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1.
Leonard S Van Schepdael A Iványi T Lázár I Rosier J Vanstockem M Vermeersch H Hoogmartens J 《Electrophoresis》2005,26(3):627-632
A capillary electrophoretic (CE) method was developed for the separation of diastereoisomers of a new human immunodeficiency virus (HIV) protease inhibitor TMC114. In total 16 isomers of this drug have been synthesized (eight pairs of enantiomers). We succeeded in the separation of the eight diastereoisomers, but no enantiomers could be separated. Because of the high similarity and water-insolubility of these isomers, the separation is a real challenge. Different CE modes were tried out: capillary zone electrophoresis (CZE), nonaqueous capillary electrophoresis (NACE), micellar electrokinetic capillary chromatography (MEKC), and microemulsion electrokinetic capillary chromatography (MEEKC). Only MEEKC offered resolution of these compounds. 相似文献
2.
Is the ring conformation the most critical parameter in lipase-catalysed acylation of cycloalkanols?
CAL-B catalysed the resolution of several five and six-membered cyclic beta-hydroxy esters efficiently with the exception of the cis-cyclohexanol (+/-)-4. When employing molecular modelling techniques the conformation turned out to be the most important determinant for their reactivity towards O-acetylation. In all cases, the R enantiomers reacted faster than the S enantiomers since the reactive intermediates of the former can adopt more favourable ring conformations and thus experience less steric hindrance in the active site. Furthermore, the minimised structure for the main conformer of R-4 showed that the axial hydrogens in the 3 and 5-positions with respect to the hydroxyl group prevent the enzymatic reaction. 相似文献
3.
Enantiomers and diastereomers of chrysanthemic, permethrinic, and deltamethrinic pyrethroic acids were separated from each other, using positively ionizable permethyl monoamino beta-cyclodextrin (PMMAbetaCD). The highest chiral resolution value was 20.0. The optimum conditions of separation were found to be 16 mM PMMAbetaCD concentration and pH 6.5, where analytes and selector were in oppositely ionized states. Selectivity of PMMAbetaCD proved to be the best among the cyclodextrin derivatives studied. 相似文献
4.
Figueroa FL Nygård C Ekelund N Gómez I 《Journal of photochemistry and photobiology. B, Biology》2003,72(1-3):35-44
The effect of different wavebands of artificial UV (UVB and UVA) and photosynthetically active radiation (PAR) was assessed in two species of the genus Ulva, U. olivascens and U. rotundata, from southern Spain in order to test for possible differences in acclimation of photosynthesis. Both species share similar morphology but are subject to different light environments: U. rotundata is an estuarine alga, inhabiting subtidal locations, while U. olivascens is an intertidal, sun-adapted organism. Algae were exposed to three different UV conditions, PAR+UVA+UVB, PAR+UVA and PAR for 7 d. Short-term exposure (6 h) was also carried out, using two PAR levels, 150 and 700 micromolm(-2)s(-1). Pigment contents and photosynthesis vs. irradiance curves from oxygen evolution were used to contrast sun- and shade adaptation between these species. O2-based net photosynthesis (Pmax) and PAM-chlorophyll fluorescence (optimal quantum yield, Fv/Fm) were used as parameters to evaluate photoinhibition of photosynthesis in the experiments. The results underline different photobiological characteristics among species: the subtidal U. rotundata had higher contents of pigments (Chl a, Chl b and carotenoids) than the sun-adapted U. olivascens, which resulted in higher thallus absorptance and P-I parameters characterized by higher photosynthetic efficiency at limiting irradiances (alpha) and lower saturating points for photosynthesis (Ek). After 7 d exposure, photoinhibition of Fv/Fm was close to 40-45% in both species. Differences between UV treatments were seen in U. rotundata after 5 d and after 7 d in U. olivascens, in which PAR+UVA impaired strongly photosynthesis (80%). Such patterns were correlated with a progressive decrease in pigment contents, specially chlorophylls. In short-term (6 h) exposures, combinations of UVA+UVB and high PAR level resulted in high rates of photoinhibition of chlorophyll fluorescence (68-92%) in U. rotundata, whereas in U. olivascens photoinhibition ranged between 42% and 53%. Photoinhibition under low PAR combined to UV radiation was lower than observed under high PAR. Net O2-Pmax revealed similar response among the species, with maximal photoinhibition rates close to 60% in algae incubated under high PAR+UVA+UVB. In the case of UV exposure in combination with low PAR, the highest photoinhibition rates were measured in U. rotundata. 相似文献
5.
Román LU Guerra-Ramírez D Morán G Martínez I Hernández JD Cerda-García-Rojas CM Torres-Valencia JM Joseph-Nathan P 《Organic letters》2004,6(2):173-176
[structure: see text] The triterpenes 8,14-seco-oleana-8(26),13-dien-3beta-ol (1) and its acetyl derivative 2 were isolated from Stevia viscida and Stevia eupatoria, respectively. Their structures were elucidated by 2D NMR, including carbon-carbon connectivity experiments, and confirmed by X-ray diffraction analysis of ketone 3. The absolute configuration was determined by NMR analysis of the Mosher esters of 1. The biogenetic implications of the new substances are discussed. 相似文献
6.
Yo. Pelovski M. Petkova Iv. Dombalov G. Liptay 《Journal of Thermal Analysis and Calorimetry》1994,42(2-3):485-490
The ability of some siliconates to hydrophobize and modify the surface of different kinds of asbestos was studied. A 6 wt% aqueous solution of potassium methylsiliconate was used in various quantities. After treatment, the asbestos samples were analysed by IR-spectroscopy, TG-DTA and electron microscopy. Structural changes were found on the asbestos surface, including the appearance of chemical bonds. The studies revealed that the sorption and lyophilic properties of asbestos are lowered, these being the basic preconditions for its injurious action on health. 相似文献
7.
8.
Iván da Silva Germán R. Castro Zakariae Amghouz Aránzazu Espina Sergei A. Khainakov Santiago García-Granda José R. García 《Journal of Thermal Analysis and Calorimetry》2014,117(3):1179-1186
(C4N2H12)CrO(H1.5PO4)2·H2O has been synthesized hydrothermally using piperazine as organic template. Its crystal structure was solved ab initio using synchrotron powder X-ray diffraction data [monoclinic, a = 16.9649(4) Å, b = 9.8609(2) Å, c = 7.14375(14) Å, and β = 94.896(3)°, space group P21/a, Z = 4]. 1D structure is composed by isolated infinite anionic chains [CrO(H1.5PO4)2]n (vertex-sharing {CrO6} octahedra joined by phosphate moieties). Their 2D plate-like morphology is propitiated by a very strong inter-chain interaction (P–O···H···O–P symmetric hydrogen bonds). KAS isoconversional method was applied to determine the activation energy for both thermal and thermo-oxidative decomposition of (C4N2H12)CrO(H1.5PO4)2·H2O. 相似文献
9.
10.
This study reports 5 years of (1998-2003) data on continuous solar-irradiation measurements from a scanning spectroradiometer (SUV-100) in Valdivia, Chile (39 degrees S), accompanied by evaluation of the impact of ultraviolet radiation (UVR) on marine macroalgae of this site. UVR conditions showed a strong seasonal variation, which was less pronounced toward longer wavelengths. Daily maximum dose rates (clear days) averaged in winter-summer: UV-B(290-315 nm) 0.30-2.1, UV-B(290-320 nm) 0.70-3.7, UV-A(315-400 nm) 20.6-62.1, UV-A(320-400 nm) 20.2-60.5 W m(-2), and photosynthetically active radiation (PAR) 969-2423 micromol m(-2) s(-1). The corresponding daily doses (all the days) ranged: UV-B(290-315 nm) 2.6-40.7, UV-B(290-320 nm) 6.7-78.5, UV-A(315-400 nm) 228-1539, UV-A(320-400 nm) 224-1501, and PAR 2008-13308 kJ m(-2) d(-1). Taking into consideration action spectra of a biological interest, the risk of UV exposure could be up to 37 times higher in summer than in winter. The photosynthetic activity (as maximum quantum yield of chlorophyll fluorescence, F(v)/F(m)) of the brown alga Lessonia nigrescens from the infralittoral zone was markedly more sensitive to UVR than of the green alga Enteromorpha intestinalis from the upper midlittoral, and the UV-B wave band increased markedly photoinhibition. In L. nigrescens, maximal photoinhibition (40%) took place at weighted (the action spectrum for photoinhibition of photosynthesis) UVR doses of 800 kJ m(-2), irrespective of the season (corresponding midsummer daily dose in Valdivia is 480 kJ m(-2)). In winter, when this alga was at its most sensitive, the weighted UV dose causing 35-40% photoinhibition was around 200 kJ m(-2). In E. intestinalis, weighted doses of 800 kJ m(-2) resulted in low photoinhibition (<10 %) and no clear seasonal patterns could be inferred. These results confirm that midday summer levels of UV-B and their daily doses in southern Chile are high enough to produce stress to intertidal macroalgae. 相似文献