), S. 127-142 
    ISSN: 0006-3525
    Keywords: collagen mimetics ; triple helix ; peptoid ; template ; biophysics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Collagen peptidomimetics have been synthesized as an alternative to natural collagen. The incorporation of unnatural residues such as peptoids in the collagen sequences can demonstrate potent and specific biological activity and enhance the biostability against enzymatic degradation. Furthermore, the use of achiral peptoids simplifies synthetic strategies by reducing racemization problems. The peptoid residue N-isobutylglycine (Nleu) has been successfully incorporated into a series of collagen mimetics composed of Gly-Pro-Nleu, Gly-Nleu-Pro, and Gly-Nleu-Nleu. The discovery of template-assembled collagen mimetics and metal binding ability has laid the foundation for new opportunities in the design of novel collagen mimetic complexes. This review summarizes the synthesis and integrated biophysical analyses of the structures of these collagen mimetics. Solid phase segment condensation techniques have been utilized for the synthesis of the single chain and template-assembled analogues. The characterization of the collagen-like structures has been established by temperature-dependent optical rotation measurements, CD, NMR spectroscopy, and molecular modelling simulations. © 1998 John Wiley & Sons, Inc. Biopoly 47: 127-142, 1998
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  • 54
    ISSN: 0006-3525
    Keywords: non-natural amino acid ; peptide ; squarylium dye ; thin film ; poly(3-methylthiophene) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We designed a polypeptide that behaves as a photodevice by using a non-natural amino acid with replacement of an α-hydrogen by a squarylium dye and succeeded in syntheses of the non-natural amino acid derivative containing a squarylium and its peptide with trialanine Ala-Ala-Ala. Strong dye-dye interactions were confirmed by absorption and CD spectra for the peptide in 2,2,2-trifluoroethanol solution and in water suspension. The non-natural amino acid derivative could be deposited onto a PMeT/Au electrode by the micelle disruption method. © 1998 John Wiley & Sons, Inc. Biopoly 47: 179-183, 1998
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  • 55
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    Biopolymers 47 (1998), S. 263-263 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 56
    ISSN: 0006-3525
    Keywords: electrostatically driven Monte Carlo method ; cluster analysis ; global energy minimum ; perturbed conformations ; conformational space ; lowest energy conformations ; polypeptide chain ; melittin, membrane-bound portion ; Empirical Conformational Energy Program for Peptides 3 ; annealing methods ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electrostatically driven Monte Carlo (EDMC) method has been greatly improved by adding a series of new features, including a procedure for cluster analysis of the accepted conformations. This information is used to guide the search for the global energy minimum. Alternative procedures for generating perturbed conformations to sample the conformational space were also included. These procedures enhance the efficiency of the method by generating a larger number of low-energy conformations.The improved EDMC method has been used to explore the conformational space of a 20-residue polypeptide chain whose sequence corresponds to the membrane-bound portion of melittin. The ECEPP/3 (Empirical Conformational Energy Program for Peptides) algorithm was used to describe the conformational energy of the chain. After an exhaustive search involving 14 independent runs, the lowest energy conformation (LEC) (-91.0 kcal/mol) of the entire study was encountered in four of the runs, while conformations higher in energy by no more than 1.8 kcal/mol were found in the remaining runs with the exception of one of them (run 8). The LEC is identical to the conformation found recently by J. Lee, H.A. Scheraga, and S. Rackovsky [(1998) “Conformational Analysis of the 20-Residue Membrane-Bound Portion of Melittin by Conformational Space Annealing,” Biopolymers, Vol. 46, pp. 103-115] as the lowest energy conformation obtained in their study using the conformational space annealing method. These results suggest that this conformation corresponds to the global energy minimum of the ECEPP/3 potential function for this specific sequence; it also appears to be the conformation of lowest free energy. © 1998 John Wiley & Sons, Inc. Biopoly 46: 117-126, 1998
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  • 57
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    Biopolymers 46 (1998), S. 195-200 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 58
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    Biopolymers 46 (1998), S. 201-214 
    ISSN: 0006-3525
    Keywords: band broadening ; dispersion ; DNA ; gels ; electrophoresis ; fluorescence recovery ; photobleaching ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We determined quantitatively the band broadening effect during gel electrophoresis by measuring the longitudinal dispersion coefficient Dx, with a fluorescence recovery after photobleaching setup, coupled to an electrophoretic cell. We carried out measurements as a function of the electric field, the average pore size, and the molecular length of DNA fragments. Our results are in good agreement with the predictions of the biased reptation model with fluctuations described by T. A. Duke et al. [(1992) Physics Review Letters, vol. 69, pp. 3260-3263]. This agreement is observed on single-stranded DNA [persistence length ≅ 4 nm; B. Tinland et al. (1997) Macromolecules, vol. 30, pp. 5763-5765] in polyacrylamide gels and on double-stranded DNA (persistence length ≅ 50 nm) in agarose gels, two systems where the ratio between the average pore size and the Kuhn length is larger than 1. © 1998 John Wiley & Sons, Inc. Biopoly 46: 201-214, 1998
    Additional Material: 12 Ill.
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  • 59
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    Biopolymers 46 (1998), S. 403-415 
    ISSN: 0006-3525
    Keywords: molecular dynamics ; DNA curvature ; DNA flexibility ; TATA box functionality ; TATA box binding protein (TBP) ; TBP recognition ; TBP binding ; TBP transcriptional activation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four 1.5 ns molecular dynamics (MD) simulations were performed on the d(GCTATAAAAGGG) · d(CCCTTTTATAGC) double helix dodecamer bearing the Adenovirus major late promoter TATA element and three iso-composition mutants for which physical and biochemical data are available from the same laboratory. Three of these DNA sequences experimentally induce tight binding with the TATA box binding protein (TBP) and induce high transcription rates; the other DNA sequence induces much lower TBP binding and transcription. The x-ray crystal structures have previously shown that the duplex DNA in DNA-TBP complexes are highly bent. We performed and analyzed MD simulations for these four DNAs, whose experimental structures are not available, in order to address the issue of whether inherent DNA structure and flexibility play a role in establishing these observed preferences. A comparison of the experimental and simulated results demonstrated that DNA duplex sequence-dependent curvature and flexibility play a significant role in TBP recognition, binding, and transcriptional activation. © 1998 John Wiley & Sons, Inc. Biopoly 46: 403-415, 1998
    Additional Material: 6 Ill.
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  • 60
    ISSN: 0006-3525
    Keywords: vibrational CD ; solution conformation ; alanine oligopeptides ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solution conformation of a number of small, linear alanine oligomers was investigated via ir (or vibrational) CD (VCD). We find that these oligopeptides assume distinct solution conformations that depend primarily on chain lengths, and to a lesser degree on temperature, ionic strength, and pH. As expected, the longer chain oligomers exhibit more distinct VCD features and, presumably, more stable solution structures. At the level of the hexamer, however, aggregation of the peptide occurs. The fast time scale of VCD allows solution structures to be detected that may not be observable using slower techniques such as various forms of nmr spectroscopy. The VCD results reported here confirm that it is generally possible to obtain conformational information for small, linear homo- and heterooligopeptides via VCD spectroscopy. In this respect, the sensitivity of VCD is similar to that of electronic CD. Furthermore, the temperature dependence of the VCD results indicate that at elevated temperatures, the increasing number of conformational states results in a loss of discernible conformers, and consequently, a broadening and weakening of the VCD features. © 1998 John Wiley & Sons, Inc. Biopoly 46: 455-463, 1998
    Additional Material: 7 Ill.
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  • 61
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    Biopolymers 47 (1998), S. 5-22 
    ISSN: 0006-3525
    Keywords: hemoproteins ; model systems ; miniaturized proteins ; mimochromes ; helix structures ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The present paper highlights and reviews current research in the field of hemoprotein models. Hemoproteins have been extensively studied in order to understand structure-function relationships, and to design new molecules with desired functions. A wide number of synthetic analogues have been developed, using quite different approaches. They differ in molecular structures, ranging from simple meso-substituted tetraaryl-metalloporphyrins and peptide-porphyrin conjugates.In this paper we summarize the state of the art on peptide based hemoprotein models. We also report here the approach used by us to develop a new class of molecules, named mimochromes. They can be regarded as miniaturized hemoproteins, because mimochromes are low molecular weight compounds with some structural and functional properties common to those of the parent high molecular weight protein. The basic structure of mimochromes is a deuteroporphyrin ring covalently linked to two helical peptide chains. Two molecules of this series have been fully characterized. All the information derived from their structural analysis has been applied to the design of new analogues with additional functions. © 1998 John Wiley & Sons, Inc. Biopoly 47: 5-22, 1998
    Additional Material: 15 Ill.
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  • 62
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    Biopolymers 46 (1998), S. 503-516 
    ISSN: 0006-3525
    Keywords: discrete charge model of DNA ; dielectric cylinder in water ; effective dielectric constant ; salt effects ; Debye shielding factor ; potential variations in DNA surface ; Boltzmann averaged bending angles ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have studied electrostatic properties of DNA with a discrete charge model consisting of a cylindrical dielectric core with a radius of 8 Å and a dielectric constant Di = 4, surrounded by two helical strings of phosphate point charges at 10 Å from the axis, immersed in an aqueous medium with dielectric constant Dw = 78.54. Eliminating the dielectric core makes potentials in the phosphate surface less negative by about 0.5 kT/e. Salt effects are evaluated for the model without a dielectric core, using the shielded Coulomb potential. Smearing the phosphate charges increases their potential by about 2.5 kT/e, due mostly to the self-potential of the smeared charge. Potentials in the center of the minor and major grooves vary less than 0.02 kT/e along their helical path. The potential in the center of the minor groove is from 1.0 to 1.7 kT/e, more negative than in the center of the major groove, depending on dielectric core and salt concentration. So multivalent cations and also larger cationic ligands, such as some antibiotics, are likely to adsorb in the minor groove, in agreement with earlier computations by A. and B. Pullman. Dielectric effects on the surface potential and the local potential variations are found to be relatively small. Bending of DNA is studied by placing a multivalent cation, MZ+, in the center of the minor or major groove, curving DNA around it for a certain length, and calculating the free energy difference between the bent and the straight configuration. Boltzmann averaged bending angles, 〈β〉, are found to be maximal in 0.03M monovalent salt, for a length of about 50 or 25 Å of curved DNA when an MZ+ ion is adsorbed in the minor or the major groove, respectively. When the dielectric constant of water is used throughout the calculation, we find maximal bends of 〈β〉 = 11° for M2+ and 〈β〉 = 16° for M3+ in the minor groove, 〈β〉 = 13° for M3+ in the major groove. The absence of bends in DNA adsorbed to mica in the presence of Mg salts supports the role of Mg2+ in “ion bridging” between DNA and mica. The treatment of the effective dielectric constant between two points outside a dielectric cylinder in water is appended. © 1998 John Wiley & Sons, Inc. Biopoly 46: 503-516, 1998
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  • 63
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    Biopolymers 47 (1998), S. 63-73 
    ISSN: 0006-3525
    Keywords: protein de novo design ; novel macromolecules ; topological templates ; Template Assembled Synthetic Proteins (TASP) ; biosensors ; protein folding ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ultimate goal in protein de novo design is the creation of novel macromolecules with tailor-made receptor, sensory, and catalytic functions. Despite considerable progress in understanding basic rules of secondary structure formation and protein stability, the well-known protein folding problem is still far from being solved and, in general, only a limited number of designed proteins are folded uniquely. In this article the state-of-the-art in protein design is demonstrated on some selected examples, indicating that the construction of protein-like macromolecules mimicking some essential features of natural proteins seems to be within reach. Thus, protein design and mimicry has become an interdisciplinary challenge with most intriguing perspectives. © 1998 John Wiley & Sons, Inc. Biopoly 47: 63-73, 1998
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  • 64
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    Biopolymers 47 (1998), S. 451-463 
    ISSN: 0006-3525
    Keywords: bacteria ; antibiotics ; linear amphipathic α-helical antimicrobial peptides ; peptide-lipid interactions ; membrane permeation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The increasing resistance of bacteria to conventional antibiotics resulted in a strong effort to develop antimicrobial compounds with new mechanisms of action. Antimicrobial peptides seem to be a promising solution to this problem. Many studies aimed at understanding their mode of action were described in the past few years. The most studied group includes the linear, mostly α-helical peptides. Although the exact mechanism by which they kill bacteria is not clearly understood, it has been shown that peptide-lipid interactions leading to membrane permeation play a role in their activity. Membrane permeation by amphipathic α-helical peptides can proceed via either one of the two mechanisms: (a) transmembrane pore formation via a “barrel-stave” mechanism; and (b) membrane destruction/solubilization via a “carpet-like” mechanism. The purpose of this review is to summarize recent studies aimed at understanding the mode of action of linear α-helical antimicrobial peptides. This review, which is focused on magainins, cecropins, and dermaseptins as representatives of the amphipathic α-helical antimicrobial peptides, supports the carpet-like rather the barrel-stave mechanism. That these peptides vary with regard to their length, amino acid composition, and net positive charge, but act via a common mechanism, may imply that other linear antimicrobial peptides that share the same properties also share the same mechanism. © 1999 John Wiley & Sons, Inc. Biopoly 47: 451-463, 1998
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  • 65
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    Biopolymers 48 (1998), S. 39-55 
    ISSN: 0006-3525
    Keywords: modified nucleotides ; site-specific probes ; RNA structure ; RNA function ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Modified nucleotides can be incorporated site specifically into RNA by the use of total chemical synthesis as well as by use of a variety of recombinant RNA techniques. The range of nucleotide analogues includes modifications to base, sugar, and phosphate for structure-function analysis and for cross-linking studies as well as to answer specific mechanistic questions in RNA catalysis. We describe how RNA containing site-specific modifications are prepared, concentrating in particular on routes involving chemically synthesized oligoribonucleotides, and give examples of their application in studies of the hammerhead and hairpin ribozymes. © 1998 John Wiley & Sons, Inc. Biopoly 48: 39-55, 1998
    Additional Material: 9 Ill.
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  • 66
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    Biopolymers 48 (1998), S. 29-37 
    ISSN: 0006-3525
    Keywords: amide synthase ; catalytic antibodies ; Diels-Alderase ; ideal catalyst platform ; in vitro selection ; Lewis acid ; modified uridines ; modified RNA ; ribozymes ; SELEX ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this manuscript the catalytic ability of RNA is examined and compared to other biopolymers. Despite having considerably fewer catalytically enabling properties when compared to proteins, the power of in vitro selection has allowed for RNA and DNA catalysts to be isolated. RNA catalysis has been expanded by incorporating modified bases to enrich the structural and functional diversity of RNA. Successful examples of new RNA chemistry using base modifications include carbon-carbon bond forming reactions and creation of highly specific active sites that are capable of recognizing small organic molecules without the need for nucleic acid templating or intercalation. In fact, the scope of functional modifications available for use in the RNA platform may eventually surpass those that are found in proteins and there are already hints that well chosen modifications allow nucleic acid catalysts to take advantage of mechanisms not available to selected protein catalysts for similar reactions. The chemical versatility of RNA is just emerging and future research directions will likely entail more creative methods for functional modification that will lead to new catalysts. © 1998 John Wiley & Sons, Inc. Biopoly 48: 29-37, 1998
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  • 67
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    Biopolymers 48 (1998), S. 137-153 
    ISSN: 0006-3525
    Keywords: RNA ; pseudoknot ; Turnip Yellow Mosaic Virus ; Mouse Mammary Tumor Virus ; Beet Western Yellows Virus ; Simian Retrovirus type-1 ; Hepatitis Delta Virus ; translational frameshifting ; ribozyme ; nmr ; x-ray diffraction ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Recently, several high-resolution structures of RNA pseudoknots have become available. Here we review the progress in this area. The majority of the structures obtained belong to the classical or H-type pseudoknot family. The most complicated pseudoknot structure elucidated so far is the Hepatitis Delta Virus ribozyme, which forms a nested double pseudoknot. In particular, the structure-function relationships of the H-type pseudoknots involved in translational frameshifting have received much attention. All molecules considered show interesting new structural motifs. © 1999 John Wiley & Sons, Inc. Biopoly 48: 137-153, 1998
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  • 68
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 737-748 
    ISSN: 0887-624X
    Keywords: inverse microemulsion polymerization ; MADQUAT ; nucleation ; photopolymerization ; molecular weights ; flocculants ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of inverse microemulsions of 2-methacryloyl oxyethyl trimethyl ammonium chloride stabilized by a blend of nonionic emulsifiers (a sorbitan sesquioleate and a sorbitan monooleate) and initiated by UV light in the presence of Azobis(isobutyronitrile) (AIBN) was investigated. The effect of initiator concentration, light intensity, emulsifier concentration, and dispersed phase weight fraction on the polymerization rate (Rp), number of polymer particles (Np), and polymer molecular weight (Mw) was studied. The application of this process to tubular reactors is discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 737-748, 1998
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  • 69
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1217-1226 
    ISSN: 0887-624X
    Keywords: polypropylene ; pyrene ; two-solute system ; pulse radiolysis ; solute ionic species ; solute excited states ; low-temperature radiolysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A pulse radiolysis study of isotactic polypropylene (PP) film has been carried out with the main aims of investigating charge trapping in an undoped system and solute radical ion generation in an pyrene (Py) doped matrix. In PP, pulse radiolysis gives electron-positive hole pairs. The electron can be stabilized in the undoped system as a trapped electron, et-. The transient absorption spectrum of et- in the near-IR (up to 1800 nm) was observed in the temperature range 30-100 K. This IR absorption was not detected in the case of oxidized PP. In such a matrix electrons can be scavenged by oxidation products generating respective radical-anions (absorption in the UV RANGE, λ 〈 350 nm). In a doped matrix transient absorption bands centered at 450 and 500 nm were observed which can be assigned to the Py radical cation and anion, respectively. The recombination of these ionic species leads to monomer excited-state formation observed during and after the 17 ns pulse. Contrary to the Py-doped polyethylene no excimer emission was detected at room temperature even if Py content in PP was close to 0.02 mol dm-3. The rate of Py radical-ion decay was found to be temperature dependent. Two linear parts of the Arrhenius plot were observed which intersected at ca. 240 K, the glass transition temperature, Tg, for PP. The activation energies calculated for two parts of Arrhenius plot were equal to 111 and ca. 0.78 kJ mol-1 for T 〉 Tg and T 〈 Tg, respectively. Some preliminary results concerning the ionic processes in PP containing two solutes (Py, 3,3′-dimethyldiphenyl) were presented. The mechanism of ionic recombination in PP will be proposed and discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1217-1226, 1998
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  • 70
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1345-1348 
    ISSN: 0887-624X
    Keywords: acid functional ; telechelic ; benzyl alcohol ; poly(ε-caprolactone) ; polymerization ; living ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 71
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 883-888 
    ISSN: 0887-624X
    Keywords: temperature sensitive ; particle ; emulsion polymerization ; morphology ; adsorption ; enzyme ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two kinds of temperature-sensitive composite polymer particles were prepared by seeded emulsion copolymerizations of (dimethylamino)ethyl methacrylate and ethylene glycol dimethacrylate with 0.14 μm-sized polystyrene and 0.26 μm-sized poly(methylmethacrylate) seed particles. To evaluate the usefulness as a carrier for biomolecules, the enzymatic activities of trypsin adsorbed on these two composite polymer particles were measured at temperatures above and below each lower critical solution temperature (LCST). In both cases, adsorbed trypsin retained its enzymatic activity during repeated adsorption/desorption measurements. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 883-888, 1998
    Additional Material: 7 Ill.
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  • 72
    ISSN: 0887-624X
    Keywords: (1→6)-2,5-anhydro-D-glucitol ; HPLC ; optical resolution ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cyclopolymerization of 3,4-di-O-allyl-1,2 : 5,6-dianhydro-D-mannitol (1) was carried out using BF3·OEt2 and t-BuOK. The polymer obtained by the polymerization with BF3·OEt2 mainly consisted of (1→6)-bonded 3,4-di-O-allyl-2,5-anhydro-D-glucitol as the five-membered constitutional repeating unit, though it contained a small amount of other cyclic repeating units. On the other hand, during the polymerization using t-BuOK, the stereoregular polymer (1→6)-linked 3,4-di-O-allyl-2,5-anhydro-D-glucitol (2) was synthesized via a regio- and stereoselective mechanism. Cleavage of the allyl ether linkage in polymer 2 occurred to produce the polymer consisting of only 2,5-anhydro-D-glucitol units, i.e., (1→6)-2,5-anhydro-D-glucitol (3). Chromatographic enantioseparation of chloroquine and tröger base has been performed on (3,5-dimethylphenyl)carbamate and 4-methylbenzoate derivatives of 3 as a chiral stationary phase for high-performance liquid chromatography. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 901-909, 1998
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  • 73
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 939-947 
    ISSN: 0887-624X
    Keywords: fluorine ; perfluoropolyether ; polyester ; segmented ; thermoplastic ; interfacial synthesis ; thermal transitions ; dynamic-mechanical properties ; chemical resistance ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Linear segmented polyesters containing soft perfluoropolyether (PFPE) and hard aromatic segments are obtained by an interfacial polycondensation reaction of an acyl chloride-ended fluorinated prepolymer with various aromatic diphenols in the presence of phase transfer catalysts (PTC) as accelerators. Experimental conditions for reaching high molecular weights are discussed. The calorimetric analysis (DSC) of all the polyesters synthesized shows a typical biphasic morphology, where a very low Tg (〈 -110°C) corresponding to the segregated PFPE moiety, is always accompanied by another Tg or a higher melting temperature, depending on the nature of the hard phase. Dynamic-mechanical analysis (DMA) has been carried out confirming the DSC results and suggesting diversified mechanical behaviors at the various temperatures in line with the amorphous or semicrystalline nature of the polymer. Chemical resistance was finally tested by dipping in several solvents and chemicals. The new polyesters show high contact angles, a moderate swelling in many organic solvents and excellent stability in aggressive hydrolytic environments. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 939-947, 1998
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  • 74
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1919-1928 
    ISSN: 0887-624X
    Keywords: emulsion polymerization ; vinylidene chloride ; kinetics ; sodium lauryl sulfate ; potassium persulfate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Emulsion polymerization of vinylidene chloride was carried out at 50°C using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator, respectively. Contrary to the results so far reported, the stirring rate did not affect the progress of the polymerization and such an abnormal kinetic behavior as the rate of polymerization suddenly drops in the course of polymerization was not observed. The number of polymer particles produced was proportional to the 0.7 power of the concentration of emulsifier forming micelles and to the 0.3 power of the initial initiator concentration, respectively, and was independent of the initial monomer concentration. The rate of polymerization was in proportion to the 0.3 power of the concentration of emulsifier forming micelles, to the 0.5 power of the initial initiator concentration, to the 0.2 power of the initial monomer concentration, and to the 0.45 power of the number of polymer particles, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1919-1928, 1998
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  • 75
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1961-1964 
    ISSN: 0887-624X
    Keywords: Poly(4,4′-phenylene-3,3′,4,4′-biphenyltetracarboxyimide) ; poly(4,4′-oxydiphenylenepyromellitimide) ; precursor solution ; aprotic polar solvent ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 76
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1969-1972 
    ISSN: 0887-624X
    Keywords: hydrosilation ; polymer ; siloxane ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
    Additional Material: 2 Ill.
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  • 77
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1995-1999 
    ISSN: 0887-624X
    Keywords: poly-γ-D-glutamic acid ; biopolymer ; covalent modification ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methods for the covalent modification in aqueous solution of poly-γ-D-glutamic acid from Bacillus licheniformis have been studied. Co-derivatization of a synthetic UV-absorbent amine and ethanolamine, using a water-soluble carbodi-imide coupling agent, yielded a water-soluble modified polymer. Derivatization of the polymer was accompanied by cleavage of the γ-linked polypeptide backbone, and a reduction in molecular mass from 170 to 10 kDa. A procedure was developed for the removal of noncovalently bound ligands by treatment with 5 M CaCl2. The polymer sidechains also reacted in aqueous solution with p-nitrophenyl acetate to form covalent linkages. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 1995-1999, 1998
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  • 78
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2037-2042 
    ISSN: 0887-624X
    Keywords: radical polymerization ; vinylcyclopropane ; vinylsilane ; desilylation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and radical polymerization of novel vinylcyclopropanes; 1-carboethoxy-2-trimethylsilyl-2-vinylcyclopropane (1a) and 1-carboethoxy-2-(1-trimethylsilyl)-vinylcyclopropane (1b), were examined. 1a and 1b were prepared by the coupling reaction of 2-trimethylsilylbutadiene with ethyl diazoacetate, which was prepared from glycine ethyl ester hydrochloride. The radical polymerization of 1a and 1b was carried out at 60°C in bulk for 40 h in the presence of 2,2′-azobis(isobutyronitrile) (5 mol % vs. monomer). Poly(1) consisted of a 1,5-ring-opened unit. Desilylation reaction of poly(1) proceeded quantitatively in aqueous hydrochloric acid. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2037-2042, 1998
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  • 79
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2021-2027 
    ISSN: 0887-624X
    Keywords: 2,2′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride ; aromatic polyimides ; solubility ; thermal behavior ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new aromatic tetracarboxylic dianhydride having a crank and twisted noncoplannar structure, 2,2′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, was synthesized by the reaction of 4-nitrophthalonitrile with biphenyl-2,2′-diol, followed by hydrolysis and cyclodehydration. The biphenyl-2,2′-diyl-containing aromatic polyimides having inherent viscosities up to 0.66 dL/g were obtained by the conventional two-step procedure starting from the dianhydride monomer and various aromatic diamines. Most of the polyimides were readily soluble in amide-type solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone. The aromatic polyimides had glass transition temperatures in the range of 205-242°C, and began to lose weight around 415°C, with 10% weight loss being recorded at about 500°C in air. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2021-2027, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2069-2079 
    ISSN: 0887-624X
    Keywords: Candida antarctica lipase ; Novozym 435® ; polyester ; enzymatic polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preliminary enzymatic polymerization studies in the simple stoichiometric adipic acid/butane-1,4-diol system using lipase B from Candida antarctica, immobilized as Novozym 435®, suggest that in solvent-free conditions a step-growth mechanism operates involving the sequential addition of an AB synthon by esterification mode only. Conversely, in toluene as solvent there is a change to the more facile transesterification mode in line with the conventional polyesterification procedure, pointing to a change in specificity of the lipase. Evidence is drawn from qualitative studies using a series of synthetic intermediates, enabling authentication of product mixtures together with an indication of the comparative reactivity of species along the proposed reaction pathway. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2069-2080, 1998
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  • 81
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2111-2117 
    ISSN: 0887-624X
    Keywords: dendritic polymer ; blends ; coatings ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hybrid blends of poly(amidoamine) PAMAM dendrimers with two linear high polymers, poly(vinyl chloride), PVC, and poly(vinyl acetate), PVAc, are reported. The interaction between the blend components was studied using dynamic mechanical analysis, xenon nuclear magnetic resonance (NMR) spectroscopy, and tensile property measurements. The data suggest a much higher degree of interaction between components of PVAc-containing blends compared to those containing PVC. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2111-2117, 1998
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  • 82
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2135-2146 
    ISSN: 0887-624X
    Keywords: SCLC polyurethanes ; azobenzene mesogenic group ; alkyl spacer ; bilayer smectic phases ; hydrogen bonding ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of side chain liquid crystal polyurethanes (CnCNPs), in which the spacer length was varied from 2 to 12 methylene units, were synthesized by the addition polymerization of α-[bis(2-hydroxyethyl)amino]-ω-(4-cyanoazobenzene-4′-oxy)alkanes (CnCN-diols) with hexamethylene diisocyanate. The liquid crystalline properties of CnCNPs were characterized by means of differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction. Polyurethanes with spacer length 4 or higher exhibited mesomophic properties. C4CNP and C5CNP exhibited an enantiotropic nematic mesophase, while C6-C12CNPs exhibited enantiotropic bilayer smectic mesophases. CnCNPs have a high tendency to crystallize; crystallization is kinetically controlled. Polyurethane's backbone crystallization is closely related to hydrogen bonding. To establish the role of hydrogen bonding in mesophase formation as well as crystallization, Fourier transform infrared spectroscopy studies of CnCNPs were carried out at different temperatures focusing on H-bonds between the N—H and C=O groups of the urethane backbone. With increasing temperature, C=O and N—H stretching bands were evenly shifted to higher wavenumbers, with two exceptions (C4CNP and C5CNP) discussed in detail in the text. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2135-2146, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2169-2176 
    ISSN: 0887-624X
    Keywords: free radical ; initiation ; styrene ; acrylonitrile ; copolymerization ; nitroxide trapping ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The competitive reactions of cyanoisopropyl radicals with the mixed monomers styrene and acrylonitrile have been investigated using the nitroxide radical trapping technique. When the trap concentration is kept low, second, third, and even fourth generation (in terms of successive monomer addition) carbon radicals have been observed as trapped products. The ratio of rate constants for the addition of styrene and acrylonitrile to cyanoisopropyl radicals is 2.7 at 75°C and 5.3 at 105°C. These values are compared with the ratios for reactions of these two monomers with a number of other radicals and discussed in terms of the polarities of the radicals and monomers. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2169-2176, 1998
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  • 84
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2193-2200 
    ISSN: 0887-624X
    Keywords: N-phenylated polyamides ; 4,4′-dianilinobiphenyl ; solubility ; thermal behavior ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New N-phenylated aromatic-aliphatic and all aromatic polyamides were prepared by the high-temperature solution polycondensation of 4,4′-dianilinobiphenyl with both aliphatic (methylene chain lengths of 6-11) and aromatic dicarboxylic acid chlorides. All of the aromatic-aliphatic polyamides and the wholly aromatic polyamides exhibited an amorphous nature and good solubility in amide-type and chlorinated hydrocarbon solvents, except for those aromatic polyamides containing p-oriented phenylene or biphenylylene linkages in the backbone; the latter were crystalline and insoluble in organic solvents except m-cresol. The N-phenylated aromatic-aliphatic polyamides and aromatic polyamides had glass transition temperatures in the range of 79-116°C and 207-255°C, respectively, and all the polymers were thermally stable with decomposition temperatures above 400°C in air. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2193-2200, 1998
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  • 85
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2237-2245 
    ISSN: 0887-624X
    Keywords: NMR ; polysiloxane, polysiloxane-block-polyimide ; solution imidization ; kinetic analysis ; structure analysis ; spin-lattice relaxation time ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polysiloxane-block-polyimides were synthesized by solution imidization of the polyamic acids derived from the combination of 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and diamino(polysiloxane) (PSX (Mw = 750)) in N-methyl-2-pyrrolidone (NMP). Their structures were analyzed by 1H-, 13C-, and 29Si-NMR spectra as well as by IR spectroscopy. The solid-state NMR spectrum was also measured to determine the spin-lattice relaxation time of the copolyimides. The observed relaxation times of both aromatic and polysiloxane segments were similar in the copolyimides having 10-30 wt % of PSX, while those in the copolyimide with 50 wt % of PSX was significantly different. This may be attributed to the morphology change due to the increase in PSX composition in the polymer backbone. The reduced viscosity of the copolyimides could be controlled by changing the monomer ratio in the feed or by adding an end-capping reagent such as phthalic anhydride into the polymerization system. The kinetic study of the solution imidization revealed that the imidization reaction obeyed second-order kinetics. The activation energy calculated for this imidization was 99.2 kJ/mol, being similar to that for the imidization of the DSDA-based aromatic polyimides. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2237-2245, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2229-2235 
    ISSN: 0887-624X
    Keywords: polyarylates ; aromatic polyether ; 2,2-bis(4-hydroxyphenyl)-1,2-diphenylethanone ; solubility ; thermal behavior ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New polyarylates having benzopinacolone units were synthesized from 2,2-bis(4-hydroxyphenyl)-1,2-diphenylethanone and aromatic dicarboxylic acid chlorides. The polymers having an inherent viscosity of 0.71-0.94 dL/g were obtained by the two-phase method using toluene as an organic solvent. The polymers were easily soluble in various organic solvents and had high glass transition temperatures in the range of 200-240°C. An aromatic polyether having benzopinacolone unit was also prepared. However, its inherent viscosity was low because of the occurrence of a side reaction. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2229-2235, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 31-38 
    ISSN: 0887-624X
    Keywords: triblock copolymers ; polycondensations ; telechelic character ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Telechelic oligo(ether-ketone)s containing two trimethylsiloxy end groups and one methyl group per repeating unit were prepared by polycondensation of 4-fluoro-2′-methyl-4′-(trimethylsiloxy)benzophenone. The telechelic character was achieved by cocondensation of a small amount of silylated bisphenol-P. The end groups of the silylated oligo(ether-ketone)s were acetylated by means of acetyl chloride. On the basis of 1H-NMR end group analyses two samples of α,ω-bis(acetoxy) oligo(ether-ketone)s with DP = 14 and DP ∼ 28 were obtained. These oligo(ether-ketone)s and a 70 or 140 fold molar amount of silylated 3,5-bis(acetoxy)benzoic acid were polycondensed at 270°C in bulk. The resulting A-B-A triblock copolymers were fractionated by dissolution in tetrahydrofuran. In three out of four experiments a small fraction of precipitated material rich in oligo(ether-ketone) was isolated. The purified triblock copolymers were characterized by inherent viscosities and NMR spectra. For those samples containing the long oligo(ether-ketone) block a low degree of crystallinity was observed after annealing. Four additional polycondensations were conducted with an initial reaction temperature of 290°C. In this way a completely soluble and amorphous triblock copolymer was obtained. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 31-38, 1998
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  • 88
    ISSN: 0887-624X
    Keywords: liquid crystalline polymers ; epoxy resins ; thermotropic ; polymer chain extension ; catalytic polyaddition ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This work is a continuation of the authors' earlier investigations of liquid crystalline epoxy resins prepared from diglycidyl ether of 4,4′-dihydroxybiphenyl (DGE-DHBP), which was used as a mesogenic agent, and aliphatic dicarboxylic compounds, which were used as flexible spacers. In this paper, the synthesis and characterization of liquid crystalline epoxy resins, prepared from DGE-DHBP and difunctional aromatic compounds are described. Three series of liquid crystalline epoxy resins were prepared by chain extension of DGE-DHBP with isomeric hydroxybenzoic and benzenedicarboxylic acids as well as diphenols. An isophthalic-terminated polyether was applied to decrease the temperature of phase transitions. The syntheses were carried out by catalytic polyaddition in the melt. Triphenylphosphine was applied as the catalyst. The resulting epoxy resins were investigated by DSC, polarizing microscope as well as by X-ray and IR spectroscopy. The phase transition temperatures and the type of mesophase of the resulting products depend on the character of the functional groups in the chain extender and on the position of the functional groups in the aromatic ring. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 21-29, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1987-1994 
    ISSN: 0887-624X
    Keywords: triphenylamine-based bis(o-aminophenol)s ; aromatic polybenzoxazoles ; solubility ; thermal behavior ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two new triphenylamine-based bis (o-aminophenol) monomers, 4,4′-diamino-3,3′-dihydroxytriphenylamines, were successfully synthesized by the cesium fluoride-mediated condensation of 2-(benzyloxy)-4-fluoronitrobenzene with aniline derivatives, followed by simultaneous deprotection and reduction. Aromatic polybenzoxazoles having inherent viscosities of 0.58-1.05 dL/g were obtained by the low-temperature solution polycondensation of the bis(aminophenol)s with various aromatic dicarboxylic acid chlorides and the subsequent thermal cyclodehydration of the resultant poly(hydroxyamide)s. All the polybenzoxazoles were amorphous, and most of them were soluble in organic solvents such as m-cresol and o-chlorophenol. Flexible and tough films of polybenzoxazoles could be cast from the DMAc solutions of some aromatic poly(hydroxyamide)s, followed by thermal cyclodehydration. The glass transition temperatures and 10% weight loss temperatures of the polybenzoxazoles under nitrogen were in the range of 262-327 and 610-640°C, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1987-1994, 1998
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  • 90
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2013-2019 
    ISSN: 0887-624X
    Keywords: asymmetric polymerization ; anionic polymerization ; (2-fluorophenyl)(4-fluorophenyl)(2-pyridyl) methyl methacrylate ; optically active polymer ; helix ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel racemic methacrylate, (2-fluorophenyl)(4-fluorophenyl)(2-pyridyl)-methyl methacrylate1 (2F4F2PyMA), was synthesized and polymerized with chiral complexes of N,N′-diphenylethylenediamine monolithium amide (DPEDA-Li) with (-)-sparteine (Sp), (2S, 3S)-(+)-2,3-dimethoxy-1,4-bis(dimethylamino)butane (DDB), and (S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine (PMP) in toluene at -78°C. The monomer showed higher resistance against methanolysis compared with triphenylmethyl methacrylate (TrMA) and several other analogues. In the asymmetric anionic polymerization of 2F4F2PyMA, PMP was found to be a more effective chiral ligand than DDB and Sp and gave quantitatively an optically active polymer with nearly perfect isotacticity. Enantiomer selection was observed in the polymerization of racemic 2F4F2PyMA with the chiral lithium complexes. Chiral recognition ability of the optically active poly(2F4F2PyMA) was examined by an enantioselective adsorption experiment. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2013-2019, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2521-2530 
    ISSN: 0887-624X
    Keywords: poly(methylphenylsiloxane) ; poly(methyl methacrylate) ; graft copolymer ; spin-spin relaxation ; degradation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(methylphenylsiloxane)-poly(methyl methacrylate) graft copolymers (PSXE-g-PMMA) were prepared by condensation reaction of poly(methylphenylsiloxane)-containing epoxy resin (PSXE) with carboxyl-terminated poly(methyl methacrylate) (PMMA), and they were characterized by gel permeation chromatography (GPC), infrared (IR), and 29Si and 13C nuclear magnetic resonance (NMR). The microstructure of the PSXE-g-PMMA graft copolymer was investigated by proton spin-spin relaxation T2 measurements. The thermal stability and apparent activation energy for thermal degradation of these copolymers were studied by thermogravimetry and compared with unmodified PMMA. The incorporation of poly(methylphenylsiloxane) segments in graft copolymers improved thermal stability of PMMA and enhanced the activation energy for thermal degradation of PMMA. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2521-2530, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2563-2570 
    ISSN: 0887-624X
    Keywords: thioxanthone derivatives ; water-compatible photoinitiator ; absorption spectrum ; fluorescence ; photopolymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Six amine-linked thioxanthones, i.e., 2-(2-hydroxy-3-[bis(2-hydroxyethyl)amino]propoxy)thioxanthone (HAPTX) and its 4-methyl, 1,3-dimethyl, 1,4-dimethyl, 3,4-dimethyl, and 1,3,4-trimethyl substituted derivatives, were synthesized as water-compatible photoinitiators and identified with FTIR, MS, NMR, and elementary analysis. The absorption and fluorescence properties were studied. Their photoinitiating polymerization efficiencies were tested with a recording dilatometer utilizing acrylamide as monomer in aqueous solution. The results show that the six amine-linked thioxanthones can independently initiate acrylamide polymerization efficiently without additional external amines as co-initiators. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2563-2570, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2593-2600 
    ISSN: 0887-624X
    Keywords: phenylenediamine ; oxidative polymerization ; enzyme ; horseradish peroxidase ; CD spectrum ; organic solvent ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ortho-, meta-, and para-phenylenediamines were polymerized using hydrogen peroxide as an oxidant and horseradish peroxidase as a catalyst in mixed solvents of 1,4-dioxane and water. The yield of the polymers was strongly dependent on solvent composition, and maximum yields were obtained at 15-30% 1,4-dioxane. The analysis of circular dichroic spectra of the enzyme suggested that enzyme structure was significantly modified at high 1,4-dioxane contents, which may be responsible for the decrease of catalytic activity of the enzyme. On the basis of IR and electronic spectra of the polymers, it was considered that o- and p-phenylenediamine polymers retain disubstituted benzene nuclei, which suggests that the polymerization proceeded mainly via N - N coupling. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2593-2600, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2667-2668 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 95
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2691-2698 
    ISSN: 0887-624X
    Keywords: N-substituted pyrrole ; liquid crystalline polymer ; polypyrrole ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three liquid crystalline N-substituted pyrroles were synthesized from 6-(1-pyrrolyl)hexanol with phenolic derivatives having a mesogenic core of cyclohexylbenzene or biphenyl by Mitsunobu reaction. These pyrroles had two anodic peaks at 1.4 and 1.8 V (vs. SCE). The former was due to an oxidation of the pyrrole moiety and the latter was due to an oxidation of the mesogenic moiety. These pyrrole monomers were polymerized by electrochemical and chemical methods. The potentiostatic method and the chemical method using FeCl3 gave a soluble and fusible polymer, respectively. A polymer having a mesogenic core of cyclohexyl benzene obtained by the chemical method and a polymer having a mesogenic core of biphenylketone obtained by the potentiostatic method had a liquid-crystalline phase. The phase was identified as smectic A by polarizing microscopy and XRD analysis. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2691-2698, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2715-2719 
    ISSN: 0887-624X
    Keywords: polymerization ; acrylamide ; peroxomonosulfate ; ultrasound ; mechanism ; rate parameters ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of acrylamide (M) in the presence of ultrasound and peroxomonosulfate (PMS) was carried out for the first time for various concentration ranges of monomer and initiator and various temperatures at a constant frequency of 1 Mhz. The rate of polymerization Rp was found to increase with increase in the concentration of monomer and initiator and found to depend on [M] and [PMS]1/2. The rate of disappearance of initiator (-d[PMS]/dt) was also followed simultaneously under the experimental conditions and found to increase linearly with increase in [PMS]. A probable reaction mechanism was proposed on the basis of the observed results, and the individual rate constant were evaluated. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2715-2719, 1998
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  • 97
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2741-2748 
    ISSN: 0887-624X
    Keywords: stereoregular polymers ; chiral polyamides ; ω-amino acids ; glycine ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stereoregular, enantiomerically pure, chiral polyamides of the -AB- type, containing a natural (glycine) and a synthetic [(S)-5-amino-4-methoxypentanoic acid (AMP)] component have been prepared by the active ester polycondensation method. Thus, polyamide 7 was obtained by polycondensation of the conveniently activated H2NGly-AMPCO2R unit (6). In this reaction, 7 appeared accompanied by a considerable amount of cyclic (Gly-AMP)2 (8), which makes the isolation and purification of 7 difficult. The formation of cyclic byproducts could be avoided by preparing and polymerizing the oligoamide H2NGly-AMP-AMPCO2R (11), which has the terminal carboxyl group activated as the pentachlorophenyl ester. The resulting polyamide (12) was obtained in 85% yield and free of macrolactams, such as 8. The new polyamides 7 and 12 were characterized by elemental analysis and infrared and 1H- and 13C-nuclear magnetic resonance spectroscopies. Thermal studies revealed that 12 is crystalline and yields films with spherulitic texture by slow evaporation of formic acid solutions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2741-2748, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2315-2330 
    ISSN: 0887-624X
    Keywords: thermal degradation mechanism ; poly(styrene-co-methacrylonitrile) ; pyrolysis gas chromatography ; back-biting reaction ; depolymerization ; boundary effect ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of thermal degradation of homopolymers of styrene (St) and methacrylonitrile (MAN) and their copolymers was investigated theoretically and experimentally by the pyrolysis gas chromatography using a Curie-point pyrolyzer. Poly(St-co-MAN)s generate dimers and trimers as well as monomers by flash pyrolysis. Parameter α was proposed to account for the competition between the back-biting reaction and depolymerization. The back-biting parameter α is defined as the ratio of rate constants, α = kbb/kdp, where kbb is the rate constant for the back-biting reaction and kdp is that for depolymerization. The back-biting process is followed by β-scission, where dimer and trimer are generated, and directly correlated with the C - H bond dissociation energies in the polymer chain. Using the back-biting parameter α, where 1/α is equal to the zip length n in depolymerization, the boundary effect for the difference of monomer yields from the homopolymers of St and MAN and their copolymers is well explained. The calculated values of boundary effect parameters, βSt and βMAN, agreed well with the experimental results. It was found that thermal degradation mechanisms of homo- and copolymers of vinyl compounds can be analyzed comprehensively using the back-biting parameter α and the boundary effect parameter β. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2315-2330, 1998
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    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2347-2357 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hyperbranched homopolyester of gallic acid (GA) was prepared by polycondensation of acetylated gallic acid in bulk. Copolyesters of gallic acid and 3-hydroxybenzoic acid (3-HBA) or β-(4-hydroxyphenyl)propionic acid (HPPA) were prepared via the silylated monomers. The degree of branching was varied in both series via the molar fraction of gallic acid. A model reaction with silylated 4-methoxybenzoic acid suggests that all three acetoxy groups of gallic acid can react by ester interchange reactions under the chosen reaction conditions. Furthermore, highly branched copolyesters derived from equimolar ratios of HPPA and 2-, 3-, or 4-hydroxybenzoic acid, vanillic acid, or 4-hydroxycinnamic acid were synthesized. All these copolyesters were found to be amorphous with glass transition temperatures (Tg's) far below that of the hyperbranched poly(gallic acid). © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2347-2357, 1998
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 100
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2381-2387 
    ISSN: 0887-624X
    Keywords: bacterial polyesters ; epoxidation of polyesters ; polyhydroxyalkanoates ; crosslinking polyesters ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(3-hydroxyoctanoate-co-3-hydroxy-10-undecenoate)s (PHOUs) with controlled amounts of unsaturated repeating units were epoxidized to various extents with m-chloroperbenzoic acid (MCPBA) in homogeneous solution. The epoxidation reaction was second order, with an initial rate constant of 1.1 × 10-3Lmol-1.s-1 at 20°C, regardless of the unsaturated unit content in PHOU. No substantial change in either molecular weight or molecular weight distribution occurred as a result of epoxidation, but the melt transition temperature and enthalpy of melting both decreased as the unsaturated groups were increasingly converted into epoxide groups. In contrast, the glass transition temperature (Tg) increased by approximately 0.25°C for each 1 mol % of epoxidation, irrespective of the composition of the PHOU. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2381-2387, 1998
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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