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  • 1
    ISSN: 1434-1948
    Keywords: Imaging agents ; Lanthanides ; NMR spectroscopy ; DNA cleavage ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydration state of a series of [Ln(DO2A)(H2O)n]+ complexes in aqueous solution at pH = 6.4-7.0 was studied by measuring the lanthanide-induced 17O shifts (LIS) of water [Ln includes elements from Ce to Yb; DO2A = 1,7-bis(carboxymethyl)-1,4,7,10-tetraazacyclododecane]. Their contact contribution, obtained from Reilley plots, indicated a decrease in the inner-sphere water coordination number of the [Ln(DO2A)(H2O)n]+ complexes from n = 3 (Ce-Eu), to n = 2 (Tb-Yb). A temperature-dependent UV/Vis absorption study of the 578-582 nm 7F0 → 5D0 transition band of [Eu(DO2A)(H2O)n]+ in aqueous solution showed that this complex is present in an equilibrium between eight- and nine-coordinate species with n = 2 and n = 3, respectively. The hydration equilibrium parameters (2 ↔ 3), K2-3298 = 4.0 ± 0.2, ΔH2-30 = -12.1 ± 1 kJ mol-1 and ΔS2-30 = -28.9 ± 3 J mol-1 K-1,correspond to an average hydration number of 2.65-2.85 in the temperature range 273-363 K. A variable temperature, multiple field 17O NMR study combined with direct EPR measurements of the transverse electronic relaxation rates has been used to obtain the parameters characterizing water exchange, rotation and electronic relaxation, all influencing the proton relaxivity of [Gd(DO2A)(H2O)2-3]+. The small increase in the water exchange rate of [Gd(DO2A)(H2O)2-3]+ (kex298 = (10 ± 5) × 106s-1) relative to that of[Gd(DOTA)(H2O)]- (4.8 × 106 s-1) is a consequence of an unfavorable interplay of charge and hydration equilibria. The value of τR298 = 40 ± 1 ps is short, and the electronic relaxation rate (1/T2e ≍ 1.2 × 1010 s-1) is fast relative to [Gd(DOTA)(H2O)]- (1.3-2.4 × 109 s-1 for B = 0.34 T). These parameters negate to some extent the expected increase in proton relaxivity of the [Gd(DO2A)(H2O)2-3]+ complex.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99338_s.pdf or from the author.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 15 (1969), S. 208-214 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Experiments have been carried out to measure the permeation of tritium-labeled toluene through polyethylene films fully swollen with chlorobenzene, mesitylene, cumene, toluene, ethylbenzene, cyclohexane, tetrahydronaphthalene, and decahydronaphthalene. The results show characteristic Arrhenius temperature dependence over the range 25 to 40°C. The permeation of toluene through the films appears to be enhanced by increased solubility of the swelling agent (estimated from the work of others) in the film and there also appears to be a rough correlation between permeability of toluene and the boiling points and vapor pressures of the swelling agents. The range of permeabilities measured at 25°C. is 2.09 × 10-7 to 0.51 × 10-7 sq.cm./sec., the extremes of measured permeation activation energy, Ep, are 11.41 to 16.68 kcal./mole, and the pre-exponential factor, Po, falls within the interval 36.59 to 1.29 × 105 sq.cm./sec. A very definite linear relationship or compensation effect is evident between Po and Ep. Except as mentioned above, none of these quantities appears to correlate uniformly with the following properties of swelling solvent: molecular weight, dipole moment, specific gravity, vapor pressure, boiling point, heat of vaporization, critical temperature, viscosity, surface tension, molar volume, molecular area or other molecular dimensions.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 7 (1993), S. 43-45 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The versatility of the quadrupole ion trap as a mass spectrometer in which the mass resolution may be varied over a wide range has been demonstrated. Mass resolution of 0.8 × 107 and 1.2 × 107 have been obtained for ions of m/z 414 and m/z 614, respectively, well in excess of the normal value of 3m, where m is the mass of ion. At the highest mass resolution, peak-widths at half-maximum are but 52 × 10-6 u. While it has been shown previously that enhanced mass reslution in the quadrupole ion trap can be achieved by reduction of the mass scanning rate, the range of mass resolutions reported here were achieved by reducing the mass scanning rate, in stages, by an overall factor of ca 5.5 × 104.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 7 (1993), S. 929-934 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: When the working point of a precursor ion confined within a quadrupole ion trap is moved to the vicinity of a boundary of the stability diagram, fragmentation of the precursor ion can be induced by virtue of energy gained from the radio-frequency trapping field. This behaviour is known as the ‘border effect’. When the isolated precursor ion is subjected to a cooling period of variable duration, in the presence of helium buffer gas and prior to experiencing the ‘border effect’, a high degree of control of the fragmentation pattern is achieved. The cooling period causes decreases in both ion kinetic energy and ion axial excursions. From this preliminary study, it is suggested that the deposition of internal energy during the ‘border effect’ can be varied by changing the duration of the cooling period. In addition to a degree of control of internal energy deposition, the amount of energy which can be deposited in this manner, though unknown, appears to exceed those energy levels achievable with resonance excitation and the ‘border effect’ without collisional cooling, in that an additional fragmentation channel is accessed.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Commercial gas chromatography quadrupole ion-trap mass spectrometer (GC/ITMS) instruments have been used in a novel way for the study of negative ions formed from perfluorotributyl-amine and polychlorinated biphenyl compounds. Negative ions, formed during a normal electron impact ionization period in which 70 eV electrons were used, were isolated in an ion trap by the application of a negative DC voltage to the ring electrode that caused all positive ions to be ejected from the ion trap; in the subsequent analytical scan, negatives ions were detected with an electron multiplier biased normally so as to detect positive ions. The major negative-ion species detected from FC-43 were m/z 252 to m/z 633; 34 other negative-ion species were detected also, though in low abundance. The observed negative-ion mass range extended from m/z 252 to m/z 633. The signal-to-noise ratio of negative-ion mass spectra was enhanced by operation of the GC/MS instrument in GC mode and averaging the mass spectra acquired. In an examination of 3 hexachlorobiphenyl compounds, the molecular anion cluster around m/z 360 for the non-ortho-substituted congener 169 was observed with a signal-to-noise ratio of ca. 20 for 90 pg injected on column: the response for congener 169 was greater than that for congener 156 (mono-ortho-substituted) which, in turn, was greater than that for congener 153 (di-ortho-substituted).
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 18 (1955), S. 417-421 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of seven vinyl esters of perfluoro acids has been prepared by the mercury catalyzed reaction of the acids with acetylene. Certain physical properties of the monomers are given. Homopolymers gave clear, flexible films with the exception of vinyl caprylate and caprate, which formed waxy films. Copolymerization of vinyl perfluorobutyrate proceeded readily with vinyl acetate and methyl methacrylate, but less readily with styrene, maleic anhydride, and acrylonitrile.
    Additional Material: 2 Tab.
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  • 7
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crosslinking and degradation of seven polyacrylates by 1000 kvp. electrons has been investigated. Gel content-radiation dose analysis reveals the energy dissipation per main-chain fracture, Ed, to be the same (530 ± 100 electron volts) for methyl, n-butyl, sec-butyl, isobutyl, and tert-butyl acrylate polymers. The energy dissipation per crosslinked unit formation, Ec, is 80-90 e.v. for methyl, n-butyl, isobutyl and neopentyl acrylate polymers. Ec may be slightly higher for poly-sec-butyl acrylate. Poly-tert-butyl acrylate possesses a uniquely high Ec of 300 e.v. The presence of hydrogen atoms alpha to the alcoholic oxygen of the ester group is believed to contribute strongly to the crosslinking reactions of polyacrylates under ionizing radiations. Poly-1,1-dihydroperfluorobutyl acrylate exhibits an initial Ec of ∼45 e.v. and an Ed of ∼450 e.v. Beyond 15 megareps the ration of main-chain fracture to crosslink formation increases.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0173-0835
    Keywords: Two-dimensional nonequilibrium pH gradient gel electrophoresis ; Rat kidney ; Polyacrylamide gel electrophoresis ; Lead exposure ; Glutathione S-transferase ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Glutathione S-transferases (GST) are a family of detoxification isoenzymes that catalyze the conjugation of xenobiotics and their metabolites with reduced glutathione. Lead exposure in rats is known to induce GST isoenzymes in the liver and kidney. These changes in expression have potential use as biomarkers of lead exposure. Because two-dimensional electrophoresis (2-DE) enables one to analyze both protein abundance changes and chemical changes in protein structure, 2-DE was used to determine the effect of in vivo lead exposure on GST isoform expression in rat kidney cytosols. Male Sprague-Dawley rats were exposed to inorganic lead, and proteins were separated by conventional ISO-DALT and NEPHGE-DALT techniques and blotted for immunological identification. Lead exposure caused detectable inductions in both GSTP1 and GSTM1 and quantifiable charge modification in GSTP1. These preliminary data confirm the utility of 2-D electrophoretic GST analysis as indicative of lead exposure and toxicity and support its use for further elaboration of lead's effects on renal protein expression.
    Additional Material: 2 Ill.
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  • 9
    ISSN: 0173-0835
    Keywords: Cortex ; Cytoplasm ; Two-dimensional polyacrylamide gel electrophoresis ; Kidney ; Medulla ; Proteomics ; Rat ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: The rodent kidney is a target of many xenobiotics and is typified by regionally specific structure and function. This renders distinct regions of the kidney differentially susceptible to toxic exposure and effect. To characterize these differences at the proteome level, protein patterns from male rat kidney cortex and medulla cytosols were examined by two-dimensional electrophoresis (2-DE) and image analysis and prominent proteins identified immunologically or by matrix-assisted laser desorption/ionization - mass spectrometry (MALDI-MS) and electrospray/ionization - tandem mass spectrometry (ESI-MS/MS) sequence tag identification. An average of 727 protein spots were resolved and matched to the cortex cytosol reference pattern, and 716 in the medulla. Of this total, 127 proteins were found to differ in abundance (86 higher in cortex; 41 higher in medulla) (P 〈 0.001). Of those proteins that were detectable in both cortex and medulla, the abundance of 97 differed significantly while 30 proteins were found to be unique to one region or the other (26 in cortex, 4 in medulla). Twenty protein spots were identified and their regional differences are discussed. These results both confirm and expand our understanding of the molecular heterogeneity characterizing structurally and functionally distinct regions of the kidney and serve as a useful foundation for future nephrotoxicologic studies.
    Additional Material: 4 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Electrophoresis 18 (1997), S. 642-646 
    ISSN: 0173-0835
    Keywords: Two-dimensional electrophoresis ; Tissue slice ; Testis ; Protein mapping ; Toxicity test ; Dinitrobenzene ; Trinitrobenzene ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Advances in tissue slice technology and a recent novel application of this technique to reproductive toxicology using bovine testis have demonstrated the remarkable utility of this approach. The objective of the present study was to combine this in vitro toxicity test system with large-scale two-dimensional polyacrylamide gel electrophoresis (2-DE) to detect and study alterations in testicular-slice protein patterns as molecular correlates of 1,3,5-trinitrobenzene (TNB) and 1,3-dinitrobenzene (DNB) toxicity. Previous studies have shown that testicular slices remain viable for 〉 24 h and, as measured by protein synthesis inhibition, TNB causes dose-related injury. Tissue-slices were prepared from bovine testicles incubated for 2, 4 or 6 h and exposed to either 100 μM, 500 μM or 1 mM DNB or TNB in the incubation medium. Slices were collected, solubilized, and separated by large scale 2-DE. Resulting protein patterns were then examined by image analysis, which revealed coefficients of variation in protein spot abundance comparable to patterns from fresh rodent tissue samples. Furthermore, specific protein alterations indicated dose-related inductions and declines in protein abundance, some progressive over time. The results of this investigation demonstrate the potential toxicologic utility of combining in vitro tissue-slice technology with high-resolution 2-DE protein mapping. The consolidation of these methods offers a novel approach for toxicity screening and testing, reduces experimental cost, and reduces the use of laboratory animals.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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