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  • 1
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 12,12-Dimethyl-1,4,7,10-tetraazacyclotridecane (I), 11,13-dimethyl-1,4,7,10-tetraazacyclotridecane (II), 11,11,13-trimethyl-1,4,7,10-tetraazacyclotridecane (III) and 1,4,7,10,12,12-hexamethyl-1,4,7,10-tetraazacyclotridecane (IV) have been synthesized and their properties are described.While the Ni2+ and Cu2+ complexes of I-III have square planar geometries, those of IV are pentacoordinate according to their absorption spectra. Similarly, while the Co2+ complex of I is octahedral and readily oxygenated, the analogous complex with IV is pentacoordinate and not sensitive to oxygen.The rate of complexation of these ligands with Cu2+ and Ni2+ decreases in the order I 〉 II 〉 III ≫ IV, indicating that the number as well as the position of the methyl groups are important. Finally for Cu2+ the formation of the thermodynamic stable end product is slown down by methyl substitution in α-position to the coordinating nitrogen atoms (ligand II and III) so that an intermediate can be observed, whereas with I Cu2+ directly forms the end product.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 58 (1975), S. 1881-1886 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stability constants of the Ni2+ and Co2+ complexes with 1,5-diazacyclooctane-N,N′-diacetic acid (H2DACODA) have been determined potentiometrically in 0.5M KNO3 at 25°. Only M(DACODA) and M(DACODA)OH- were observed.In addition the formation and dissociation kinetics of the pentacoordinate complexes M(DACODA) has been studied in aqueous solution using a stopped-flow technique. Formation follows the rate law vf = kf [M2+] [HDACODA-]/[H+], which can be interpreted as a bimolecular process either between M2+ and DACODA2- (kM,LML) or between MOH+ and HDACODA- (kMOH,HLML). The second order rate constants kM,LML are much higher than those expected from water exchange and can only be explained by a strong internal conjugate base effect. In the limiting case, however, this is equivalent to the second possible explanation, which assumes MOH+ and HDACODA- as reactive species. The dissociation rate is given by vd = (kML + kHML [H+]) · [M(DACODA)].
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0009-286X
    Keywords: Chlorine alkali electrolysis ; Diaphragm cell ; Cell design ; Shamrock chlorine cell ; Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Biomedical Materials Research 11 (1977), S. 111-123 
    ISSN: 0021-9304
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: The enzymatic activity of α-chymotrypsin (CT), immobilized on hydrogelcoated polymer film supports, has been investigated. The support was prepared by radiation-graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) and methacrylic acid (MAAc) on silicone rubber films. The enzyme was covalently coupled to the carboxylic group of MAAc via the N-hydroxysuccinimide (NHS) ester active intermediate.Increasing MAAc contents of the hydrogel resulted in increased attachment of CT. The integrity of the CT active site after attachment was assessed by an active site titration with diisopropyl fluorophosphate (DFP). As the MAAc content of the hydrogel was increased, an increasing fraction of the attached CT retained its activity to DFP. A greater fraction of CT was active towards DFP when adsorbed than when coupled.The rates of hydrolysis of some synthetic model substrates by the immobilized CT were also measured. The negative charge on the hydrogel had a large effect on the rates of these hydrolyses. The pH optimum for the hydrolysis of N-acetyl-L-tyrosine ethyl ester (ATEE) by immobilized CT was higher than that of free CT. Increasing MAAc content of the hydrogel resulted in larger shifts in the pH optimum. The maximum rates of ATEE hydroylsis per mg CT declined sharply with increasing MAAc content of the hydrogel. This is probably related to the increasing repulsive force between the ATEE (negatively charged above ⋍ pH 9.5) and the hydrogel with increasing MAAc content. The activity of immobilized CT to ATEE is small compared to that of free CT, partly due to this charge effect. Conversely, the rate of hydrolysis of BAEE, a positively charged substrate, by immobilized CT at pH 11, is almost fourfold greater than that by free CT at its pH optimum.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Biomedical Materials Research 11 (1977), S. 609-624 
    ISSN: 0021-9304
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: The vital first phase of the overall materials study to protract the life of total joint replacements is the identification of the fracture toughness and fatigue properties of bone cements. Information gained from fatigue testing, performed in a manner which simulates in vivo conditions, and fracture toughness, which is a measure of the propensity of a crack to propagate, is the first step towards the prediction of the life of the total joint replacement. Part I of this study identified the fracture toughness characteristics of two acrylic bone cements, while the present work has been concerned with determining the fatigue behavior by means of tests conducted in a rotating bending fatigue apparatus. Fatigue specimens were fabricated under conditions which approximated clinical procedures and then tested while immersed in bovine serum at 37°C in order to simulate in vivo conditions. In addition, a similar study was completed on specimens tested in air at ambient temperature for purposes of comparison. Testing was conducted in both of these environments on specimens containing zero and 10.0 wt % BaSO4. Cyclic loading frequency was maintained between 1200 and 1400 cycles/min in order to insure that crack propagation was the sole mechanism of failure, i.e., failure via cyclic thermal softening was obviated.Results of this phase of the study, when analyzed by a Student t-test at the 90% confidence level with four degrees of freedom, indicate that the fatigue life of specimens tested in bovine serum at 37°C is superior to that of specimens tested in air at ambient temperature. The addition of BaSO4 to Simplex-P cement, while not significant at the 90% confidence level, was significant in increasing the fatigue life in air at the 80% confidence level; however, this effect was not noticeable when testing in bovine serum at 37°C. Examination of the fracture surfaces enabled calculation of the critical stress intensity factor which when compared with values from an earlier work showed good agreement.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 9 (1977), S. 75-79 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 13C and 15N n.m.r. results for a series of diazo compounds are reported. It is found that the diazo carbon is shielded by an extraordinary amount compared with normal sp2 hybridized carbons. The 15N chemical shifts reveal that the terminal nitrogen is deshielded relative to the central one. This is contrary to that expected from charge effects but support is found for this phenomenon in other systems. One-bond 13C—14N coupling in diazomethane is also reported for the first time. INDO MO calculations of the charges and finite perturbation calculations of 13C—14N and C—H couplings are compared with the experimental results.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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