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  • Chemistry  (38)
  • Polymer and Materials Science  (20)
  • General Chemistry  (5)
  • 1995-1999  (40)
  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 299-305 
    ISSN: 0887-624X
    Keywords: polygluconamides ; stereoregular polyamides ; stereoregular nylons ; chiral polyamides ; chiral nylons ; aminoaldonic acids ; sugar polyamides ; carbohydrate monomers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two stereoregular polygluconamides, one (3) of polypeptide-type and the other (16) being a polycaproamide containing four stereocenters in the main chain of the repeating unit, have been prepared from D-glucosamine and D-glucose, respectively. The new polyamides were characterized by elemental analysis, and IR, 1H- and 13C-NMR spectroscopies. The molecular weights for 3 and 16 were estimated as 25,000 and 67,000, respectively, on the basis of viscosimetric measurements. Both polyamides display high optical activity; they are highly hydrophilic and readily soluble in water as well as in a variety of organic solvents including chloroform. Polyamide 16 is highly crystalline and yields resistant films with spherulitic texture. © 1995 John Wiley & Sons, Inc.
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1959-1968 
    ISSN: 0887-624X
    Keywords: optically active polyamides ; helical nylons ; nylon-3 ; poly(β-amide)s ; poly(β-aspartate)s ; poly(α-isobutyl-β-L-aspartate) ; stereoselective polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Different polymerization methods were used for the preparation of poly(α-isobutyl-β-D,L-aspartate)s containing variable ratios of D- to L-aspartic units and the microstructure of the resulting stereocopolymers was examined by NMR spectroscopy. Anionic ring-opening polymerization in solution of enantiomeric mixtures of α-isobutyl-β-D- and L-aspartalactams was found to proceed stereoselectively rendering block copolymers composed of right- and left-handed helical sequences. Configurationally statistical copolymers were obtained instead when the enantiomeric lactam mixtures were polymerized in the bulk. Random stereocopolymers could be prepared also by polycondensation in solution of mixtures of pentachlorophenyl α-isobutyl-β-D and -L-aspartates. The conformation in solution and the crystal structure of the resulting copolymers were investigated in connection with their stereochemical configuration and these features compared with those displayed by optically pure poly(α-isobutyl-β-L-aspartate). © 1996 John Wiley & Sons, Inc.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1157-1167 
    ISSN: 0887-624X
    Keywords: zirconocene catalysts ; ethylene ; 1-hexene ; copolymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The PM3(tm) semiempirical method has been used to optimize the structures for the reactants and transition states of the first and second ethylene insertion processes into zirconocene catalytic systems. The results obtained for these reactions are compared with calculations published in the literature performed at different ab-initio theoretical levels. The agreement between our calculations and those reported in the literature is satisfactory. Taking advantage of the reduced computational effort required in semiempirical calculations two additional processes related with the so-called comonomer effect were also studied: ethylene/1-hexene copolymerization, and chain termination reaction, both in the homopolymerization and in copolymerization of ethylene with 1-hexene comonomer. The calculated activation energies support some experimental findings such as the higher polymerization activities in the presence of comonomers and also the molecular weight reduction of the copolymers due to the more favorable β-elimination reactions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1157-1167, 1998
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Heteroatom Chemistry 8 (1997), S. 85-89 
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The transition-state geometries of retroene elimination reactions of propene from allylamines have been calculated by using the semiempirical AM1 method. The most favored geometry resembles a half chair or a flattened boat. It is also found that the transition states are of polar character and that the negative charge on the N atom decreases in the transition state; thus, the reaction is favored by electron donor substituents on the nitrogen atom, as observed experimentally. © 1997 John Wiley & Sons, Inc.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Heteroatom Chemistry 8 (1997), S. 97-102 
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diallyltetramethylpiperidinophosphine 1, diallyldiisopropylaminophosphine 2, and diallylmesitylphosphine 3 were pyrolyzed in a stirred flow reactor over the temperature range 400-450°C, using toluene as carrier gas, producing, in all cases, mixtures of phosphorus-containing products. The pyrolysis of 1 produced 1-tetramethylpiperidino-1-phosphabutadiene, in addition to a mixture of phosphines and polyphosphines. Compound 2 produced the azadiphosphole 4, the phosphinine 5, allylphosphine, and diisopropylaminophosphine as major phosphorated products. The pyrolysis of 3 produced a mixture of phosphines and polyphosphines. The complex mixture generated by the three diallylphosphines indicates the formation of free radicals during their pyrolyses. AM1 calculations on the transition state of an expected retroenetype propene elimination reaction showed that, due to the phosphaalkene character of the transition state, the structure of the latter is very rigid and sensitive to steric effects. Steric hindrance of the substituents on the phosphorus atom compels the molecule to distort the half-chair transition structure, causing a rise in the activation energy to values in the range of a homolytic P(SINGLE BOND)C bond dissociation energy. © 1997 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. 41-54 
    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: This article describes the hydrolytic degradation of a series of nylons based on methylated L-tartaric acid and diamines. These polytartaramides were prepared by a solution polycondensation process using bis(pentachlorophenyl)-2,3-O-dimethyl-L-tartrate and N,N′-bis(trimethylsilyl)alkanediamines with 6, 8, or 12 methylene groups. The stereoregular optically active polyamides obtained were soluble in chloroform and showed intrinsic viscosities between 1.0 and 2.7 dL g-1. The degradation of these polytartaramides in the form of discs has been investigated in buffered salt solutions of pH 2.3, 7.4, and 10.6, and at temperatures of 37, 55, and 70°C. The degradation was monitored by following the changes in molecular weight, mass loss, chemical constitution, and thermal properties. Our results show that these polytartaramides degrade slowly at 37°C, with a degradation rate highly depending upon the number of methylenes in the diamine unit of the polyamide. The pH of the medium has also a great influence on degradation, as well as the temperature, with an important hydrolysis rate enhancement at 70°C. © 1995 John Wiley & Sons, Inc.
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  • 7
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 389-401 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An asymptotic analysis based on Taylor series expansions is used for first-order correction terms to the Henry's law approximation to describe solvation phenomena in multiple solute-multiple solvent systems. The magnitude of these correction terms in solvent systems very near their critical points is of particular concern, as shown in model fluid calculations with the aid of integral equation theory. The results clearly demonstrate that close proximity to the critical point in pure and mixed solvent systems causes the Henry's law approximation to show large errors in predicting solubilities, especially near the critical azeotrope of a mixed solvent system. Theoretical results also show that cross solubility enhancements in a two solutesupercritical solvent system cause cooperative synergism (both solute solubilities are increased relative to the corresponding single solute situations) or reverse synergism (both depressed relative to the single solute situation). It appears to be consistent with the available data. In computer simulations, the solute's infinitely dilute reference state is often used as a basis for describing solute thermodynamic behavior. These simulations are best achieved in the canonical ensemble because of the weak composition dependence of free energies in terms of characteristic variables of this ensemble.
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  • 8
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 2300-2305 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The relative merits of various approaches using computer simulation methods for estimating first-order correction terms to Henry's law in dilute supercritical mixtures are investigated. Three thermodynamic formulations are provided for the calculation of these properties. One method, termed the fluctuation integral approach, requires the explicit calculation of solute-solvent pair correlation functions at the infinite dilution limit, which is a difficult task for simulations given the conflicting demands of both small numbers of solute species (for approximating the infinite dilution limit) as well as the need for large numbers of solute species to improve simulation statistics. A second approach, called the pressure gradient method, does not require the explicit, determination of these solute-solute functions and, as a result, is not as sensitive to the choice of system size and other difficulties associated with establishing an adequate ensemble size and/or number of solute species to be used in the simulations. The third approach uses the exact formulation for the property of interest using Kirkwood-Buff theory. This approach, however, requires all the solute pair correlation functions to be established, making it the most sensitive to issues concerning number of solute species used in the simulations, and so on. An examples is given showing simulation results for these approaches, illustrating their respective strengths and drawbacks.
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  • 9
    ISSN: 1434-1948
    Keywords: Amides ; Chirality ; Clusters ; Copper ; Sodium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new heterometallic sodium(I)-copper(II) compound Na4Cu2 (2) · 10.5 H2O (3), where H8[2] stands for N,N′,N′′,N′′′-methanetetrayltetrakismethylenetetrakis(oxamic acid), has been synthesized and its crystal structure determined by single-crystal X-ray diffraction. The structure of 3 consists of cationic [Cu2(η4:η4-2)]4- dinuclear units, coordinated sodium cations, and water molecules. In the crystal, the dinuclear copper entities are joined through discrete aggregates of eight sodium atoms linked by oxamato and water bridges, leading to a three-dimensional polymeric network.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 1031-1043 
    ISSN: 1434-193X
    Keywords: Carbonates, ring-opening ; Epoxides, ring-opening ; Lactones ; Reduction, diastereoselective ; Polyalcohols ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For preparing tris(γ-lactone) 3 the mono(γ-lactone) 6 was synthesized from the dichlorodiol 12 (99.8% ee). Bisepoxide 9 - derived from dichlorodiol 12 (99.8% ee) - was ring-opened with the Gilman cuprate from 2-lithio-1,5-hexadiene and CuI giving almost exclusively the monoepoxide 21; in five more steps, γ-lactone 30 with the same stereotriad as the target molecule 6 but a different protecting group was obtained. Monoepoxide 33 - also derived from dichlorodiol 12 - was ring-opened with the same Gilman cuprate affording compound 35. It was transformed into the correctly protected γ-lactone 6 in seven steps, key reactions being the ozonolysis 35 → 36 and the diastereoselective reduction 36 → anti-37.
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