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  • 1
    ISSN: 0173-0835
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: It has been found that the double bond of free, unreacted acrylamide in a gel can react with a free -SH group of proteins, forming a cysteinyl-S-propionamide adduct. When β-lactoglobulin was incubated at concentration levels lower than those of free acrylamide, left after polymerizing a 5% T, 4% C gel (barely 12 mM), under anaerobic conditions in 0.1 M borate, pH 9.5, for 1 h and then the tryptic digests analyzed by high performance liquid chromatography (HPLC), two new peptides were detected. The two new peaks were recovered and sequenced by the Edman degradation procedure. They correspond to the sequence from Leu-149 to lle-162. Residue No. 160 was found to be a cysteinyl-S-propionamide reaction product. Interestingly, only this residue, out of a total of 5 Cys residues, had reacted. No other amino acids (including -NH2 terminus and free -NH2 in Lys) reacted with free acrylamide. The addition of free acrylamide to the -SH group could be completely inhibited if: (i) the gel was extensively washed prior to sample application, or (ii) the gel was incubated for 1 h in 100 mM free Cys.
    Additional Material: 2 Ill.
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  • 2
    ISSN: 1434-193X
    Keywords: Aryl triflates ; Vinyl triflates ; Palladium(0) catalyst ; Carbon dioxide ; Electron transfer ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electrochemical reduction of aryl and vinyl triflates in the presence of CO2 and a catalytic amount of palladium results in the formation of aromatic and α,β-unsaturated carboxylic acids. Aryl and vinyl triflates usually undergo palladium-catalysed cross-coupling reactions with nucleophiles. Their reactivity has been reversed in the presence of an electron source, so that they react with electrophiles such as CO2. The reaction proceeds through an activation of the C-O bond of the aryl or vinyl triflate by oxidative addition to a palladium(0) complex, followed by an activation by electron transfer of the thus formed aryl- or vinylpalladium(II) complexes.
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  • 3
    ISSN: 1434-193X
    Keywords: Receptor selectivity ; Agonist activity ; Distance geometry ; Conformation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To identify the peptide conformation that is preferentially recognized by the receptor, we have synthetized by solid-phase method a series of deltorphin I analogs with increasing selectivity for δ- and μ-opioid receptor. Structure-selectivity relationship of these peptides were evaluated on the basis of receptor-binding properties and conformational features, computed by two-dimensional NMR spectra and distance-geometry techniques. These compounds in solution are present with a large number of conformers with no defined secondary structural elements. The analysis of the average properties of these compounds indicate the presence of some distinct conformational preferences that can be related to the observed opioid receptor selectivities. Selectivity for the δ- and μ-opioid receptors can be ascribed to the spatial arrangement of the aromatic moieties. In addition, substitutions in position 2 and 4 are important for the correct arrangement and must be taken into account in the design of δ-opioid receptor-selective ligands.
    Additional Material: 6 Ill.
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  • 4
    ISSN: 0173-0835
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: It has often been debated whether the presence of persulfate in a polyacrylamide gel could lead to the oxidation of cysteine (Cys) in proteins to cysteic acid. In fact, direct incubation of bovine serum albumin (BSA) with peroxodisulfate and periodate barely alters the isoelectric point (pI) and does not produce any cysteic acid. In contrast, caroate (peroxomonosulfate) and perphathalate strongly lower the pI of BSA. In the former case it as demonstrated that 4- Cys (of a total of 35) were converted into cysteic acid. Perphthalate was found to be, by far, the strongest oxidant: 15 (of 35) Cys residues were oxidized to cysteic acid and all methionine groups were destroyed.
    Additional Material: 2 Ill.
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  • 5
    ISSN: 0173-0835
    Keywords: Two-dimensional polyacrylamide gel electrophoresis ; Bull seminal plasma proteins ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: A two-dimensional polyacrylamide gel electrophoresis map of bull seminal plasma proteins has been established. About 250 spots were detected after silver staining and polypeptides from 24 spots have been N-terminally sequenced. Major proteins already described in bull seminal plasma, like PDC-109 and aSFP, have been located on the map; proteins not yet reported in male reproductive tracts have been evidenced; for some polypeptides showing a previously unknown N-terminal sequence, structural similarities with proteins described in other organisms have been found. A reference map of seminal plasma proteins could be useful in relating protein pattern changes to physiopathological events influencing the reproductive sphere.
    Additional Material: 1 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. S20 
    ISSN: 0749-1581
    Keywords: ESR, EPR ; C60 ; C70 ; MNDO ; INDO. MO calculations ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: EPR spectra of free-radical adducts of C60 and C70 are described and discussed. In the case of addition to C60 the prototype radical is HC60 or perhaps MuC60. The H/Mu hyperfine anomaly in these radicals is explained. The spectra of alkyl-C60 and fluoroalkyl-C60 radicals are also described, including factors determining the equilibrium configuration over the C60 surface of radicals of the general formula XYZCC60. The structure of the higher adducts R3C60 and R5C60 is mentioned. In the case of H addition to C70, four of the five possible isomers of HC70 have been identified, but only one of the 2792 isomers of H3C70 is reported.
    Additional Material: 4 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. 312-317 
    ISSN: 0749-1581
    Keywords: tricyclohexylmethyl radical ; ESR spectra ; MNDO/UHF calculations ; NMR spectra ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ESR spectrum of the tricyclohexylmethyl radical was obtained from tricyclohexylmethyl chloride and was studied in solution in the range 275-455 K. It has a half-life of about 30 min at room temperature. The complex hyperfine structure of the radical was analysed with the help of MNDO/UHF calculations. Hyperfine interactions with three beta protons, twelve gamma protons and six delta protons were resolved. The alpha and the three beta carbon atoms are coplanar. The temperature dependence of the beta and six of the gamma proton hyperfine interactions was ascribed to torsional motions of the cyclohexyl rings about the Cα—Cβ bond. The radical has C3h symmetry, the Cα and Cβ atoms being coplanar. Evidence for the existence of hexacyclohexylethane at about 200 K was obtained for the first time.
    Additional Material: 4 Ill.
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