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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 69 (1986), S. 1971-1989 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nitrocyclohexene undergoes facile SnCl4-induced, [4 + 2]-cycloadditions with simple cycloalkenes to produce nitronates. The nitronates can be transformed sterospecifically into a number of other functional groups (alcohol, ketone, oxime, amine) by hydrolytic, reductive, and oxidative processes. The mechanism of the [4 + 2]-cycloaddition is believed to involve formation of a zwitterionic intermediate which can collapse via competing pathways to form the observed products. 1,3-Dipolar cycloadditions of the nitronates are described.
    Additional Material: 5 Tab.
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  • 2
    ISSN: 0009-2940
    Keywords: Gas-phase dissociation ; Appearance energies ; Calculations, AM1 ; Pyridinium cations, N-benzyl-2,4,6-substituted ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Collisionally activated dissociations (CADs) of various pyridine-ring substituted N-benzylpyridinium cations in the gas phase form the substituted pyridine and benzyl carbocation. Appearance energies (AEs) are estimated quantitatively from the appearance thresholds of the corresponding fragment ion from the laser-desorbed pyridinium cations. MO calculations predict that such unimolecular dissociation processes lead initially to ion-molecule pairs (IMPs): some such IMPs are of significantly lower energy than the fully dissociated products. The AEs have also been compared with the energy differences [ΔΔHf=ΔHf(Py) + ΔHf(R+)  -  ΔHf(Py+R)] determined by AM1 calculations: in many cases these are quite close to the calculated energy differences; discrepancies are discussed.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2715-2725 
    ISSN: 0887-624X
    Keywords: semi-IPN ; PEG ; TMPTA ; phase separation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Semi-interpenetrating polymer networks (semi-IPNs) of poly(ethylene glycol) (PEG) in poly(trimethylolpropane triacrylate) (TMPTA) were synthesized from PEG melts in neat TMPTA monomer, using PEG of molecular weights from 4000 to 100,000 g/mol. Differential scanning calorimetry and transmission electron microscopy were used to examine phase separation occurring during network formation. The degree of phase separation was observed to depend upon the rate of PEG aggregation relative to the rate of network formation during TMPTA polymerization. Higher molecular weight PEG and acrylate-functionalized PEG formed more phase-mixed networks compared to lower molecular weight PEG; acetatefunctionalized PEG showed no difference from unmodified PEG in the extent of phase mixing. For networks that demonstrated phase separation, the PEG was observed to be in two states: some being phase mixed and solvent inextractable, and some being phase separated and solvent extractable. Phase-mixed networks could be obtained from this thermodynamically incompatible polymer pair utilizing rapid photopolymerization systems to overcome PEG phase aggregation and kinetically entrap the PEG in a nonequilibrium phase-mixed state. These mixed-phase semi-IPNs of PEG and TMPTA may be useful in biological applications where the presence of PEG is desired throughout the bulk matrix rather than as a surface graft to reduce biological interactions. © 1994 John Wiley & Sons, Inc.
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1499-1514 
    ISSN: 0887-624X
    Keywords: PTFE ; surface modification ; benzophenone ; UV light ; diphenyl ketyl radical anion ; benzhydrol anion ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(tetrafluoroethylene) (PTFE) films were surface modified in a solution of benzophenone and sodium hydride in dry dimethylformamide by ultraviolet (UV) light irradiation. The extent of surface modification was characterized after durations of UV light irradiation from 5-20 min at temperatures from 19-60°C. The modified films were analyzed by electron spectroscopy for chemical analysis, diffuse reflectance ultraviolet-visible light spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, dynamic contact angle measurement, and low-voltage scanning electron microscopy. PTFE surfaces produced by this modification demonstrated extensive defluorination, oxygen incorporation, surface unsaturation, and reduction in both advancing and receding dynamic water contact angles in a manner that was more extensive at long durations of irradiation and at high temperatures. Morphological damage depended upon treatment conditions, but extensive surface modification could be obtained without substantial morphological damage to PTFE films. Control experiments indicated that the surface modification proceeded by photoexcitation of either diphenyl ketyl radical anion or benzhydrol anion, the products of reaction of benzophenone with sodium hydride. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1499-1514, 1997
    Additional Material: 5 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3467-3482 
    ISSN: 0887-624X
    Keywords: surface modification ; photograft polymerization ; PTFE ; benzophenone ; diphenyl ketyl radical anion ; acrylic acid ; acrylamide ; PEG monoacrylate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The objective of this study was to explore and optimize the photograft polymerization of acrylate monomers and macromonomers upon premodified poly(tetrafluoroethylene) (PTFE) substrates, with a view toward applying these grafted materials as biomaterials. PTFE films were photochemically reduced by exposure to short wavelength ultraviolet (UV) light in the presence of the reducing agents, i.e., diphenyl ketyl radical anion, generated from a solution of benzophenone and sodium hydride in dimethylformamide (Noh et al., J. Polym. Sci. A, Polym. Chem., 35, 1499 (1997)). The photochemically reduced PTFE films were subsequently modified by photograft polymerization of acrylic acid, acrylamide, and poly(ethylene glycol) monoacrylate (PEG-Ac) by employing long wavelength UV irradiation with benzil dimethyl ketal as an initiator. The photochemically reduced PTFE films were good substrates for photograft polymerization, leading to surfaces with chemical compositions close to those of the respective homopolymers as determined by electron spectroscopy for chemical analysis. Photograft polymerization of PEG-Ac on the photochemically reduced surface was also explored with different concentrations (1, 2, 4, 6, and 8%; v/v) and molecular weights (200, 400, 1000, and 2000 g/mol) of PEG-Ac, different durations (5, 10, and 20 min) of long wavelength UV irradiation, and different concentrations (0.1, 0.2, 0.4, and 0.8%; v/v) of benzil dimethyl ketal. Higher concentrations and lower molecular weights of PEG-Ac generally led to more extensive photograft polymerization, whereas the concentration of benzil dimethyl ketal and duration of UV irradiation did not substantially influence the extent of photograft polymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3467-3482, 1997
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 32 (1988), S. 821-825 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 44 (1994), S. 383-386 
    ISSN: 0006-3592
    Keywords: PEG coating ; islet of Langerhans ; insulin ; diabetes mellitus ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Poly(ethylene glycol) (PEG) has been used previously to alter immune interactions and systemic clearance of therapeutic proteins. We present herein chemical approaches for the conceptually similar treatment of therapeutic cells and tissues whereby immune and cell adhesive interactions may be reduced or interrupted, in the context of the transplantation of xenogeneic islets of Langerhans for the treatment of insulin-dependent diabetes mellitus. Visible-light-initiated interfacial photopolymerization of multifunctional PEG-based macromers was performed directly upon the surface of rat islets of Langerhans to produce conformal barrier hydrogel coatings with thickness of order 10 μ;m. The islets continued to be normal in ultrastructure and function as reflected by response to a glucose challenge in vitro. © 1994 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 43 (1994), S. 772-780 
    ISSN: 0006-3592
    Keywords: bioadhesion ; peptides ; poly(ethylene glycol) ; polymer networks ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Novel artificial extracellular matrices were synthesized in the form of semi-interpenetrating polymer networks containing copolymers of poly(ethylene glycol) and acrylic acid (PEG-co-AA) grafted with synthetic bioadhesive peptides onto exposed carboxylic acid moieties. These substrates were very resistant to cell adhesion, but when they were grafted with adhesive peptides they were highly biospecific in their ability to support cell adhesion. Extensive preadsorption of adhesive proteins or peptides did not render these materials cell adhesive; yet covalent grafting of adhesive peptides did render these materials highly cell adhesive even in the absence of serum proteins. Polymer networks containing immobilized PEG-co-AA were grafted with peptides at densities of 475 ± 40 pmol/cm2. Polymer networks containing immobilized PEG-co-AA N-terminally grafted with GRGDS supported cell adhesion efficiencies of 42 ± 4% 4 h after seeding and became confluent after 12 h. These cells displayed cell spreading and cytoskeletal grafted with inactive control peptides (GRDGS, GRGES, or no peptide) supported cell adhesion efficiencies of 0 ± 0%, even when challenged with high seeding densities (to 100,000 cell/cm2) over 14 days. These polymer networks are suitable substrates to investigate in vitro cell-surface interactions in the presence of serum proteins without nonspecific protein adsorption adhesion signals other than those immobilized for study.
    Additional Material: 5 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 35 (1989), S. 793-802 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A piston reactor has been developed to examine some aspects of particle formation during the pyrolysis of silane (SiH4). This reactor generates conditions intermediate between a static pyrolysis reactor and a shock tube reactor. It effectively excludes contributions of wall reactions to the pyrolysis experiments. The apparent kinetics for this reactor do not conform to values published in the literature. A model that incorporates silane-particle reactions can account for the deviations. In addition, emission of visible light accompanies the sooting reactions. The source of this emission seems to be the sum of incandescence from the hot particles and continuum radiation from another source.
    Additional Material: 12 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 15 (1992), S. 669-676 
    ISSN: 0935-6304
    Keywords: Selective GC detection of metals ; Atomic emission detection ; Microwave-induced plasma ; Metal-containing compounds ; Metalloporphyrins ; Organomanganese ; Organotitanium ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Element-selective GC detection by microwave-induced plasma atomic emission spectroscopy has been used to examine a wide variety of compounds containing metals, non-metals, and metalloids. “Recipes”, or new selective detection schemes for use with the software of the computer-controlled system, have been developed for the selective detection of boron, aluminum, gallium, titanium, vanadium, chromium, manganese, rhenium, palladium, and platinum. Figures of merit including limits of detection, linear dynamic range, and spectral selectivity over carbon have been established for most of these elements. Gas chromatography - atomic emission detection (GC-AED) has been applied to the selective detection of vanadium, nickel, and iron in metalloporphyrins present in crude oil, manganese-selective detection of methylcyclopentadienylmanganese tricarbonyl (MMT) in gasoline, and titanium-selective detection of reaction mixtures containing titanium catalysts or titanium boride molecular precursors.
    Additional Material: 10 Ill.
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