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11.
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
12.
The first 3-D open-framework TiGaPO complex, constructed from Ti(III)O(6), Ti(IV)O(6), GaO(4), and PO(4) polyhedra, contains pyridinium cations in a 1-D pore network and can be oxidized in air at 543 K with retention of the original framework structure. 相似文献
13.
Salma Kassem Alan T. L. Lee David A. Leigh Augustinas Markevicius Daniel J. Tetlow Naoyuki Toriumi 《Chemical science》2021,12(6):2065
Peptides attached to a cysteine hydrazide ‘transporter module’ are transported selectively in either direction between two chemically similar sites on a molecular platform, enabled by the discovery of new operating methods for a molecular transporter that functions through ratcheting. Substrate repositioning is achieved using a small-molecule robotic arm controlled by a protonation-mediated rotary switch and attachment/release dynamic covalent chemistry. A polar solvent mixtures were found to favour Z to E isomerization of the doubly-protonated switch, transporting cargo in one direction (arbitrarily defined as ‘forward’) in up to 85% yield, while polar solvent mixtures were unexpectedly found to favour E to Z isomerization enabling transport in the reverse (‘backward’) direction in >98% yield. Transport of the substrates proceeded in a matter of hours (compared to 6 days even for simple cargoes with the original system) without the peptides at any time dissociating from the machine nor exchanging with others in the bulk. Under the new operating conditions, key intermediates of the switch are sufficiently stabilized within the macrocycle formed between switch, arm, substrate and platform that they can be identified and structurally characterized by 1H NMR. The size of the peptide cargo has no significant effect on the rate or efficiency of transport in either direction. The new operating conditions allow detailed physical organic chemistry of the ratcheted transport mechanism to be uncovered, improve efficiency, and enable the transport of more complex cargoes than was previously possible.Peptides are transported in either direction between chemically similar sites on a molecular platform, substrate repositioning is achieved using a cysteine hydrazide transporter module and a small-molecule robotic arm controlled by a rotary switch. 相似文献
14.
Colin F. Chignell Ann G. Motten Robert H. Sik Carol E. Parker Krzysztof Reszka 《Photochemistry and photobiology》1994,59(1):5-11
The photochemistry of 5,5-dimethyl-l-pyrroline N -oxide (DMPO) has been studied in benzene, cyclohexane and aqueous buffer solutions (pH 7.4) by means of electron paramagnetic resonance (EPR) and the spin trapping technique. Ultraviolet irradiation of DMPO in aqueous buffer with unfiltered UV radiation from a Xe arc lamp results in photoionization of the spin trap and the generation of the DMPO cation radical, DMPO+ . The aqueous electron, eaq − , was trapped by DMPO and detected as the DMPO/H adduct. The DMPO+ - reacted with the water to yield the DMPO/OH adduct. Ultraviolet irradiation of DMPO in nitrogen-saturated benzene gave an unidentified carbon-centered DMPO adduct that was replaced by hydroperoxyl and alkoxyl adducts of DMPO when oxygen was present. Experiments employing 17 O2 gas indicated that the oxygen in the DMPO alkoxyl adduct was derived from molecular oxygen. However, UV irradiation of DMPO in cyclohexane yielded the cyclohexyl and cyclohexyloxyl adducts of DMPO in nitrogen-saturated and air-saturated solutions, respectively. These observations suggest that in aprotic solvents UV irradiation of DMPO generates a carbon-centered radical (R− ), derived from the trap itself, which in benzene reacts with oxygen to yield an alkoxyl radical (RO− ), possibly via a peroxyl radical (ROO− ) intermediate. In cyclohexane R− abstracts a hydrogen atom from the solvent to yield the cyclohexyl radical in the absence of oxygen and the cyclohexyloxyl radical in the presence of oxygen. These findings indicate that when DMPO is used as a spin trap in studies employing short-wavelength UV radiation (λ < 300 nm) the photochemistry of DMPO cannot be ignored. 相似文献
15.
Boris U. Stambuk Mary Ann Franden Arjun Singh Min Zhang 《Applied biochemistry and biotechnology》2003,106(1-3):255-263
The kinetics and regulation of d-xylose uptake were investigated in the efficient pentose fermentor Candida succiphila, and in Kluyveromyces marxianus, which assimilate but do not ferment pentose sugars. Active high-affinity (K
m
∼ 3.8 mM; V
max ∼ 15 nmol/[mg·min]) and putative facilitated diffusion low-affinity (K
m
∼ 140 mM; V
max ∼ 130 nmol/[mg·min]) transport activities were found in C. succiphila grown, respectively, on xylose or glucose. K. marxianus showed facilitated diffusion low-affinity (K
m
∼ 103 mM; V
max ∼ 190 nmol/[mg·min]) transport activity when grown on xylose under microaerobic conditions, and both a low-affinity and an
active high-affinity (K
m
∼ 0.2 mM; V
max ∼ 10 nmol/[mg·min]) transport activity when grown on xylose under fully aerobic conditions. 相似文献
16.
Jack Deruiter Deborah Ann Carter Wilmer Scott Arledge Patrick J. Sullivan 《Journal of heterocyclic chemistry》1987,24(1):149-153
The reactions of 4-isopropylidene-1-aryl-3-methyl-2-pyrazolin-5-ones 4a-d were investigated under a variety of conditions. In the presence of thiols or piperidine, 4a-d failed to yield conjugate addition products, presumably due to the steric bulk provided by the two methyl substituents of the isopropylidene side chain. Reaction of 4a-d with hydrazine derivatives gave the 1-aryl-3-methyl-2-pyrazolin-5-ones 3a-d and isopropyl-hydrazones. Treatment of 4a with potassium cyanide yielded a stable conjugate addition product which exists as a mixture of tautomers in different solvents. Also, oxidation of 4a with hydrogen peroxide gave a spiroepoxide 22 , while m-chloroperbenzoic acid oxidation afforded both the spiroepoxide 22 , and a small quantity of a hydroxyspiroepoxide 23. 相似文献
17.
Ronald C. Crouch Ann O. Davis Timothy D. Spitzer Gary E. Martin Maged M. H. Sharaf Paul L. Schiff Charles H. Phoebe Albert N. Tackie 《Journal of heterocyclic chemistry》1995,32(3):1077-1080
Elucidation of minor natural product structures has been significantly augmented by inverse-detection; further improvement has been afforded by the development of micro inverse-detection probes. We report here the elucidation of the structure of a new alkaloid, quindolinone (5H, 10H-indolo[3,2-b]quinolin-11-one), from the West African plant Cryptolepis sanguinolenta. All nmr data for this minor, preparative hplc-isolated alkaloid, including 1H-15N one? bond heteronuclear shift correlation (HMQC) data, were recorded on an 800 μg sample of the alkaloid dissolved in 140 μl of 100% d6-DMSO using a 400 MHz spectrometer. 相似文献
18.
Mexiletine— and lysine hydrochloride—o-phthalaldehyde and mexiletine hydrochloride—, cysteine—, cysteamine—, homocysteine— and lysine hydrochloride—fluorescamine derivatives were subjected to Triton and β-cyclodextrin enhancement treatments. Of several classical fluorescence-enhancing reagents tested (Triton, β-cyclodextrin, sodium dodecyl sulphate, Brij), Triton provided the best results, followed by β-cyclodextrin. Increases in fluorescence emission by a factor of up to about 10 (mexiletine—fluorescamine—Triton X-100) were observed, with a generally negligible influence of the enhancing reagents on the excitation and emission maxima. Fluorescence enhancement by the addition of a suitable reagent solution to the final analyte solution may, in specific instances, enhance the detectability of native or chemically induced fluorophores. 相似文献
19.
Werner Fuss Wolfram E Schmid Sergei A Trushin Paul S Billone William J Leigh 《Chemphyschem》2007,8(4):592-598
Photochemical pericyclic reactions are believed to proceed via a so-called pericyclic minimum on the lowest excited potential surface (S(1)), which is common to both the forward and backward reactions. Such a common intermediate has never been directly detected. The photointerconversion of 1,3-butadiene and cyclobutene is the prevailing prototype for such reactions, yet only diene ring closure proceeds with the stereospecificity that the Woodward-Hoffmann rules predict. This contrast seems to exclude a common intermediate. Using ultrafast spectroscopy, we show that the excited states of two cyclobutene/diene isomeric pairs are linked by not one, but by two common minima, p* and ct*. Starting from the diene side (cyclohepta-1,3-diene and cycloocta-1,3-diene), electrocyclic ring closure passes via the pericyclic minimum p*, whereas ct* is mainly responsible for cis-trans isomerization. Starting from the corresponding cyclobutenes (bicyclo[3.2.0]heptene-6 and bicyclo[4.2.0]octene-7), the forbidden isomer is formed from ct*. The path branches at the first (S(2)/S(1)) conical intersection towards p* and ct*. The fact that the energetically unfavorable ct* path can compete is ascribed to a dynamic effect: the momentum in C=C twist direction, acquired--such as in other olefins--in the Franck-Condon region of the cyclobutenes. 相似文献
20.
Kaale E Govaerts C Hoogmartens J Schepdael AV 《Rapid communications in mass spectrometry : RCM》2005,19(20):2918-2922
Aminoglycoside antibiotics are widely used to treat serious Gram-negative and Gram-positive bacterial infections. The lack of a UV chromophore presents a problem in the analysis of aminoglycosides. Derivatization with 1,2-phthalic dicarboxaldehyde (OPA) in the presence of a thiol made it possible to introduce a UV chromophoric thioisoindole moiety. A qualitative mass spectrometry study was carried out to confirm the molecular identity of the products formed. The conditions described earlier to derivatize gentamicin and kanamycin yielded products in which all primary amino groups are fully derivatized. On the other hand, with tobramycin and amikacin, there was also formation of incompletely derivatized products that contained one thioisoindole group less than the fully derivatized product. This study has therefore brought an additional insight into the nature of the OPA-aminoglycoside derivatives studied. 相似文献