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  • 1
    ISSN: 1434-1948
    Keywords: Boranes ; Ruthenium ; Sandwich Complexes ; Diboroles ; Triple-decker ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition products of lithium alkyls and the pentaalkyl-2,3-dihydro-1,3-diborole derivatives 5a-f react with [{(C5Me5)RuCl}4] and [{(C5Me4Et)RuCl}4] to form the violet sandwich compounds 2*c-f and 2∧c, f. These formally 16 VE complexes are in fact electron-poor 18 VE species, because a high-lying combination of σ(B-C) orbitals interacts with the dxz orbital of the Ru atom. Addition of tert-butyl isocyanide to 2*a, or 2*d leads to the isonitrile complexes 6*a, and 6*d, as indicated by the spectroscopic data and X-ray structure analyses. At low temperature the interaction of 2*a, c, or e with H2 yields the classic dihydride complexes 7*a, c, and e, respectively, which have been studied by NMR. Oxidative addition of H3B·THF to the ruthenium atom of 2*a or c, followed by a reductive elimination of H2 and migration of the boranediyl group gives the yellow closo-RuC3B3 ruthenacarboranes 8*a and 8*c, respectively. The reaction of [(C2H4)2RhCl]2 and 2*c generates the tetranuclear complex 9*c.
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  • 2
    ISSN: 0935-9648
    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
    Additional Material: 2 Ill.
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  • 3
    ISSN: 0887-624X
    Keywords: thermally stable polymers ; sucrose-based comonomers and the additive ; octa-O-allylsucrose ; octa-O-crotylsucrose ; penta-O-methylsucrose trimethacrylate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of methyl methacrylate polymers have been prepared containing sucrose-based crosslinkers and additives. Thermogravimetry and long-term aging studies at 200°C show that sucrose-based alkyl and allyl ethers provide unprecedented thermal stability to linear, as well as crosslinked, poly (methyl methacrylate) or PMMA. Linear PMMA and PMMA crosslinked with trimethylolpropane trimethacrylate (TMPTMA) both degrade at 284°C. PMMA containing octa-O-crotylsucrose (1 mol %) degraded at 322°C. Depending on concentration, PMMA containing octa-O-allylsucrose (0.1-1.0 mol % and higher) degraded between 334 and 354°C, and PMMA containing 1′,6,6′-trimethacryloyl-2,3,3′,4,4′-penta-O-methylsucrose (0.1-1.0 mol %) degraded between 309 and 320°C. PMMA containing (1 mol % each) sucrose-based esters, ester-ether derivatives, all degraded at or below the degradation temperature of pure PMMA. Long-term air aging studies revealed that PMMA containing penta-O-methylsucrose trimethacrylate, octa-O-allylsucrose, and octa-O-crotylsucrose did not flow or sag after heating for 24 h at 200°C, but the polymers did show yellowing. While linear and crosslinked samples of PMMA containing compounds other than sucrose ethers lost more than 50% of their original weight within 15 h at 200°C, PMMA containing sucrose-based ethers lost about 8 and 20% of their original weight after 1 and 8.5 days, respectively. Herein we propose a unique mechanism by which saccharide ethers may be imparting this unprecedented thermal stabilization to PMMA. While tertiary hydrogens alpha to oxygens in saccharide ethers are stable to chain transfer during normal polymerization temperatures, they readily chain transfer at 200°C where PMMA is unstable. Chain transfer of these hydrogens is followed by fragmentation to produce alkyl, allyl or crotyl radicals, which combine with the macroradicals and terminate depropagation. © 1995 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 36 (1998), S. 2397-2413 
    ISSN: 0887-624X
    Keywords: epoxy allyl sucroses ; epoxy crotyl sucroses ; sucrose-based epoxy monomers ; thermosets ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two sets of sucrose-based epoxy monomers, namely, epoxy allyl sucroses (EAS), and epoxy crotyl sucroses (ECS), were prepared by epoxidation of octa-O-allyl and octa-O-crotyl sucroses (OAS and OCS, respectively). Synthetic and structural characterization studies showed that the new epoxy monomers were mixtures of structural isomers and diastereoisomers that contained varying numbers of epoxy groups per sucrose. EAS and ECS can be tailored to contain an average of one to eight epoxy groups per sucrose. Quantitative 13C-NMR spectrometry and titrimetry were used independently to confirm the average number of epoxy groups per sucrose. Sucrose-based epoxy monomers were cured with diethylenetriamine (DETA) in a differential scanning calorimeter (DSC), and their curing characteristics were compared with those of diglycidyl ether of bisphenol A (DGEBA) and diepoxycrotyl ether of bisphenol A (DECEBA). EAS and DGEBA cured at 100 to 125°C and exhibited a heat of cure of about 108.8 kJ per mol epoxy. ECS and DECEBA cured at 150 and 171°C, respectively, and exhibited a heat of cure of about 83.7 kJ per mol epoxy. Depending upon the degree of epoxidation (average number of epoxy groups per sucrose) and the concentration of DETA, glass transition temperatures (Tgs) of cured EAS varied from -17 to 72°C. DETA-cured ECS containing an average of 7.3 epoxy groups per sucrose (ECS-7.3) showed no DSC glass transition between -140 and 220°C when the ratio of amine (NH) to epoxy group was 1:1 and 1.5:1. Maximum Tgs obtained for DETA-cured DGEBA and DECEBA polymers were 134 and 106°C, respectively. DETA-cured bisphenol A-based epoxy polymers degraded at about 340°C, as observed by thermogravimetric analysis (TGA). DETA-cured sucrose-based epoxy polymers degraded at about 320°C. Sucrose-based epoxies cured with DETA were found to bind aluminum, glass, and steel. Comparative lap shear tests (ASTM D1002-94) showed that DETA-cured epoxy allyl sucroses with an average of 3.2 epoxy groups per sucrose (EAS-3.2) generated a flexible adhesive comparable in bond strength to DGEBA. However, DETA-cured ECS-7.3 outperformed the bonding characteristics of both DGEBA and EAS-3.2. All sucrose-based epoxy polymers were crosslinked and insoluble in water, N,N-dimethylformamide, tetrahydrofuran, acetone, and dichloromethane. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2397-2413, 1998
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  • 5
    ISSN: 0899-0042
    Keywords: Xenopus oocytes ; stereochemistry ; chiral chromatography ; chiral benzodiazepines ; enantioselective modulation of GABAA receptor ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Xenopus laevis oocytes injected with Poly(A)+-RNA isolated from neuronal tissue express membrane proteins peculiar to the origin of mRNA. The translation of gamma aminobutyric acid type A (GABAA) receptors has been shown by dose/ response behavior of GABA and the reversible blockade of the GABA-induced current by picrotoxin. This current was analyzed quantitatively under two electrode voltage-clamp conditions. This methodology has been applied for the first time to study the functional properties of the receptor as a function of the stereochemistry of the ligands. The (+)-S and (-)-R enantiomers of a water-soluble benzodiazepine derivative, 7-chloro-1,3-dihydro-3-hemisuccinyloxy-5-phenyl-1,4-benzodiazepin-2-one (OXHEM), obtained by preparative high performance liquid chromatographic (HPLC) resolution on chiral stationary phase, act as agonists in the in vitro modulation of the chloride channel. The (+)-S-OXHEM enantiomer was the more active. Chirality 9:286-290, 1997. © 1997 Wiley-Liss, Inc.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 10 (1998), S. 364-369 
    ISSN: 0899-0042
    Keywords: (±)nicotine ; (±)nornicotine ; chiral separation ; enantiomers ; normal phase HPLC ; mobile phase additive ; cellulose-based chiral stationary phase ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper describes the enantiorecognition of (±)nicotine and (±)nornicotine by high-performance liquid chromatography using two derivatized cellulose chiral stationary phases (CSPs) operated in the normal phase mode. It was found that different substituents linked to the cellulose backbone significantly influence the chiral selectivity of the derivatized CSP. The results showed that, in general, the tris(4-methylbenzoyl) cellulose CSP (Chiralcel OJ) surpasses tris(3,5-dimethylphenyl carbamoyl) cellulose CSP (Chiralcel OD). On the former column, the resolution (±)nicotine and (±)nornicotine enantiomers depended largely on mobile phase compositions. For the separation of the nicotine enantiomers, the addition of trifluoroacetic acid to a 95:5 hexane/alcohol mobile phase greatly improved the enantioresolution, probably due to enhanced hydrogen bonding interactions between the protonated analytes and the CSP. For (±)nornicotine separation, a reduction in the concentration of alcohol in the mobile phase was more effective than the addition of trifluoroacetic acid. Possible solute-mobile phase-stationary phase interactions are discussed to explain how different additives in the mobile phase and different substituents on the cellulose glucose units of the CSPs affect the separation of both pairs of enantiomers. Chirality 10:364-369, 1998. Published 1998 Wiley-Liss, Inc.This article is a US Government work and, as such, is in the public domain in the United States of America.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 10 (1998), S. 564-572 
    ISSN: 0899-0042
    Keywords: asymmetric hydrogenation ; aminophosphine phosphinites ; rhodium complexes ; dehydro aminophosphonic acids ; NMR ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiral α-aminophosphonic acid derivatives are efficiently synthesized by asymmetric hydrogenation of the prochiral N-acyl-α,β-dehydroaminophosphonates. PROPRAPHOS-Rh-catalysts from readily available (S)- and (R)-Propranolol proved to be suitable in the homogenous reaction affording an enantiomeric excess of 87-92% with high rate. The aminophosphonic acid derivatives and precursors were fully characterized by 1H, 13C, and 31P NMR spectroscopy. Chirality 10:564-572, 1998. © 1998 Wiley-Liss, Inc.
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  • 8
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: External Crown Fatigue Loading of High and Ultrahigh Pressure Tubes Subjected to Corrosion - a Highly Informative Test Predicting the Crack Growth Behaviour of Tubular Components under Mode II Corrosion Fatigue ConditionsStressing high and ultrahigh pressure tubes by external static or fatigue loads has been qualified as a convenient method to simulate the load case “internal pulsating pressure” by analysing the stress state of thick walled tubes when loaded by internal pressure and external crown loads, respectively. The results of different analytical calculations were compared with that of a Finite-Element-Computation demonstrating, for tubes with nominal pressures in the range of 325-3600 bar, an excellent correspondence.Tests with 86 tube cuttings of steel X 6 CrNiMoTi 17 12 2 (W.-No. 1.4571; ASTM UNS S 31635; BS 320531) showed the following results:In air, pulsating pressures of 325 bar (corresponding to the maximum allowable operating pressures) are sustained indefinitely. Under mode II-corrosion fatigue in 0,1 N H2SO4 (30°C) failure occures after 3,8 · 107 mode cycles. A twentyfold H2SO4 concentration will lower the number of cycles to fracture to one tenth of this value without leaving mode II. Under mode II corrosion fatigue crack growth will propagate faster in radial direction than in air, so that leak-before-break under internal pressure will be likely. Crack growth rates in radial direction increased with increasing acid concentration so that the probability for leak-before-break will further increase.Highest priority for the surveillance strategy of components loaded in mode II CF has, however, the prove that crack initiation in this environment is commencing much earlier than in air, and definitely earlier than found for compact specimens tested in a mode II pulsating fatigue or rotating bending test.
    Notes: Der Scheiteldruckversuch wurde als Verfahren zur Simulation der Innendruckschwellbelastung qualifiziert. Hierzu wurde der Spannungszustand dickwandiger Rohre unter Innendruck- bzw. Scheiteldruckbeanspruchung analysiert. Die Ergebnisse verschiedener analytischer Berechnungsverfahren wurden mit denen einer FE-Rechnung verglichen, wobei sich für Rohre (PN 325 - PN 3600) für alle Berechnungsverfahren eine hervorragende Übereinstimmung ergab.An 86 Rohrabschnitten aus dem Stahl X 6 CrNiMoTi 17 12 2 (W.-Nr. 1.4571), Nenndruckstufe PN 325, Nennweite DN 45, ergab sich u.a. folgendes: In Luft wird ein Schwelldruck in Höhe des zulässigen Betriebsüberdrucks von 325 bar dauerfest ertragen; unter Modus II-Schwingungsrißkorrosion in 0,1 N H2SO4 (30°C) tritt unter dieser Beanspruchung Versagen nach 3,8 · 107 Lastspielen ein. Eine 20fach höhere H2SO4-Konzentration verringert - ohne daß Modus II verlassen wird - diesen Wert auf ein Zehntel. Bei Schwingungsrißkorrosion Modus II findet ein schnelleres Rißwachstum in die Tiefe statt als in Luft, so daß unter Innendruck Leck-vor-Bruch-Versagen eintreten könnte. Die Rißwachstumsgeschwindigkeit in radialer Richtung steigt mit zunehmender Säurekonzentration, womit sich die Wahrscheinlichkeit für Leck-vor-Bruch weiter erhöht.Höchsten Stellenwert für die Überwachungsstrategie derart beanspruchter Bauteile hat aber der Nachweis, daß die Rißinitiierung in diesem Medium viel früher beginnt als in Luft und deutlich früher als an kompakten Proben im Modus II-Schwelloder Umlaufbiegeversuch.
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  • 9
    ISSN: 0894-3230
    Keywords: γ-lactones ; base-catalysed hydrolysis ; reactivity-structure correlations ; isobenzofuranones ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate coefficients were measured for the base-catalysed hydrolysis of a series of substituted 3-(phenoxy- or thiophenoxymethylene)-(Z)-1(3H)-isobenzfuranones (3-phenoxy- or thiophenoxymethylenephthalides) in 70% (v/v) aqueous dioxane at 30.0 °C, in addition to the carbonyl stretching frequencies in chloroform and tetrachloromethane following deconvolution and band separation, when required. The Hammett reaction constants for the alkaline hydrolysis of the 3-/4-substituted phenoxy and thiophenoxy series are ca 0.75 and 1.10, respectively. These results are related to electrostatic field and resonance effects. Successful correlations between the carbonyl stretching frequencies and substituent constants and the rates of alkaline hydrolysis were found. Computational studies using the semi-empirical AM1 method correctly model both the details of the mechanistic pathway and the substituent effects. © 1998 John Wiley & Sons, Ltd.
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  • 10
    ISSN: 0894-3230
    Keywords: γ-lactones ; base-catalysed hydrolysis ; substituted isobenzofuranones ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate coefficients were measured for the base-catalysed hydrolysis of a series of γ-lactones, i.e. 39 substituted 3-(aryl- and alkylmethylene)-(Z)-1(3H)-isobenzofuranones (3-aryl- and alkylmethylenephthalides) in 70% (v/v) aqueous dioxane at 30·0 °C. A Hammett reaction constant for the 3- or 4-substituted phenyl series is ca 1·5, whereas those for the 2-substituted phenyl and 4-substituted 1-naphthyl series, using para-σ values, are ca 1·0 and 1·9. These results are related to an electrostatic field effect model. A very successful correlation between the rates of alkaline hydrolysis of all 39 phthalides and the carbonyl stretching frequencies in chloroform was found. Substituent effects in widely different environments give linearly related effects on both reactivity and physical properties. Computational studies using the semi-empirical AM1 method correctly modelled both the details of the mechanistic pathway and the substituent effects. © 1997 John Wiley & Sons, Ltd.
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