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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 971-984 
    ISSN: 0887-624X
    Keywords: radiation ; polyisobutylene ; NMR ; GC/MS ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: GC, GC/MS, GPC, and Solution NMR spectra were used to study the γ radiolysis of polyisobutylene (PIB) in vacuum to different total doses (0-900 kGy) and at different temperatures (77-423 K). NMR spectra show a large number of new resonances with relatively narrow line widths, and a variety of NMR techniques have been employed to determine and quantify the structures associated with these new resonances. Chemical shift assignments were made by comparison with those for small molecule model compounds and predictions based upon calculations according to several different schemes. Chain-end structures have been proposed that account well for the majority of the new resonances, all being the result of an initial chain scission reaction initiated by the radiation. These assignments support some previous proposals for the mechanism of radiation degradation of polyisobutylene and exclude others. For example, NMR provides no evidence for the formation of ethyl chain ends and some of the main chain unsaturated structures previously proposed. NMR also indicate that at higher doses the chain end products formed during initial stages undergo secondary reactions. GC/MS data show the formation of oligomers during irradiation, which may be due to a backbitting mechanism. © 1996 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 32 (1998), S. 334-349 
    ISSN: 0887-3585
    Keywords: antifungal ; thionin ; NMR ; structure ; scorpion ; toxins ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The three-dimensional structure of the Sorghum bicolor seed protein γ-thionin SIα1 has been determined by 2D 1H nuclear magnetic resonance (NMR) spectroscopy. The secondary structure of this 47-residue antifungal protein with four disulphide bridges consists of a three-stranded antiparallel sheet and one helix. The helix is tethered to the sheet by two disulphide bridges which link two successive turns of the helix to alternate residues i, i + 2 in one strand. Possible binding sites for antifungal activity are discussed. The same fold has been observed previously in several scorpion toxins. Proteins 32:334-349, 1998. © 1998 Wiley-Liss, Inc.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 2835-2838 
    ISSN: 0887-624X
    Keywords: NMR ; MAS ; silanes ; Ziegler-Natta ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 29Si cross-polarisation NMR was used to study the interaction between silanes and MgCl2 when co-milled. Large changes are seen for the 29Si chemical shift of the silane between the silane in solution and in the solid complex. Interpretation of the differences in chemical shift are hindered by the absence of an adequate semi-empirical theory. The 29Si chemical shift tensors confirm a strong interaction between the silane and MgCl2. © 1993 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 220 (1981), S. 773-780 
    ISSN: 1432-0878
    Keywords: Estrogen receptors ; Uterus ; Armadillo ; Autoradiography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The uptake and retention of radiolabeled estradiol by the uterus was examined in the armadillo. One pregnant and two non-pregnant armadillos were treated with 1.4 μg/kg body weight of 3H-estradiol (E2) by injection into the left ventricle, and one non-pregnant animal was injected with both the labeled hormone and 140 μg/kg body weight of unlabeled E2. One and a half hour after injection, the animals were sacrificed and the uteri were removed and processed for autoradiography. In the non-pregnant animals, nuclear localization was observed in the interstitial cells and glandular epithelium of the endometrium and the connective tissue cells and smooth muscle of the myometrium. Additionally, there was a gradation of uptake in the epithelial cells of the endometrium in that the glandular cells of the basal region were heavily labeled, while those cells in the sinusoidal, and luminal regions contained successively less label. The luminal cells were poorly labeled. In the pregnant female, the smooth muscle and glandular cells hypertrophied and their nuclei contained less label than was observed in the non-pregnant animals. The arteries of the myometrium were more easily distinguished in the pregnant animals and the nuclei of the endothelial cells and smooth muscle were more consistently labeled than those of the non-pregnant armadillos.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 230 (1983), S. 219-223 
    ISSN: 1432-0878
    Keywords: Steroid receptors ; Estradiol ; Diabetes mellitus ; Autoradiography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Previous clinical studies have indicated that during pregnancy and following administration of contraceptives women show altered carbohydrate metabolism. We performed autoradiographic studies using 3H-estradiol-17β and 3H-dihydrotestosterone on male and female baboons. Discrete sites of localization of exposed photographic emulsion were observed over nuclei of cells of the islets of Langerhans of the pancreases of baboons injected with estrogen but not over those of baboons injected with androgen. These observations that islet cells contain specific receptors for estrogen when combined with the clinical observations, suggest that estrogens have a direct effect on the islet cells that may modulate the release of insulin.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 231 (1983), S. 593-601 
    ISSN: 1432-0878
    Keywords: Lymphatic organs ; Sex steroids ; Baboon ; Autoradiography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The localization of radiolabeled estradiol and dihydrotestosterone was examined in the lymphatic organs of both male and female baboons. A total of 12 baboons were divided into two groups, each containing three males and three females. Each animal in one group, both males and females, was injected intravenously with 1 μg/kg body weight of 3H-estradiol while those in the second group were each injected with 1 μg/kg body weight of 3H-dihydrotestosterone. As controls, one male and one female from each group also received a dose of 100 μg/kg body weight of the corresponding unlabeled steroid. One and a half hours after the injections, the animals were sacrificed and the spleen, thymus, and inguinal lymph nodes removed and processed for autoradiography. The localization of 3H-estradiol was similar in both males and females. In the thymus fibroblasts and epithelio-reticular cells, but not thymocytes, localized 3H-estradiol. In lymph node and spleen, nonlymphoid tissue concentrated the labeled estrogen. Additionally, in the paracortical region of the lymph node, an unknown cell type was labeled with estrogen. Only one male baboon demonstrated nuclear localization of 3H-dihydrotestosterone. This was observed in the reticular cells in the spleen and lymph nodes. The same cell type in the organs of the remaining animals was unlabeled.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The principal components factors F1 and F2 in the equation \documentclass{article}\pagestyle{empty}\begin{document}$$ \log K = {\rm BDP}_0 + S_1 F_1 + S_2 F_2 $$\end{document} have been used to obtain S1 and S2 values for sets of hydrogen-bond bases against 32 reference acid/solvent systems. The constants S1 and S2 define an angle θ = tan-1 S2/S1 that is a measure of the electrostatic:covalent bonding ratio in the hydrogen-bond complex. It is shown that θ can vary from 53 (4-fluorophenol in CH2Cl2)to 86 degrees (Ph2NH in CCl4) depending on the reference acid and solvent. This variation in θ can lead to family dependent behaviour in plots of log K for bases against a given reference acid system vs log K for bases against another reference acid system, and precludes the construction of any general scale of hydrogen-bond basicity using log K values. Amongst a quite wide range of reference acid/solvent systems θ varies only from 64 to 73 degrees, and for bases against these reference systems a ‘reasonably general’ scale could be set up. Such a scale could be extended to bases against reference acid/solvent systems outside the 64-73 degree range provided that certain classes of base (e.g. pyridines, alkylamines) were excluded from the additional reference acid/solvent systems.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Microelectrodes can be used to measure redox half-wave potentials in aprotic solvents containing no purposely added supporting electrolyte. By employing an electrode of sufficiently small size, the accessible potential range in solution is considerably extended. The electrochemical oxidation of vinyl (enol) triflates, which are oxidized at high electrode potentials, can therefore be studied using an ultramicroelectrode. Oxidation and ionization potentials, determined by ultramicroelectrode voltammetry and He I photoelectron spectroscopy, respectively, of 2-methylprop-1-enyl, cyclohexenyl, cyclopentenyl, 1,1-diphenylethenyl and prop-2-enyl triflate are reported. The results from electrochemical measurements and photoelectron spectra were compared.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 7 (1994), S. 743-750 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An LSER analysis based on the partitioning of 15 proton acceptor heterocycles has succeeded in extracting Σβ values, but only at the cost of demonstrating solvent dependence for some of them. As noted by Abraham, the division lies between protic and aprotic organic phases. His observation that pyridine and quinoline are less effective acceptors when surrounded by solvent than in 1 : 1 association was confirmed, and possible reasons for this are discussed. Two other such cases are N-methylimidazole and pyridazine, both of which give lower Σβ values in octanol than in PGDP. For both, Σβ in PGDP is what would be expected on the basis of log Kβ. The value for pyridazine in octanol suggests that, here, the ‘α-effect’ is no longer operative; it is possible that this result can be generalized to other such heterocycles. Elsewhere, the most remarkable finding is that, where there are two proton acceptor sites in one heterocyclic ring, Σβ is the simple unattenuated sum of the separate βf values. If this result is general, it leads to a very simple way of estimating Σβ for heterocycles by calculation where data are unavailable. Evidence was also found, in certain cases, for hydrogen bonding to the π-donor heteroatom or the aromatic ring. The QSAR implications of these results are discussed.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using the solvatochromic indicator method, a scale of solvent hydrogen-bond basicity, β1 (General), has been set up using a series of double regression equations, \documentclass{article}\pagestyle{empty}\begin{document}$$ \nu = \nu _0 + s\pi _1^* + b\beta _1 $$\end{document} for 11 aniline-type indicators. A similar solvent scale, β1 (Special), has been constructed by the homomorphic comparison method using only results by Laurence et al. on the indicators 4-nitroaniline and 4-nitro-N,N-dimethylaniline. Results are available from our previous work on a general solute scale, β2H, and we have also obtained a special solute scale, β2 (pKHB) from available log K values for hydrogen-bond complexation of bases with 4-fluorophenol in CCl4. However, the two solute β2 scales are virtually identical.It is shown that there is a general connection between β1(General) and β2H, with r = 0·9775 and s.d. = 0·05 for 32 compounds, and between β1(Special) and β2H, with r = 0·9776 and s.d. = 0·06 for the same 32 compounds. The latter correlation over 60 compounds yields r = 0·9684 and s.d. = 0·07. However, there are so many compounds in these regressions for which the differences in the solvent and solute β values are larger than the total expected error of 0·07 units that the use of β1 to predict β2 or vice versa is a very hazardous procedure. About 70 new β1 values obtained by the double regression method are also reported.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
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