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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1547-1553 
    ISSN: 1434-1948
    Keywords: Imidazaboles ; Carbene-borane adducts ; Azole-borane adducts ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation and characterization of five new imidazabole derivatives is reported: 1,5-dibenzyl-4,4,8,8-tetrahydroimidazabole (2), 4,4,8,8-tetrafluoro-1,5-dimethylimidazabole (3), 4,4-difluoro-8,8-dihydro-1,5-dimethylimidazabole (4), 4,4,8,8-tetrachloro-1,5-dimethylimidazabole (5), and 4,4,8,8-tetraethyl-1,5-dimethylimidazabole (6). The structures of compounds 2-6 as dimeric carbene-borane adducts rather than dimeric N-borane adducts are discussed on the basis of NMR (2-6) and X-ray diffraction data (2, 3, 5 and 6).
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  • 2
    ISSN: 1434-1948
    Keywords: Alkaline earth metals ; Group-13 metals ; Coordination chemistry ; Bis(3,5-di-tert-butyl-1-hydroxy-2-phenyl)amine ligand ; Nonacoordinated strontium compound ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of 3,5-di-tert-butylcatechol and aqueous ammonia with boron, aluminum, gallium, or strontium chloride, or with calcium or barium acetate produce, under oxidizing conditions, neutral complexes of stoichiometric formulae ML (M = BCl), ML2, [M = Al (2), Ga (3), Ca (4), and Ba (5)], and ML3H [M = Sr (6)] [L = different oxidation states of bis(3,5-di-tert-butyl-1-hydroxy-2-phenyl)amine]. The structures of 1 and 4-6 were established by 1H- and 13C-NMR spectroscopy and of 2, 3, and 6 by X-ray diffraction. The coordination compound ClBL (1) was obtained by transmetallation of ZnL2 with BCl3. It is a tetracyclic compound with tetracoordinated boron and nitrogen atoms, the ligand being in the reduced form, bis(hydroxyphenyl)amine. The paramagnetic complexes 2 and 3 crystallized in the triclinic system and are hexacoordinated with two orthogonal planar ligands bonded to the metal atoms. The ligands appear in two different oxidation states: one as the monoanion and another as a radical dianion. Based on their X-ray diffraction molecular structures, it is deduced that both ligands have similar structures, confirming electronic delocalization and fast interconversion of their oxidation states. Ca and Ba complexes are diamagnetic and hexacoordinated, both ligands being monoanions The strontium complex crystallized in the monoclinic system, the metal atom is nonacoordinated, having two ligands as monoanions, and a third one is a neutral protonated diquinone. Its structure is a distorted helix with three paddles in a C3 geometry and its unexpected diamagnetic behaviour is due to the presence of a reduced protonated ligand.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 18 (1995), S. 501-503 
    ISSN: 0935-6304
    Keywords: High resolution GC-MS ; Mass spectrometry ; Anise oil ; Catalytic transformation ; Zeolite Y ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 39 (1996), S. 435-444 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the Brownian dynamics simulation technique, we studied the fracture process of DNA chains subjected to transient extensional flow, letting the solution with DNA molecules pass through a very small orifice (radius = 0.0065 cm), thus experiencing extensional flow of the convergent (sink) type. The DNA molecules were modeled as FENE bead-spring chains with the springs obeying a modified Warner force law, as proposed by Reese and Zimm. The fracture yield was strongly dependent on flow rate and molecular weight, reaching, in our setup, a level of 100% at a flow rate of around 0.001 cm3/s for DNA with molecular weight 26 × 106 (T7 DNA). There was found to exist a critical flow rate (Qcrit) below which fracture did not occur, in accordance with what was observed in studies on polystyrene in transient extensional flow. We found that for DNA, the critical flow rate depended on the molecular weight as Qcrit ∼ M-14 when the hydrodynamic interaction effect (HI) was not included in the simulations. When HI was accounted for, the relation was found to be Qcrit ∼ M-1.1, close to the theoretical prediction for fracture of partly extended chains in transient extensional flow. © 1996 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
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  • 5
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The sequence of a cholecystokinin (CCK) related peptide was modified to obtain analogues, which intereact selectively either with CCK-B, or with δ-opioid receptors. Two kinds of peptides were designed, namely, the cyclic peptides of the H-Tyr-cyclo(D-Pen-Gly-Trp-L-/D-3-transmecaptoproline)-Asp-Phe-NH2 sequence (compounds 1a and 1b, respectively), and the linear peptides of the H-Tyr-D-Val-Gly-Trp-L/D-3-trans-methylmercaptoproline-Asp-Phe-NH2 sequence (compounds 2a and 2b, respectively). The only difference between the chemical structures of the linear analogues compared to the cyclic ones is that one covalent bond has been eliminated and a sulfur atom is replaced by a methyl group. Molecular modeling showed that, among low-energy conformers of cyclic compounds 1, there are three-dimensional structures compatible to the model for δ- receptor- bound conformer, suggested earlier[G. V. Nikiforovich. V. J. Hruby. O. Prakash, and C. A. Gehrig (1991) Biopolymers. vol. 31. pp. 941-955]. Results of binding assays fully supported the rationale for the design of compounds 1 and 2. The cyclic analogue 1a has Ki values of 4.5 and 〉 5000 n M at δ- and μ-opioid receptors, respectively; IC50 values of 3000 n M for both CCK-A and CCK-B receptors, whereas its linear counterpart 2a has ki values of 462 and 229 nM at δ- and μ-opioid receptors, respectively; and IC50 values of 1.6 and 〉 10.000 nM for CCK-A and CCK-B receptors, respectively. The results of this study demonstrate a possibility to redirect a peptide sequence that interacts with one type of receptors (CCK-B receptors) toward interaction with another type (δ-opioid receptors) belonging to a different physiological system. This redirection could be performed by changing the conformational properties of the peptide with very minimal changes in its chemical structure. © 1995 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
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  • 6
    ISSN: 0009-2940
    Keywords: Azolylborane adducts ; Boron-imidazole adducts ; Boron-pyridine adducts ; Protic-hydric interactions ; Protic-fluoride interactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation, NMR and X-ray diffraction studies of a series of azolylboron hydrides derived from pyrrole, indole, and carbazole coordinated with tetrahydrofuran, pyridine, and imidazole are reported. The azolyl substituents are very electroattractive leading to an acidic boron atom which strongly coordinates with the Lewis bases. The stabilization of the =BH2=groups against disproportionation could be explained in terms of the interactions found between the acidic hydrogen atoms of the heterocycles (C=Hδ+ acceptor) and the hydrides (B=Hδ- donors).
    Additional Material: 8 Ill.
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  • 7
    ISSN: 0009-2940
    Keywords: Zeolites ; Titanium ; Epoxidation ; Double bond cleavage ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is unequivocally shown that acetophenone, an oxidation product in the titanium zeolite-catalyzed oxidation of α-methylstyrene, derives from 2-hydroperoxy-2-phenyl-1-propanol as intermediate, which was detected and isolated in this reaction for the first time.
    Additional Material: 2 Tab.
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  • 8
    ISSN: 0009-2940
    Keywords: Lithium 5-Methyl-1,3-dithia-5-azacyclohex-2-ylborate - 5-borane ; 5-Methyl-1,3-dithia-5-azacyclohex-2-yllithium ; Nitrogen heterocycles ; Sulfur heterocycles ; Lithium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Syntheses of the dimers of axial 5-methyl-2-dithiazinyllithium (4) and equatorial 5-methyl-2-diethiazinyllithium-5-borane (5), and lithium 5-methyl-2-dithiazinanylborate-5-borane (6) are reported. Compounds 4, 5, and 6 are configurationally and conformationally stable. The 1H-, 13H-, 13C-, 11B-, and 7Li-NMR study of th reactions of 4 and 5 with BH3—S(CH3)2, BH3 - THF, and CH3I is presented.
    Additional Material: 4 Ill.
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  • 9
    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.
    Additional Material: 6 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 2387-2397 
    ISSN: 0887-624X
    Keywords: poly(vinyl chloride) ; nucleophilic substitution ; stereospecific mechanisms ; solvent influence ; microstructural sensitivity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nucleophilic substitution in poly(vinyl chloride) (PVC) with sodium benzenethiolate has been studied in two kinds of solvent differing in the molecular structure in the vicinity of the carbonyl group. From the evolution of the content of isotactic (mm), heterotactic (mr), and syndiotactic (rr) triads; and of mmmm, mmmr and rmmr isotactic pentads, in the unmodified parts of the polymer, as followed by 13C-NMR, it is unambiguously inferred that any chlorine but the central one of either the isotactic triad at mmr tetrads or the heterotactic triad at rmrr pentads is unreactive. Only a small fraction of mmr tetrads reacts occasionally by the central chlorine of its mr triad instead of the mm. Of those structures, the mmr, especially when located at the end of long isotactic sequences, proves to be highly reactive compared to the rmrr structure. By comparing quantitatively the microstructural changes with degree of substitution and taking into account that the reaction is of SN2 type, the mechanisms of substitution through the three foregoing reactive chlorines have been stated. They are found to be independent of the type of solvent and to account for all the changes in triad and pentad content as experimentally found. Instead, the solvent dependence of the ratio between the mmr- and rmrr-based processes of substitution is such that the depletion of mmr compared to that of rmrr structure may be controlled. The conformational sensitivity of this behavior is discussed on the basis of side work in our laboratory. As a whole, the results of the present work provide some original concepts as to the role of the tacticity dependent microstructure and the related local conformations in the chemical reactions of PVC. © 1996 John Wiley & Sons, Inc.
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