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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 29 (1991), S. 309-316 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The irradiation of triarylsulfonium salts produces Brönsted acid along with diarylsulfide products. This photochemical conversion has been applied in several areas of polymer film technology including imaging and curing of films. This paper discusses the dependency of acid generation in polymer films on the structures of both polymer and sulfonium salt. The results suggest that the structures of both polymer and sulfonium salt. The results suggest that the efficiency of acid generation is dependent on the interaction between polymer structure and the charged sulfonium salt. Studies have been carried out for both deep-UV and electron beam irradiation of polymer films. The variation of acid generation with sulfonium salt loading has been determined. Finally the effect of accelerating voltage on the amount of acid generation following electron beam irradiation is discussed. ESR spectroscopy has been done on films after uv irradiation to determine the nature of the radicals which are formed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 16 (1993), S. 408-422 
    ISSN: 0887-3585
    Keywords: heme ; flavin ; electron transfer proteins ; crystal packing ; molecular modeling ; energy minimization ; electrostatic interactions ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Flavocytochrome b2 and cytochrome c are physiological electron transfer partners in yeast mitochondria. The formation of a stable complex between them has been demonstrated both in solution and in the crystalline state. On the basis of the three-dimensional structures, using molecular modeling and energy minimization, we have generated a hypothetical model for the interaction of these redox partners in the crystal lattice. General criteria such as good charge and surface complementarity, plausible orientation, and separation distance of the prosthetic groups, as well as more specific criteria such as the stoichiometry determined in the crystal, and the involvement of both domains and of more than one subunit of flavocytochrome b2 led us to discriminate between several possible interaction sites. In the hypothetical model we present, four cytochrome c molecules interact with a tetramer of flavocytochrome b2. The b2 and c hemes are coplanar, with an edge-to-edge distance of 14 Å. the contact surface area is ca. 800 Å2. Several electrostatic interactions involving the flavin and the heme domains of flavocytochrome b2 stabilize the binding of cytochrome c. © 1993 Wiley-Liss, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A new mass spectrometry technique using an inductively coupled plasma (ICP) ionization source and an ion-trap mass spectrometer (ITMS) detector is described and evaluated for elemental and isotopic analysis. Initial results obtained with the ICP-ITMS technique include sub-ppb detection of bare ions for, most elements, complete destruction of typical polyatomic matrix ions (e.g., CIO+, ArO+, and ArCl+), and effective neutralization of strong Ar+ ion currents. The latter effects allow observation of clearer mass spectra at m/z 〈 80 and potentially improved detection of ‘problem’ elements in ICP-MS (e.g., K, Ca, V, Fe, As, and Se). Formation of poly-oxide and -hydroxide ions of metals with high oxide bond strengths were observed and require system modifications to alleviate.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1045-4861
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: A neonatal incubator has been custom modified to enable measurement of initial platelet retention on biomaterials in vitro under clinically relevant hemodynamic conditions. To calibrate this device, platelet retention on several materials having microconduit geometry (0.7-1.0 mm i.d.) has been measured after perfusion with citrated whole blood (containing 111 Indium-labelled platelets) at a shear rate of 312 s-1, 37°C, and 80 cm H2O transmural pressure. The relative reactivity of these materials toward platelets was: glass 〈 Fibrinogen(Fg)-coatedglass 〈 Fg-coated polyethylene 〈 polyethylene ∼ = Expanded polytetrafluoroethylene. Interindividual variation is relatively large (coefficient of variation = 35.5 ± 9.3%), but comparison to intraindividual controls reduces the variability to 14.8 ± 10.3%, a level which is suitable for economical testing of platelet retention to biomaterials in the presence or absence of drugs. This approach may have particular value in the study of the mechanism of platelet interactions with artificial microvascular grafts under perfusion conditions which are relevant to the first moments of flow, when initial platelet deposition occurs.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Biomedical Materials Research 26 (1992), S. 1449-1461 
    ISSN: 0021-9304
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: Compliance matching between the host vessel and vascular grafts used for smalldiameter arterial replacements is thought to be important for longterm patency. However, currently available grafts elicit fibroplastic reactions, resulting in decreasing compliance with time after implantation. Bioresorbable prostheses elicit ingrowth of myofibroblasts containing abundant contractile elements. This led us to investigate whether compliance of implanted bioresorbable prostheses decreased as a function of time and if the kinetics of change correlated with the progession of tissue ingrowth. Woven polyglactin 910 prostheses (10 mm × 4 mm i.d.) were implanted into adult NZW rabbit infrarenal aortas and replicates were harvested serially through 8 months. Control grafts were implanted, and immediately resected. Dynamic compliance was measured a t 1-mm axial increments along each explant using a pulse duplicator apparatus which exposed the harvested samples to realistic pulsatile hemodynamics. Compliance was calculated for proximal, mid, and distal segments of each graft and averaged at each time point by grouping into control (zero time, n =3), early (1-4 weeks, n = 13), and late (6-36 weeks, n = 9) explant periods. At late explant periods both proximal and distal compliance were significantly greater than mid graft compliance (p ≤ .02 and p ≤ .03, respectively). There was a significant increase in proximal compliance between early and late explant times (p ≤ .01). Measured increases in mid and distal segment compliance over time did not reach statistical significance. Myofibroblast laden tissue ingrowth into the inner capsule followed macrophage phagocytosis and was nearly complete prior to the time that an increase in compliance was demonstrated. Thus since the major histologic episodes precede the change in compliance, these are not likely initiated by this biomechanical change. We hypothesize the graft resorption coupled with the ingrowth of more compliant tissue likely leads to the increased compliance of the graft material. © 1992 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 76 (1993), S. 563-595 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cyclic tetrapeptides cyclo(-Leu-Sar-Gly-), cyclo(-Val-Sar-Sar-Gly-), and cylco(-Meleu-Gly-D-Alasar-) have been synthesized from the component amino acids (BOP-Cl coupling), using the pentafluorophenyl esters for the cyclization step (42, 13, and 30% yield, respectively). Multiple deprotonation (LDA in THF/LiBr/DMPU) and addition of highly reactive electrophiles (CF3CO2D, MeI, CH2O, CH2CHCH2Br, PhCH2Br) produce cyclic tetrapeptides with additional substituents introduced diastereoselectively (70 to 〉 98% ds) in yields ranging from 20 to 90%. The C-alkylatd products are all derived from a sarcosine-enolate moiety adjacent to another N-methylamino acid. The structures of the resulting products are determined by NMR spectroscopy (DNOE and ROESY techniques) and by hydrolysis to the parent amino acids, suitable derivatization, and analysis by chromatography on a chiral GC column. It was shown in two cases that the overall yield of cyclization/alkylation to give a disubstitued cyclic tetrapeptide is higher than that of a synthesis of the same product from the corresponding amino-acid building blocks. Surprising temperature and salt effects on the yields and selectivities of the reactions of the cyclic tetrapeptide enolates are presented, and possible mechanistic interpretations are discussed.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Als Höhepunkte auf dem Gebiet der Organoelementchemie der schwereren Elemente der vierten Hauptgruppe (Gruppe 14 des Periodensystems) in den 80er Jahren gelten die Darstellung und vollständige Charakterisierung dreier Verbindungsklassen, deren Existenz bis dahin aufgrund ihrer Reaktivität für nicht möglich gehalten wurde. Hierbei handelt es sich um 1) die dreigliedrigen Ringsysteme Cyclotrisilan, -trigerman und -tristannan, 2) Moleküle mit Element-Element-Doppelbindungen einschließlich Disilen, Digermen und Distannen sowie 3) gespannte Polycyclen mit einem Gerüst aus den schwereren Elementen der 4. Hauptgruppe, z. B. Bicyclo[1.1.0]tetrasilan, Hexagermaprisman und Octasilacuban. Die meisten dieser Verbindungen sind durch sperrige Substituenten stabilisiert. Die Verbindungen ermöglichten Untersuchungen über die Veränderungen physikalischer und chemischer Eigenschaften in Abhängigkeit vom Element und den Substituenten sowie über die thermische und photochemische Reaktivität dieser Systeme, wobei zweiwertige Carben-Analoga nachgewiesen wurden. Parallel zu den experimentellen Arbeiten wurden an nahezu allen im Beitrag diskutierten Stammverbindungen Rechnungen durchgeführt. Einige Polycyclen weisen den Weg zu Verbindungen mit einer Element-Element-Dreifachbindung.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diese Übersicht stellt neuere experimentelle Ergebnisse der Erforschung der unendlichen Geschichte der Vitamin-B12-Biosynthese vor, wobei hauptsächlich auf Arbeiten aus der Arbeitsgruppe des Autors zurückgegriffen wird. Darüber hinaus gibt sie einen persönlichen Ausblick auf die Zukunft der Naturstoff-Biosyntheseforschung. Von zentraler Bedeutung ist mittlerweile die leistungsfähige Kombination von molekularbiologischen und modernsten spektroskopischen Techniken. Jene dienen der Suche nach und der Expression von Genen, die für die Enzyme der Biosynthese codieren, diese machen die biochemischen Vorgänge im NMR-Röhrchen direkt beobachtbar. Als logische Weiterentwicklung dieser Ansätze wird die Durchführbarkeit der Eintopf-Multienzymsynthese von Naturstoffen vorgestellt. Dank der Entwicklung und Nutzung von Klonierungstechniken und der daraus resultierenden Verfügbarkeit von Enzymen für die C-C-Verknüpfung hat sich ein grundlegender Wandel im “Handwerkszeug“ des Bioorganikers vollzogen. Gleichzeitig seien aber auch die Organiker angesprochen, die sich diesen technischen Fortschritt zunutze machen wollen. Ihnen wird sich eine neue Welt natürlicher Katalysatoren erschließen, die Synthesen mit hohen Ausbeuten bei einem oftmals überraschenden, aber durchaus willkommenen Mangel an Substratspezifität versprechen. Und schließlich hoffen wir, unsere Begeisterung für diese modernen Methoden weiterzugeben, mit denen heutige wie auch künftige Generationen von Chemikern die Synthesewege der Natur zu komplexen Naturstoffen erforschen können.
    Additional Material: 24 Ill.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0570-0833
    Keywords: Bond theory ; Tin ; Germanium ; Silicon ; Strained molecules ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The organometallic chemistry of the Group 14 elements E = Si, Ge, Sn in the 1980's is highlighted by the successful construction and characterization of three systems previously thought to be too reactive to exists: (1) three-membered ring compounds including cyclotrisilane, cyclotrigermane, and cyclotristannane, (2) molecules containing E—E double bonds including disilene, digermene, and distannene, and (3) strained polycycles containing a skeleton of Group 14 elements, such as bicyclo[1.1.0]tetrasilane, hexagemaprismane, and octasilacubane. The majority of these numerous compounds now available are fully substituted with bulky ligands to suppress the reactivity intrinsic to the systems. These compounds permit examinations of (1) the variation of physical and chemical properties of a system with these elements and also with the ligands and (2) how two systems are interrelated thermally and photochemically with the intermediacy of the divalent (carbene-like) species. Theoretical calculations on virtually all of the parent compounds discussed in this review are evaluated alongside the experimental results. Some polycycles may constitute a stepping-stone on the way to compounds with a triple bond.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Mass Spectrometry Reviews 13 (1994), S. 287-339 
    ISSN: 0277-7037
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 28 Ill.
    Type of Medium: Electronic Resource
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