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  • 1
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pure pencillin N α-sulfoxide (1) and penicillin N β-sulfoxide (2) were obtained by HPLC and tested as substrates for deacetoxycephalosporin C synthetase (DXCS). Neither one of the sulfoxides was utilized under conditions of conversion of penicillin N (8) to deacetoxycephalosporin C (9). The cephalosporin C α and β-sulfoxides (3 and 4, resp.) were also prepared. Relative stabilities of the sulfoxides 3 and 4 are discussed by interpretation of the 13C-NMR spectra.
    Additional Material: 9 Ill.
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  • 2
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of protonation and hydrogen bonding in linear Schiff bases obtained from n-butylamine with butyraldehyde, crotonaldehyde, sorbaldehyde and all-trans-retinal were studied by means of 15N and 13C NMR. The protonation-induced chemical shifts (Δδ) are an order of magnitude larger for 15N than for 13C. For 15N, this effect was found to increase with the extent of conjugation, culminating in the retinylideneimine (Δδ = -146 ppm), which constitutes a model for the study of the structure of the Schiff base linkage in visual pigments and related systems. Theoretical calculations of protonation-induced Δδ values based on MINDO/ 3 are in agreement with experimental results.
    Additional Material: 4 Ill.
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  • 3
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Human fibrinogen was treated with thrombin in the presence of fibrinoligase (Factor XIIIa) and calcium ion at pH 8.5, ionic strength 0.45, and the ensuing polymerization was interrupted at various time intervals (t) both before and after the clotting time (tc) by solubilization with a solution of sodium dodecyl sulfate and urea. Aliquots of the solubilized protein were subjected to gel electrophoresis on polyacrylamide gels after disulfide reduction by dithiothreitol and on agarose gels without reduction. The degree of γ-γ ligation was determined from the former. The latter provided the size distribution of ligated end-to-end sequences produced by splitting the ligated staggered overlapped oligomers down the middle, for degrees of polymerization, x, from 1 to 10. Addition of fibrinoligase (in which the activating thrombin had been inhibited by p-nitrophenyl-p′-guanidinobenzoate, NPGB) to Kabi fibrinogen showed the presence of small amounts of ligatable oligomers. Addition of fibrinoligase to a polymerizing mixture in which the action of thrombin had been stopped before clotting by NPGB produced the same distribution of ligated end-to-end sequences that was obtained when fibrinoligase was originally present, at least for reaction times up to 0.7 of the clotting time. The kinetics of γ-γ ligation by fibrinoligase acting on a polymerized mixture stabilized by NPGB were followed. The reaction was first order in the concentration of ligatable γ-γ junctions and the initial velocity was proportional to the enzyme concentration. The time evolution of size distribution of ligated end-to-end sequences agreed with a theory based on random ligation of ligatable junctions.
    Additional Material: 6 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 23 (1984), S. 2067-2081 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Resonance Raman spectra of the nucleoside 5′-monophosphates UMP, CMP, AMP, and GMP have been obtained with 266- and 213-nm radiation, the fourth and fifth harmonics of a Nd:YAG laser. The 266-nm radiation is resonant with the states giving rise to the first absorption band of the bases. The resulting spectra are in agreement with those reported previously using similar wavelength excitation but are generally of better quality. The 213-nm radiation is resonant with those states giving rise to the second strong absorption band of the bases. The spectra obtained with this wavelength show several new features relative to the 266-nm spectra, including strong enhancement of modes of the pyrimidines with a character similar to the e2g ν8 mode of benzene, relative enhancement of ring modes at 1580 and 729 cm-1 in AMP, and strong enhancement of the 1670-cm-1 C = O mode of GMP. These enhancements are discussed in terms of previously reported preresonance behavior and predicted intensities based on CNDO bond-order changes and normal-mode calculations. The results of a preliminary study of the effect of the interaction of GMP with cis-dichlorodiammineplatinum(II) on the 213-nm resonance Raman spectrum is also discussed.
    Additional Material: 8 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 23 (1984), S. 2157-2172 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of organic solvents on the 31P-mr chemical shifts of various phosphate diesters have been investigated in water and mixed-organic solvent systems. The addition of organic solvents to cyclic phosphates and to diethyl phosphate causes large upfield shifts of the phosphorus resonance which are attributed to solvent-induced changes in the local hydration of the phosphodiester group. This is consistent with the fact that there is an inverse correlation between the hydrogen-bond-donating ability of the solvents and the magnitude of the shifts they induce. Other possible interpretations, such as solvent-induced ion pairing and solvent-induced conformational changes, appear to be eliminated. Fourier-transform ir study of the cyclic nucletides reveals that there are also large solvent-induced shifts in the frequency of the antisymmetric OPO stretching frequency, and a comparison of the two types of measurements indicates that there is a linear correlation between shifts observed in the ir and in the 31P-nmr spectra. With UpU, the solvent-induced 31P-nmr shifts are ∼3 times smaller than those observed with the cyclic phosphates and the solvent-induced shift of the OPO band is reduced (factor of ∼1.7) as compared with the cyclic phosphates. With the single-stranded polynuclotides, poly(C) and poly(U), the solvent-induced shifts in both the nmr and ir are quite small (∼0.1 ppm and ∼1 cm-1). The very small solvent effects observed with poly(U) and poly(C) are attributed to a combination of steric effects and a polyelectrolyte effect which maintains a high density of counterions with waters of hydration in the vicinity of the charged backbone and makes the phosphates much less susceptible to solvent-induced changes in hydration.
    Additional Material: 7 Ill.
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  • 6
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the crystal structure of the title compound at 98 K the dimethylamino group has pyramidal geometry. The nitrogenlone pair is not directed towards the triple bond; instead, one N—CH3 bond lies almost in the plane of the disubstituted ring, directed away from the triple bond, while the other N—CH3 bond and the lone pair are directed to opposite sides of the plane, nearer to the acetylene. There is a remarkably short intramolecular contact (2.39 Å) between a methyl H- and an acetylenic C-atom. The Taft σI parameter of the arylethynyl substituent appears to be similar to that of a carboxylic ester, judging from the bond-angle deformation at the ipso-C-atom.
    Additional Material: 5 Ill.
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  • 7
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of 2-dimethylaminobenzenediazonium tetrafluoroborate has been determined at 183 K by X-ray diffraction. The cation is very nearly planar, the strong steric interaction between the ortho-groups being diminished by in-plane angular distoritions.
    Additional Material: 3 Ill.
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  • 8
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 24 Ill.
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  • 9
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Secondary and tertiary hindered amines of the piperidyl type and many other piperidyl compounds can protect various polymers against oxidations initiated by light, heat and ionizing radiation. These amines stabilize by being converted to a series of products which can scavenge with high stoichiometry the main radicals responsible for the oxidative chain. This high stoichiometry results from the cyclical regeneration of the scavenging piperidyl species. The efficiency of the hindered amines as antioxidants in polyolefins is enhanced by their ability to associate with the unstable oxidized domains in which photo- and thermal oxidations will eventually reinitiate. Secondary amines can also slowly decompose intramolecularly hydrogen bonded hydroperoxide groups of the type found in polypropylene. This process may destroy the unstable oxidation product before the hydroperoxide can re-initiate oxidation and also generates another powerful antioxidant, a hydroxylamine. Despite the cyclical regeneration of active piperidyl radical scavengers, side reactions can produce non-scavenging products or even photo-initiators which will progressively accumulate and strangle the antioxidant activities.
    Additional Material: 1 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 29 (1984), S. 311-318 
    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: Differential scanning calorimetry (DSC) and infrared spectroscopy (IR) have been used to study the crosslinked epoxy system tetraglycidyl-4,4′-diaminodiphenyl methane cured with diaminodiphenyl sulfone. Samples cured at various temperatures were soaked in distilled water for extended periods or irradiated with 0.5 Me V electrons and 60Co gamma. DSC results show that the standard-cured (137°C for 2 h and 160°C for 5 h) dry samples have a Tg around 190°C and a large exothermic reaction at about 260°C. The latter is attributed to further reaction of curing agent with the epoxide rings. The exothermic energy is about 124 cal/g for an uncured specimen, 42 cal/g for standard cured specimen, and 20 cal/g for soaked samples containing 4% H2O. The exothermic energy is shown to decrease monotonically with the ionizing radiation dosage. IR results show a reduction in the intensity of the epoxide band as the exothermic energy is decreased.
    Additional Material: 6 Ill.
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