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971.
Peter Zipper Manfred Kriechbaum Rudolf Wilfing Helmut Durchschlag 《Monatshefte für Chemie / Chemical Monthly》1986,117(5):557-572
The X-ray induced aggregation of the sulfhydryl enzyme malate synthase in aqueous solution was monitoredin situ by time-resolved small-angle X-ray scattering. Experiments were performed in the absence/presence of various additives: formate, superoxide dismutase, catalase, NaCl, acetyl-CoA, glyoxylate, malate, pyruvate, -ketobutyrate, oxaloacetate, glycollate, lactate. The scattering curves were measured as a function of the time of irradiation and were analysed in terms of radii of gyration, degrees of aggregation, distance distribution functions, and parameters derived therefrom. Irradiation in the absence of additives resulted in a strong aggregation of enzyme particles. Each of the additives impeded aggregation, however to a different extent. The OH scavenger formate reduced aggregation efficiently; less pronounced effects were registered for superoxide dismutase and/or catalase (the scavengers for
and H2O2), and for NaCl. Very pronounced diminutions of the aggregation phenomena were provided by substrates or analogues; the efficiency of these substances as radioprotectors may be explained by their action as both scavengers and specific ligands. Based on these results some implications for the performance of conventional small-angle X-ray scattering experiments on biopolymers are derived.
Der Einfluß von Zusätzen auf die röntgeninduzierte Aggregation der Malatsynthase. Registrierung des Aggregationsvorganges in situ mittels zeitaufgelöster Röntgenkleinwinkelstreuung
Zusammenfassung Die röntgeninduzierte Aggregation des Sulfhydrylenzyms Malatsynthase in wäßriger Lösung wurdein situ mittels zeitaufgelöster Röntgenkleinwinkelstreuung messend verfolgt. Streuexperimente wurden in An- bzw. Abwesenheit verschiedener Zusätze durchgeführt: Formiat, Superoxiddismutase, Catalase, NaCl, Acetyl-CoA, Glyoxylat, Malat, Pyruvat, -Ketobutyrat, Oxalacetat, Glycolat, Lactat. Die Streukurven wurden als Funktion der Bestrahlungsdauer registriert. Die Auswertung lieferte Streumassenradien, Aggregationsgrade, Abstandsverteilungsfunktionen, und daraus abgeleitete Parameter. Die Bestrahlung in Abwesenheit von Zusätzen verursachte eine starke Aggregation der Enzymteilchen. Jeder der Zusätze verminderte die Aggregation, wenn auch in unterschiedlichem Ausmaß. Der OH Fänger Formiat verringerte die Aggregation wirksam; weniger stark ausgeprägte Effekte ergaben sich für die bzw. H2O2 Fänger Superoxiddismutase bzw. Catalase und für NaCl. Substrate und Substratanaloge reduzierten das Ausmaß der Aggregation besonders wirkungsvoll; der Schutzeffekt dieser Substanzen kann durch ihre zweifache Wirkung als Fänger bzw. spezifische Liganden erklärt werden. Ausgehend von diesen Ergebnissen werden einige Schlußfolgerungen für die Durchführung üblicher Röntgenkleinwinkelexperimente an Biopolymeren abgeleitet.相似文献
972.
Bernd Engels Jan C Sch?neboom Arno F Münster Stefan Groetsch Manfred Christl 《Journal of the American Chemical Society》2002,124(2):287-297
The six-membered cyclic allenes given in the title have been studied theoretically by means of an MR-CI approach. For all compounds, the allene structures were found to be the ground states in the gas phase. In the cases of cyclohexa-1,2-diene (1), the isobenzene 2, and the isonaphthalene 7, the most stable structures having a planar allene moiety are the diradicals 1b, 2b, and 7b, representing the transition states for the racemization of 1a, 2a, and 7a and being less stable than the latter by 14.1, 8.9, and 11.2 kcal/mol, respectively. At variance with this order, the 3delta(2)-pyran 4 and the chromene 5 have the zwitterions 4c and 5c as the most stable planar structures, which lie only 1.0 and 5.4 kcal/mol above 4a and 5a, respectively. According to the simulation of the solvent effect, 4c even becomes the ground state of 4 in THF solution. The frontier orbitals of the respective states of 2 and 4 suggest different rates and sites for the reaction with nucleophiles. For the first time, the pyran 4 has been generated and trapped. As a precursor for 4, 3-bromo-4H-pyran (9) was chosen, the synthesis of which was achieved on two routes from 4H-pyran. The treatment of 9 with potassium tert-butoxide (KOt-Bu)/18-crown-6 gave 4-tert-butoxy-4H-pyran as the only discernible product, whether styrene or furan was present, indicating the interception of 4 by KOt-Bu. Finally, the disagreement between the experiment and the theory concerning the heat of formation and the electronic nature of the isobenzene 2 is resolved by demonstrating that the experimental data can provide only an upper limit of the DeltaH(f) degrees value. 相似文献
973.
Manfred Mutter Karl-Heinz Altmann Andreas Flrsheimer JüRgen Herbert 《Helvetica chimica acta》1986,69(4):786-792
The conformational properties of Aib-containing oligopeptides having the propensity to adopt amphiphilic helical conformations were investigated by CD spectroscopy in solution. The peptides CF3COOH.H-Pro-Glu-[Ala-Aib-Glu-Aib-]4Gly-OH ( I ), HCl.H-Pro-Ala-Aib-[Gul-Ala-Ala-Aib-]2Glu-Ala-Aib-Gly-PEGM ( II ), and CF3COOH.H-Ala-Aib-[Glu-Glu-Ala-Aib-]3PEGM ( III ) were synthesized according to the general principles of the liquid-phase method for peptide synthesis. Peptides I-III exhibit helical conformations in CF3CH2OH, MeOH, and in H2O at acidic pH; however, at pH 7, only II forms a stable helix, whereas I and III are predominantly in an unordered conformation. Some general features for the construction of amphiphilic helices are discussed in the light of the experimental data. 相似文献
974.
Carotenoid Glycosyl Esters Synthesis of β-D -Glucosyl 8′-Apo-β-carotene-8′-oate and β-D -Glucosyl Vitamin-A-oate (β-D -Glucosyl Retionate) β-D -glucosyl 8′-apo-β-carotene-8′-oate (III) and β-D -glucosyl vitamin-A-oate (VI) were regio- and stereoselectively synthesized in high yields from the N-acylimidazoles I and IV, respectively, or from the N-acyltriazoles II and V, respectively, and unprotected β-D -glucose, according to the method described for the synthesis of di(β-D -glucosyl) 8,8′-diapo-carotene-8,8′-dioate [1]. It seems that this method can generally be applied for the synthesis of β-D -glucosyl esters of polyene carboxylic acids. 相似文献
975.
Fourier transform infrared (FTIR) spectroscopy has been proven to be an appropriate analytical method for the qualitative assessment of compost stability. This study focuses on quantitative determination of two time-consuming parameters: humic acid (HA) contents and respiration activity. Reactivity/stability and humification were quantified by respiration activities (oxygen uptake) and humic acid contents. These features are also reflected by a specific infrared spectroscopic pattern. Based on this relationship partial least squares regression (PLS-R) models for the prediction of respiration activities and humic acid contents were calculated. Characteristic wavenumber regions that are assigned to the biological/chemical parameter were selected for multivariate data analysis. The coefficient of determination (R2) obtained for the humic acid prediction model from infrared spectra was 87% with a root mean square error of cross-validation (RMSECV) of 2.6% organic dry matter (ODM). The prediction model for respiration activity resulted in a R2 of 94% and a RMSECV for oxygen uptake of 2.9 mg g−1 dry matter (DM). 相似文献
976.
Synthesis of isomeric and homologous spermidine and spermine derivatives and their identification by mass spectrometry. The structure of homologous and isomeric spermidines and spermines follows from mass-spectroscopical analysis of their peracetyl (see text, footnote 3) (Table 1) or tosyl-acetyl (Table 2) derivatives. In the case of the peracetyl compounds, triads of peaks are recorded which, according to the number of methylene groups between the nitrogen atoms, show mass numbers characteristic for each of the substances (Scheme 1, ions b , d , e and c ). On the basis of cyclic ions of type f (Scheme 2), occurring in the mass spectra of N-acetyl derivatives, tosylated on a secondary amino nitrogen atom, deductions can be drawn as to the number of methylene groups between neighbouring tosylated and acetylated nitrogen atoms in these compounds. 相似文献
977.
Armin Guggisberg Hans-Jürgen Veith Manfred Hesse Hans Schmid 《Helvetica chimica acta》1976,59(8):3026-3033
Localization of the keto group in Inandenin-ones . By Schmidt degradation of the spermidine alkaloids inandenine-12-on ( 1 ) and inandenine-13-on ( 2 ) from Oncinotis inandensis followed by hydrolysis, acetylation and esterification four different types of products were obtained: the dicarboxylic diesters 9 and 10 , the ω-amino-carboxylic esters 11 and 12 , the acetylated polyamines 14 and 15 , and the acetylated triaminecarboxylic esters 16 and 17 . By GLC. and mass spectral analysis of these degradation products, and by comparison with synthetic compounds it was possible to confirm the structures 1 and 2 . The same alkaloid mixture ( 1+2 ) was obtained from the leaves of Oncinotis nitida BENTH . 相似文献
978.
Vinylogous epoxyaldehydes undergo stereospecific Wittig condensations in high yields. The resulting diolefinic epoxides are cleaved at the C(1)–C(2) single bond, when treated with periodic acid, to give the corresponding aldehydes. Direct transformation into the corresponding ethyl-ester leads to an efficient synthesis of the ‘pear ester’. 相似文献
979.
Manfred Schubert-Zsilavecz 《Monatshefte für Chemie / Chemical Monthly》1991,122(6-7):545-549
Summary 4a,6-Bis-(N-methylanilino)-7-hydroxy-2,3,8-trimethyl-4a,9a-dihydro-xanthene-dione (4) was obtained by thermolysis of 6-(N-methylanilino)-7a-methyl-3a,7a-dihydroindazol-4,7-dione (1) The structure was determined on basis of 1D- and 2D-NMR techniques.Herrn Prof. Dr. G. Zigeuner zum 70. Geburtstag gewidmet 相似文献
980.
Reaction of (CH3NPF3)2 with equimolar amounts of N-methylhexamethyldisilazane yields a reaction product, which can be separated in a polymer and a crystalline fraction. High-vacuum sublimation of the crystalline part yields the already known compound (CH3N)4P3F7, the new spiro-isomer F3P(CH3N)2PF(CH3N)2PF3 and the spiro-compound F3P(CH3N)2PF(CH3N)2PF(CH3N)2PF3, an isomer of the known compound (CH3N)6P4F8. 相似文献