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  • Chemistry  (16)
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  • 1993  (16)
  • 1
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Z-Dehydrophenylalanine (ΔzPhe) possessing four oligopeptides, Boc-(L-Ala-ΔzPhe-Aib)n-OCH3 (n = 1-4: Boc, t-butoxycarbonyl; Aib, α-aminoisobutyric acid), were synthesized, and their solution conformations were investigated by 1H-nmr, ir, uv, and CD spectroscopy and theoretical CD calculation. 1H-nmr (the solvent accessibility of NH groups) and ir studies indicated that all the NH groups except for those belonging to the N-terminal L-Ala-ΔzPhe moiety participate in intramolecular hydrogen bonding in chloroform. This suggests that the peptides n = 2-4 have a 4 → 1 hydrogen-bonding pattern characteristic of 310-helical structures. The uv spectra of all these peptides recorded in chloroform and in trimethyl phosphate showed an intense maximum around 276 nm assigned to the ΔzPhe chromophores. The corresponding CD spectra of the peptides n = 2-4 showed exciton couplets with a negative peak at longer wavelengths, whereas that of the peptide n = 1 showed only weak signals. Theoretical CD spectra were calculated for the peptides n = 2-4 of several helical conformations, on the basis of exciton chirality method. This calculation indicated that the three peptides form a helical conformation deviating from the perfect 310-helix that contains three residues per turn, and that their side chains of Δz Phe residues are arranged regularly along the helix. The center-to-center distance between the nearest phenyl pair(s) was estimated to be ∼ 5.5 Å. The chemical shifts of the ΔzPhe side-chain protons (Hβ and aromatic H) for the peptides n = 2-4 indicated anisotropic shielding effect of neighboring phenyl group(s); the effect also supports a regular arrangement of the Δz Phe side chains along the helical axis. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 194 (1993), S. 2215-2224 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymers of 2-(3-methacryloyloxypropyl)-4,5-diphenyloxazole (3) with various monomers were prepared. It was observed that the oxazole rings attached to the copolymer backbone are converted efficiently to the corresponding triacylamino residues by photooxidation using meso-tetraphenylporphin as a photosensitizer in solution and in a thin film of the polymer. This photoinduced transformation in a copolymer 5c having N-isopropylacrylamide as a comonomer was found to be applicable to a positive working photoresist by development with an aqueous solution of amines to dissolve the exposed areas of the film. A new system for positive image formation by visible light is presented.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 949-955 
    ISSN: 0887-624X
    Keywords: radical polymerization ; 3-methylene-5,5′-dimethyl-2-pyrrolidinone ; exomethylene cyclic monomers ; kinetics ; monomer reactivity ratios ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3-Methylene-5,5′-dimethyl-2-pyrrolidinone (α-MDMP), a cyclic analog of N-substituted methacrylamide, was synthesized and polymerized with α,α′-azobis (isobutyronitrile) (AIBN) in solution. Poly(α-MDMP) is only soluble in dimethyl sulfoxide (DMSO) at room temperature. Thermogravimetry of poly(α-MDMP) showed 10% weight loss at 355°C in air and 400°C under nitrogen, respectively. The kinetics of α-MDMP homopolymerization with AIBN was investigated in DMSO. The rate of polymerization (Rp) can be expressed by Rp = k[AIBN]0.49[α-MDMP]1.0 and the overall activation energy has been calculated to be 73.2 kJ/mol. Monomer reactivity ratios in copolymerization of α-MDMP (M2) with methyl methacrylate (M1) are r1 = 0.71 and r2 = 0.71, from which Q and e values of α-MDMP are calculated as 0.75 and -0.43, respectively. © 1993 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 31 (1993), S. 1895-1902 
    ISSN: 0887-624X
    Keywords: 4-methylene-4H-1,3-benzodioxin-2-one ; exo-methylene cyclic monomers ; radical polymerization ; kinetics ; monomer reactivity ratios ; chemical amplification ; decarboxylation ; poly[(o-hydroxyphenyl)acetylene] ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Methylene-4H-1,3-benzodioxin-2-one (MBDOON), an α-substituted cyclic styrene derivative, was synthesized and polymerized readily with 2,2′-azobis(isobutyronitrile) (AIBN) as an initiator in solution. The kinetics of the MBDOON homopolymerization with AIBN was investigated in N-methyl-2-pyrrolidone (NMP). The rate of polymerization, Rp, can be expressed by Rp - k[AIBN]0.52[MBDOON]1.1 and the overall activation energy has been calcualted to be 75.7 kJ/mol. Monomer reactivity ratios in copolymerization of MBDOON (M2) with styrene (M1) are r1 = 0.31 and r2 = 3.20, from which Q and e values of MBDOON can be calculated as 3.0 and -0.7, respectively. Ring-substituted MBDOON monomers such as 6-chloro, 6-methyl, and 7-methoxy derivatives were synthesized and polymerized with AIBN. The 6-substituted MBDOON's readily underwent radical polymerization while the 7-methoxy-MBDOON was slower to polymerize. Poly(MBDOON) is predominantly heterotactic. (rr = 35, mr = 46, and mm = 19%). The polymer releases carbon dioxide at about 200°C and is converted with some depolymerization to poly[(o-hydroxyphenyl)acetylene]. The thermolysis temperature is very much affected by the ring substituent. The onset of carbon dioxide liberation was observed at 140°C in the case of the 7-methoxyl derivative while the 6-substituents had a smaller effect on the decarboxylation temperature. © 1993 John Wiley & Sons, Inc.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 287-291 
    ISSN: 0887-624X
    Keywords: hydrosilylation polymerization ; self-polyaddition ; silicon containing polymer ; macromonomer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 1135-1140 
    ISSN: 0887-624X
    Keywords: polyester ; polycondensation ; tetrahydrofuran ; titanium isopropoxide ; hydrolysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New polyesters 6a-6c consisting of 2,4-linked tetrahydrofuran rings were synthesized by bulk polycondensation of methyl trans- and cis-4-hydroxytetrahydrofuran-2-carboxylates (5a and 5b) and a stereoisomeric mixture of methyl 4-hydroxy-5-methyltetrahydrofuran-2-carboxylate (5c) at high temperature. These monomers were prepared from methyl glycolate or methyl lactate and diethyl maleate through a four-step reaction sequence. The polycondensation was carried out without solvent at different temperatures ranging from 150 to 220°C. Titanium isopropoxide was most effective among the catalysts examined, giving polyesters with number-average molecular weights up to 2 × 104. Polyester 6a consisting of trans-2,4-linked tetrahydrofuran rings was soluble in trifluoroacetic acid and a mixed solvent of chloroform and methanol (10/1, v/v). Polyester 6b composed of cis-2,4-linked tetrahydrofuran rings was soluble in dimethyl sulfoxide and dimethylformamide in addition to the two solvents for 6a. Polyester 6c with 5-methyl-substituted tetrahydrofuran rings was composed of a mixture of stereoisomeric units and thus was soluble in a variety of solvents including chloroform, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, and dimethylformamide. The glass transition temperatures of 6a, 6b, and 6c determined by DSC were 109, 88, and 66°C. These polyesters were found to be very slowly hydrolyzed in a neutral phosphate buffer solution at ambient temperature. © 1993 John Wiley & Sons, Inc.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Advanced Materials 5 (1993), S. 198-206 
    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
    Notes: Computer-aided materials design for semiconductors is reviewed. Reliable predictions are possible for a wide range of problems, such as the behavior of various heterovalent atomic species in III-V semiconductors, including C (conduction type), Si (DX-center), Ge (GaAs/Ge superlattices), S, Se and Te (passivation of GaAs surfaces), by using such computer-aided calculation techniques as pseudopotential methods.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 49 (1993), S. 1921-1929 
    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: Four kinds of epoxy resins: cresol novolac, tris-hydroxyphenylmethane, tetramethylbiphenol, and bisphenol A, were cured with phenol novolac epoxy resins. Characteristics of these epoxy compounds were studied by the positron annihilation lifetime (PAL) technique. Glass transition temperatures, thermal expansion coefficients, and volume of intermolecularspace holes among polymer chains were obtained from the lifetime, τ3, of the long-lived component of ortho-positronium. It was revealed that, at the glass transition temperature, Tg, the volume of the hole created among polymer chains expanded 1.4 times the volume at room temperature. The smaller flexural modulus of tris-hydroxyphenylmethane than that of the other samples was explained by the volume of intermolecular-space holes obtained from τ3. Aging effects were seen in the data of the intensities, I3, of ortho-positronium, which became smaller after heating the samples above Tg. I3 and τ3 were strongly affected by the density of cross-linkings, and their chemical structures. The larger the density of cross-linkings, the smaller I3 and higher Tg were obtained. Epoxy compounds with the higher water-absorption rates had larger intermolecular-space holes. © 1993 John Wiley & Sons, Inc.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 50 (1993), S. 1989-1998 
    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: Photochemical oxetane formation by addition of 1-methyl-2,4,5-triphenylimidazole (1a), 1,2-dimethyl-4,5-diphenylimidazole (1b), and 1-acetylimidazole (1c) to benzophenone (BP), poly(4-vinylbenzophenone) (PVBP), and poly(styrene-co-4-vinylbenzophenone) (PSVBP) was studied in the solution and solid phases. In solution, BP underwent the photoaddition smoothly to all three imidazoles 1a-1c. On the other hand, the photoaddition of PVBP and PSVBP depended on the imidazole employed, that is, 1b and 1c produced the corresponding oxetane, but 1a did not. The lack of oxetane formation from the polymeric BP and 1a is probably due to a rapid triplet-sensitized decomposition of a once-formed oxetane ring as a result of the intramolecular triplet energy transfer from a pendant benzophenone group. © 1993 John Wiley & Sons, Inc.
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Biomedical Materials Research 27 (1993), S. 901-907 
    ISSN: 0021-9304
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: A cell growth factor protein (insulin) and/or a cell-adhesion protein (fibronectin) were immobilized on surface-hydrolyzed poly(methyl methacrylate) membranes. The growth of mouse fibroblast cells STO was accelerated by the immobilized insulin. This acceleration was enhanced by introduction of spacer arms. Coimmobilization of insulin and fibronectin was very effective for the acceleration of cell growth. © 1993 John Wiley & Sons, Inc.
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