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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Monatshefte für Chemie 124 (1993), S. 1149-1156 
    ISSN: 1434-4475
    Keywords: Aroyl azide ; 4-Toluoyl azide ; Alcoholysis ; Aminolysis ; “Nucleophilic catalysis” ; Kinetics ; Steric effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Primäre Amine reagieren in nicht-nucleophilen Lösungsmitteln mit 4-Toluoyl-azid in einer einheitlichen Reaktion 2. Ordnung, die durch die Größe des Amins und die Lösungsmittel-Polarität beeinflußt wird. Das ändert sich in Gegenwart von Alkoholen, wo auch die Bildung von 4-Toluylsäureestern beobachtet wird. Diese Konkurrenzreaktion wird durch den „kleinsten“ Alkohol (Methanol) und/oder die relativ größeren Amine (Cylohexylamin bzw. 3-Pentylamin) besonders stark begünstigt. Verglichen mit der einfachen Alkoholyse von 4-Toluoylazid wird eine enorme Beschleunigung der Esterbildung, proportional zur Konzentration des nucleophilen Amins, beobachtet. Der Reaktionsmechanismus wird mit besonderer Berücksichtigung sterischer Effekte bei der Konkurrenz von Nucleophilen um das Aroylazid diskutiert.
    Notes: Summary Primary amines2[R:n-butyl(2a), cyclohexyl (2b), 3-pentyl (2c)] react with 4-toluoyl azide1 in non-nucleophilic solvents in a clear second order reaction, which is strongly dependent on the size of the amine2 and the solvent polarity (k 2 [Acetonitril; 25 °C]: 15.51 (2a), 0.83 (2b) and 0.19 (2c) 1/mol·min; ΔH#=22.1 kJ/mol, ΔS#=−170.5 J/mol·K [2b in Acetonitril]). Drastic changes occur in the presence of nucleophilic solvents. With nucleophilic amines2 added to these in the solutions a concurrent reaction with alcohols4 [R: methyl (4a), ethyl (4b),n-butyl (4c)] yielding 4-toluoyl ester5 is observed. This is especially dominating with the “smallest” alcohol methanol (4a) and/or effectively promoted by “bulky” amines (2b, 2c; up to 99%5a). Compared with the pure alcoholysis a huge acceleration of the ester formation, proportional to the cencentration of the nucleophilic amine2, is observed. The reaction mechanism is discussed with special emphasis on steric effects in the competition of nucleophiles for the aroyl azide1.
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  • 2
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The aim of the studies was to elucidate if it is possible to modify chemically the surface, and by this means specifically the ultrafiltration properties, of polyacrylonitrile membranes using photoreactions of aromatic azides. Nine azides distinguishable by different more or less hydrophilic or hydrophobic substituents were applied. Soaking in 0.05 molar solutions of the aryl azides in methanol resulted in an uptake of 1.25-1.95 · 10-4 mol/g azide in the membranes. About 1 · 10-4 mol/g aryl azide were adsorbed onto the surface of the porous membrane, which had been determined to be 79 m2/g measuring the 4-nitro phenol isotherm. With methyl 4-azido benzoate as model compound, using HPLC analysis of extracts of membrane samples, it was possible to determine conversion and composition of the product mixture in the course of UV photolysis. The photolysis rate decreased with irradiation time, after 32 minutes 59% conversion were observed. Consequently, shorter exposure times should provide modifications exclusively near the outer surface of the membrane. Soluble photolysis products were the methyl esters of 4-nitroso, 4-nitro and 4-amino benzoic acid, resp.; the yields were 3, 13, and 5%, resp. Only traces of the azo- and azoxy-compounds were detected. It was demonstrated with the help of UV reflectance and FT-IR ATR spectroscopy, applied to photo-modified PAN membranes, that a surface functionalisation via formation of secondary amines occures. It is expected to create PAN membranes with specifically modified surfaces by the developed photo-modification strategy because the various aromatic azides have different functional groups but analogous photoreactivity.
    Notes: Durch Photoreaktionen aromatischer Azide sollte die ternwirksame Oberfläche von Ultrafiltrationsmembranen aus Polyarcrylnitril chemisch modifiziert werden, um deren Ultrafiltrations-Eigenschaften gezielt zu verändern. Neun mit unterschiedlich hydrophilen bzw. hydrophoben Gruppen substituierte Azide wurden eingesetzt. Durch Träanken mit 0,05 molaren Lösungen der Arylazide in Methanol naöhmen die Membranen insgesamt 1,25-1,95 · 10-4 mol/g auf. Davon wurden ca. 1 ·10-4 mol/g an der Oberfläche der Porenmembran (79 m2/g, mit Hilfe der p-Nitrophenol-Adsorptions-isotherme ermittelt) adsorbiert. Die HPLC-Analyse der Extrakte von Membranproben gestattete für 4-Azidobenzoesäuremethylester als Modellverbindung die Ermittlung von Umsatz und Produktverteilung bei der UV-Photolyse. Die Umsatzgeschwindigkeit nimmt mit der Belichtungsdauer ab, nach 32 min waren 59% Azid photolysiert. Als lösliche Photolyseprodukte wurden 4-Nitroso-, 4-Nitro bzw. 4-Aminodenzoesäuremethylester in 3%, 13% bzw. 5% Ausbeute gefunden, die Azo- bzw. Azoxy-Verbindungen traten nur in Spuren auf. Mit Hilfe von UV-Reflexions- und FT-IR-ATR-Spektroskopie an PAN-Membranen konnte eine Funktionalisierung der Membranoberfläche durch sekundäre Amin-Strukturen als Ergebnis der Photomodifizierung nachgewiesen werden. Die entwickelte Photomodifizierungsvariante sollte durch Einsatz von Arylaziden mit Prinzipiell analoger Photogreaktivität, aber unterschiedlichen funktionellen Gruppen die Herstellung spezifisch oberflächenmodifizierter PAN-UF-Membranen gestatten.
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  • 3
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The aim of the studies was to characterize the ultrafiltration properties of a variety of photochemically modified membranes, made by a new approach starting with two types of PAN-UF membranes and using nine aromatic azides bearing different more or less hydrophilic or hydrophobic substituents. The influence of the surface functionalization (hydrophilization, introduction of charges/hydrophobization) realized by this means onto the water permeability, the dextrane selectivity, and the permeabilities during and after UF, resp., after simple contact with solutions of ovalbumine and lysozyme was the major subject. Modified membranes made using the aryl azides with hydrophilic groups, 4-azidobenzoic acid, Ib, (4-azidophenyl)trimethylammonium iodide, If, sodium (4-azido)-benzene sulfonate, Id, showed enhanced water fluxes and reduced dextrane retention. All the other azides caused reduced water permeability, enhanced dextrane selectivity, and significant flux reductions as a consequence of contact with ovalbumin solutions (pH = 5.0). The strongest effects were achieved with the two expecially hydrophobic compounds, 2-naphthyl azide, Ih, and 2-naphthoyl azide, IX. On the other hand, a pronounced positive effect of photo-modification on the protein fouling behaviour became evident in the UF of lysozyme (0.05%, pH = 10.5). Using the membranes modified with Id a much higher filtrate flux (Jv = 48.1 l/m2h) was observed as compared with the original PAN membrane (Jv = 13.1 I/m2h). The perspectives and the limitations of the developed modification strategy are discussed.
    Notes: Nach einem neuartigen Verfahren mit Hilfe von neun, mit verschieden hydrophilen bzw. hydrophoben Substituenten synthetisierten aromatischen Aziden unterschiedlich photochemisch modifizierten Polyacrylnitril-Ultrafiltrations-Membranen wurden in UF-Versuchen charakterisiert. Dabei sollte der Einfluß der so erzielten Oberflächenfunktionalisierungen (Hydrophilierung, Einführung von Ladungen oder Hydrophobierung) auf das Trennverhalten (Wasserdurchläassigkeit und Selektivitäat für Dextrane, Permeabilität während und nach der UF bzw. nach einfachem Kontakt mit Ovalbuminund mit Lysozym-Lösungen) studiert werden. Die Modifizierung mit den Arylaziden, die hydrophile Gruppen enthalten (4-Azidobenzoäure, Ib, (4-Azidophenyl)-tri-methylammoniumiodid, If, Natrium-4-azidobenzolsuflfonat, Id), führt zu einer erhöhten Durchlässigkeit der Membranen für Wasser und Dextrane. Alle anderen Azide, darunter besonders stark die deutlich hydrophoben 2-Naphthoylazid, Ih, und 2-Naphthoylazid, IX, verringern die Wasserpermeabilität, erhöhen das Rückhaltevermögen für Dextrane und verstärken die Effekte der Wechselwirkungen mit Ovalbumin (pH = 5,0). Das wird in Flußreduzierungen verglichen mit der unmodifizierten PAN-UF-Membran sichtbar. Ein positiver Effekt der Photomodifizierung wird besonders deutlich bei der UF von Lyasozym (0,05%, pH = 10,5) mit der mit Id modifizierten Membran (Jv = 48,1 l/m2h) im Vergleich zur Ausgangs-Membran (Jv = 13,1 1/m2h). Die Perspektiven und die Grenzen des Modifizierungsverfahrens werden abschließend diskutiert.
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  • 4
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Heterogeneous surface modification of polyacrylonitrile (PAN) ultrafiltration (UF) membranes is realized with UV irradiation-initiated graft polymerization of acrylic acid (AA) from the gas phase onto photoinitiator (benzophenone, BP)-coated samples. In the absence of monomer, PAN functionalization by ketyl radicals dominates after UV excitation of sorbed BP. With AA, graft and total polymer yield increase with BP loading and UV irradiation time. Average molecular weight and distribution of PAA homopolymer - formed in parallel during graft polymerization - are analyzed with gel permeation chromatography. Morphology of PAN-gr-AA UF membranes is checked with scanning electron micrographs (SEMs) and atomic force microscopy. Chemical changes are characterized with FTIR-ATR spectroscopy and SEM/EDX analyses, indicating a pronounced surface selctivity of the graft polymer modification (localized in the upper 5-μm membrane thickness). The amount of grafted PAA systematically reduces membrane permeability and increases dextrane retention, as verified in UF experiments. Photo graft polymer modificationof UF membranes will be applied to adjust membrane performance by controlling surface hydrophilicity and permeability using other monomers and/or further graft polymer functionalization. © 1995 John Wiley & Sons, Inc.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 56 (1995), S. 325-343 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Excitation with low temperature helium or helium/water plasma and subsequent exposure to air of polyacrylonitrile (PAN) ultrafiltration membranes was used to hydrophilize the surface of these materials. We analyzed the effectiveness of this approach as a function of plasma operating variables including gas phase composition, plasma power, treatment time, and system pressure. Following the changes in physical and chemical composition of the PAN surface resulting from these modifications was a major aspect of this work. Techniques such as the captive bubble contact angle method, ellipsometry, ESCA, and FTIR-ATR were all used. In addition, the formation and lifetime of peroxides during these processes were determined. At low powers (≤ 25 W) and short treatment periods (≤ 30 s), the main chemical conversion of PAN surfaces was simultaneous hydrophilization and stabilization via PAN cyclization. Relatively small water permeability changes were observed as a result of such treatment. © 1995 John Wiley & Sons, Inc.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 58 (1995), S. 1567-1576 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The hydrophilicity of poly(vinyl alcohol) (PVA) was lowered by acetalization with propionic aldehyde. After UV irradiation of pendent styrylpyridinium groups, these prepolymers form networks of different hydrophobicity depending on the degree of acetaization. PVA films containing different amounts of propionic acetals were doped with 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl. Then, the ESR spectra of the spin probe entrapped in the polymeric network were monitored while allowing different solvents to diffuse into the polymer. The rate of spin probe mobilization depends on the hydrophilicity/hydrophobicity of both the polymer network and the solvent. However, the modified polymers, even the more hydrophobic ones, are hydrophilic in comparison to “really” hydrophobic polymers. This is probably caused by the character of the parent polymer (PVA), unreacted hydroxy groups. S++uiations of the ESR spectra have shown that in polymers with a higher degree of acetalization domains of different hydrophobicity are built in which the spin probes have a different mobility. © 1995 John Wiley & Sons, Inc.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 60 (1996), S. 1147-1161 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Chemical reactions toward acyl azide activated polyacrylonitrile (PAN) and conditions for membrane surface modifications are described. Ultrafiltration (UF) membranes were prepared from PAN homopolymer and copolymer with methyl acrylate. Besides hydrazide formation and nitrosation, a new method to introduce acyl azide groups into carboxyl modified PAN, using azido transfer with diphenyl phosphoryl azide, was developed. Chemical conversions were characterized, especially with Fourier transform infrared spectroscopy. The heterogeneous modifications are not chemically selective due to side reactions and/or incomplete conversion. The pore structure is altered predominately via modified polymer swelling causing changed UF fluxes and selectivities. However, for the modification via PAN reaction with hydroxyl amine, acid hydrolysis, and azido transfer, the initial membrane separations performance is qualitatively preserved. Using the acyl azide ḿethod, amylo-glucosidase (AG) (EC 3.2.1.3) was immobilized onto the modified PAN UF membranes, enabling hydrolysis of starch or maltose to glucose. Enzyme activity was assayed depending on previous chemical modification (azide content) and immobilization (pH) conditions as well as hydrolysis parameters (substrate, conversion during diffusion or UF). The best results (up to 600 mU/cm2 at 40°C and pH 5.0) were obtained after modification of PAN membranes via carboxyl creation and azido transfer. AG convalently bound to PAN is not influenced much in its catalytic properties (Km = 3.48 and 3.1 mmol/L for free and bound AG, respectively, with maltose at 40°C and pH 5.0). Under UF conditions, AG effective activity can be improved by the convective flow through the membrane. UF selectivity for the polymer starch determines effective substrate concentrations in the membrane, thus affecting observed activities and product purities in the filtrate. © 1996 John Wiley & Sons, Inc.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 55 (1995), S. 1495-1505 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The photoreactive amphiphile p-(stearyl amido) benzoyl azide (SABAz) was synthesized and grafted onto surface of thin polyacrylonitrile (PAN) films by irradiation with UV light. Two different techniques were applied, namely, Langmuir-Blodgett (LB) deposition and casting from solution. A high degree of order and a hydrophobic surface were established by reflection-absorption FT-IR spectroscopy (RA-IR) and contact angle measurements. The stability against treatment with water, tetrahydrofuran, and chloroform was tested. A considerable amount of amphiphilic molecules remains on the surface also after treatment with chloroform. RA-IR spectra taken from photomodified PAN films prepared by both techniques are almost identical after chloroform treatment, indicating a similar coupling mechanism. © 1995 John Wiley & Sons, Inc.
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  • 9
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Covalent end-on grafting of poly(ethylene glycol) (PEG) onto a polysulfone (PSf) surface using α-4-azidobenzoyl-ω-methoxy-PEG (ABMPEG) is described. Photoreactive ABMPEG was synthesized by reacting monomethoxy-PEG (MPEG) with 4-azidobenzoyl chloride, yielding complete substitution of the hydroxyl groups. After adsorption from aqueous solutions, ABMPEG was photo-grafted under wet conditions onto PSf ultrafiltration (UF) membranes. Contact angle (CA) measurements showed the increased hydrophilicity of modified membranes and the irreversibility of the modification. Bovine serum albumin (BSA) adsorption decreased by 70% and the permeability decay after protein adsorption became less severe for the modified membranes compared to unmodified reference membranes.
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  • 10
    Publication Date: 2009-03-24
    Print ISSN: 0024-9297
    Electronic ISSN: 1520-5835
    Topics: Chemistry and Pharmacology , Physics
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