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71.
Asymmetric trans-bioreduction of activated alkenes by KYE1 from Kluyveromyces lactis and Yers-ER from Yersinia bercovieri, two ene-reductases from the Old Yellow Enzyme family, showed a broad substrate spectrum with a moderate to excellent degree of stereoselectivity. Both substrate- and enzyme-based stereocontrols were observed to furnish opposite stereoisomeric products. The effects of organic solvents on enzyme activity and stereoselectivity were outlined in this study, where two-phase systems hexane and toluene are shown to sustain bioreduction efficiency even at high organic solvent content. 相似文献
72.
A study of the static stereochemistry of 1,1,2,2-tetraphenyldisilane (1) and 1,1,2,2-tetramesityldisilane (2) by empirical force field calculations, X-ray diffraction, and 1H NMR reveals that the preference for the anti conformation, exhibited by the unclamped 1,1,2,2-tetraarylethanes, is sustained in the analogous disilanes, although in somewhat attenuated form. This anti preference stands in contrast to the gauche preference of 1,1,2,2-tetraalkyldisilanes. Examination of 3JHH coupling constants for R2HSiSiHR2; (R = phenyl, mesityl, 2,6-dimethyl-phenyl, t-butyl, cyclohexyl) suggests the existence of a Karplus relation for H-Si-Si-H systems. 相似文献
73.
74.
Kurt Egger 《Fresenius' Journal of Analytical Chemistry》1961,182(3):161-166
Zusammenfassung 14 Glykoside der Aglykone Kaempferol, Quercetin und Myricetin werden auf ihr Verhalten im Perlon-Dünnschichtchromatogramm geprüft. Es wird gezeigt, daß 3-Monoside, 3-Bioside und 3,7-Glykoside scharf voneinander getrennt werden und an den stark verschiedenen Rf-Werten erkannt werden können. Der Einfluß des Aglykons ist gering; der entscheidende Faktor für den Rf-Wert ist die Glykosidierung.
Herrn Prof. Dr. L. Hörhammer, Herrn Doz. Dr. H. Wagner und Herrn Dr. W. Leeb, München, danke ich sehr für die freundlicherweise erteilte praktische Einführung in die Polyamid-Dünnschichtchromatographie, sowie für die Überlassung einer Probe von Kaempferol-3-rhamnoglucosid. Die Durchführung der hier dargestellten Versuche hielt sich eng an die in den Münchner Laboratorien entwickelten Verfahren.
Die Untersuchungen wurden von der Görres-Gesellschaft zur Pflege der Wissenschaften und von der Deutschen Forschungsgemeinschaft gefördert, wofür an dieser Stelle gedankt sei. Der BASF Ludwigshafen danke ich für die großzügige Überlassung des Polyamids. 相似文献
Summary 14 glycosides of the aglycons quercetin, kaempferol and myricetin were examined for their behaviour in chromatography with polyamide. The results show that the 3-monosides can be easily differentiated from the 3-biosides, as well as from both the 3,7-glycosides, by their sharply different Rf-values. The influence of the aglycon is small; the decisive factor for the Rf-value is the glycosidation.
Herrn Prof. Dr. L. Hörhammer, Herrn Doz. Dr. H. Wagner und Herrn Dr. W. Leeb, München, danke ich sehr für die freundlicherweise erteilte praktische Einführung in die Polyamid-Dünnschichtchromatographie, sowie für die Überlassung einer Probe von Kaempferol-3-rhamnoglucosid. Die Durchführung der hier dargestellten Versuche hielt sich eng an die in den Münchner Laboratorien entwickelten Verfahren.
Die Untersuchungen wurden von der Görres-Gesellschaft zur Pflege der Wissenschaften und von der Deutschen Forschungsgemeinschaft gefördert, wofür an dieser Stelle gedankt sei. Der BASF Ludwigshafen danke ich für die großzügige Überlassung des Polyamids. 相似文献
75.
When α,β-unsaturated γ-dimethoxymethyl cyclohexenones are excited to the S2(π,π*) state, certain unimolecular reactions can be observed to compete with S2 → S1 internal conversion. These reactions do not occur from the S1(n,π*) or the lowest T(π,π* and n,π*) states. They comprise the radical elimination of the formylacetal substituent (cf. 8 , 9 → 32 + 33 ), γ → α formylacetal migration (cf. 6 → 27 , 8 → 30 , 9 → 34 , 12 → 37 ), and a cyclization process involving the transfer of a methoxyl hydrogen to the α carbon and ring closure at the β position (cf. 6 → 28 , 8 → 31 , 12 → 38 , 20 → 40 + 41 ). The quantum yield of the ring closure 20a → 40a + 41a is 0.016 at ≤ 0.05M concentration. It is independent of the excitation wavelength within the π→π* absorption band (238–254 nm), but Φ ( 40a + 41a ) decreases at higher concentrations. According to the experimental data the reactive species of these specifically π→π*-induced transformations is placed energetically higher than the S1(n,π*) state, and it is either identical with the thermally equilibrated S2(n,π*) state, or reached via this latter state. The linear dienone 14 undergoes a similar π→π*-induced cyclization (→ 42 ) whereas the benzohomologue 26 proved unreactive, and the dienone 22 at both n → π and π→π* excitation only gives rise to rearrangements generally characteristic of cross-conjugated cyclohexadienones. 相似文献
76.
The enantiomerically pure (+)-3-methoxy-1, 3, 5 (10)-estratrien-11, 17-dione 11 (with trans-anti-trans configuration) was synthesized in a highly stereocontrolled fashion from (±)-t-butyl 4-methoxy-1-benzocyclobutene carboxylate (8) and the (+)-carboxylic acid 6 , obtained from 4 in two steps, followed by one crystallization of the (+)-ephedrine salt. The key step 10→11 (Scheme 2) involves a thermal intramolecular cycloaddition reaction. 相似文献
77.
Silvia E. Braslavsky Alfred R. Holzwarth Harald Lehner Kurt Schaffner 《Helvetica chimica acta》1978,61(6):2219-2222
Freshly prepared solutions of biliverdin dimethyl ester ( 2 ) in ethanol showed fluorescence maxima at 710 and 770 nm [ΦF = 1.1. 10?4 (room temperature) and 5.0 10?4 (77 K)]. The maxima of monoprotonated 2 at 77 K were shifted to 725 and 806 nm and the quantum yield was increased to 2.6. 10?2. This acid effect was reversible by neutralization with base. When a neutral solution was kept standing in the dark at room temperature, or when an acidic solution was neutralized by base, an additional fluorescence maximum at 500 nm with a mirror image excitation spectrum with λmax = 470 nm developed, which disappeared on addition of acid and which is attributed to a chemical change of 2 . 相似文献
78.
Photobiological effects of UVA and UVB light in zebrafish embryos: evidence for a competent photorepair system 总被引:2,自引:0,他引:2
Dong Q Svoboda K Tiersch TR Monroe WT 《Journal of photochemistry and photobiology. B, Biology》2007,88(2-3):137-146
The consequences of UVB and UVA irradiation on hatch rate, mortality, and malformation were studied in embryonic zebrafish (Danio rerio). The use of zebrafish embryos has expanded from traditional developmental models to diverse studies, including many techniques utilizing light exposure. To characterize useful indicators of photodamage, the responses and threshold limits of UV radiation as a function of embryonic stage and fish source were evaluated. Significant differences in UVB susceptibility were observed in embryos at 3, 6-7, 12, and 24h post-fertilization (hpf), with the 1000-cell stage (3 hpf) having greatest tolerance to UVB. Embryos derived from zebrafish raised in outdoor ponds were more tolerant to UVB than were embryos from laboratory-raised fish. Combinations of UVB and UVA exposure were used to confirm the presence of a competent photorepair system in zebrafish that could return otherwise malformed embryos to a normal phenotype. Overall, embryonic zebrafish had large tolerances (LD(50) of 850 J/cm(2)) to UVA, confirming their suitability for photoactivation and photorepair studies. 相似文献
79.
[Cl3PNPCl3][MoNCl4], a Compound having Columns of Stacked Anions The title compound is formed by the reaction of [Cl3PNPCl3]Cl with MoNCl3 in CH2Cl2 and subsequent precipitation with CCl4 in from of orange-red crystals. According to the 31P-NMR spectrum, the compound exists as its isomer phosphaneiminate [Cl5Mo(NPCl2NPCl3)] in CD2Cl2/CH3CN solution. The crystal structure of [Cl3PNPCl3][MoNCl4] is isotypic with that of [Cl3PNPCl3][MoOCl4] and shows the same kind of two-dimensional disorder. X-ray diffraction patterns show planes of diffuse scattering as well as Bragg reflexions. The latter correspond to an averaged structure with a = 1590.0, b = 1141.6, c = 418.0 pm, space group Pba2, Z = 2. In the averaged structure (606 reflexions, R = 0.071) the atom sites have fractional occupation. The real structure consists of square-pyramidal [MoNCl4]? ions stacked to form columns with alternating MoN distances of 175 and 243 pm. The packing of the columns is disordered in that the [MoNCl4]? pyramids point either in the +c or ?c direction. The [Cl3PNPCl3]+ ions are stacked in the c direction and show two types of disorder, namely a displacement parallel to c and a rotation by 120° about the P? P axis. 相似文献
80.
The alkalimetal phosphoraneiminates [KNPCy3]4, ( 1 ) [KNPCy3]4·2OPCy3 ( 2 ) and [CsNPCy3]4·4OPCy3 ( 3 ) (Cy = cyclohexyl) which are obtainable by the reaction of pottassium amide or cesium amide with Cy3PI2 or Cy3PBr2 in liquid ammonia, as well as the lithium derivative [Li4(NPPh3)(OSiMe2NPPh3)3(DME)] ( 4 ) have been characterized by crystal structure determinations. 4 has been formed by the insertion reaction of silicon greaze (‐OSiMe2)n into the LiN bonds of [LiNPPh3]6 in DME solution (DME = 1, 2‐dimethoxyethane). 1 : Space group P&1macr;, Z = 2, lattice dimensions at 193 K: a = 1389.8(1); b = 1408.1(1); c = 2205.2(2) pm; α = 78.952(10)?; β = 81.215(10)?; γ = 66.232(8)?; R1 = 0.0418. 2 : Space group Pbcn, Z = 4, lattice constants at 193 K: a = 2943.6(2); b = 2048.2(1); c = 1893.8(1) pm; R1 = 0.0428. 3 : Space group Cmc21, Z = 4, lattice dimensions at 193 K: a = 2881.6(2); b = 2990.2(2); c = 1883.7(2) pm; R1 = 0.0586. 4 ·1/2DME: Space group R&3macr;c, Z = 12, lattice dimensions at 193 K: a = b = 1583.5(1); c = 11755.3(5) pm; R1 = 0.0495. All complexes have heterocubane structures. In 1‐3 they are formed by four alkali metal atoms and by the nitrogen atoms of the (μ3‐NPCy3‐) groups, whereas 4 forms a "heteroleptic" Li4NO3 heterocubane. 相似文献