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71.
A range of room temperature 1,3-dipolar cycloaddition reactions of imines of 2-amino-γ-lactone and thiolactone, catalysed by a combination of AgOAc or Ag2O with NEt3 or DBU, are described. The spiro lactones/thiolactones are formed regio- and stereoselectively as single cycloadducts in good yield via the syn dipoles and an endo-transition states. 相似文献
72.
THREE EXPONENTIAL FLUORESCENCE DECAY OF HORSE LIVER ALCOHOL DEHYDROGENASE REVEALED BY IODIDE QUENCHING 总被引:1,自引:0,他引:1
David R. Demmer † Douglas R. James † Ronald P. Steer Ronald E. Verrall 《Photochemistry and photobiology》1987,45(1):39-48
Abstract— The time resolved fluorescence decay of horse liver alcohol dehydrogenase was measured using a frequency doubled picosecond dye laser and time-correlated single-photon counting detection. A flow-cell technique is described which eliminates the photodegradation artifacts which commonly occur with laser excitation. A procedure is introduced which uses fluorescence quenching to reveal minor fluorescence lifetime components. The decay of the unquenched tryptophanyl fluorescence could be described by a double exponential decay law, but experiments conducted in the presence of iodide ion showed that the fluorescence decay must be more complex than this. A model is presented in which the fluorescence decay consists of three exponential components, only two of which are susceptible to quenching by iodide ion. Several possibilities are presented for the origin of this minor decay component, the most reasonable of which is that it arises from conformational heterogeneity in the solvent-exposed tryptophanyl residue. 相似文献
73.
A method of analysing steady-state fluorescence quenching in compartmentalized systems is proposed which allows the evaluation of partition and binding constants where both association processes occur simultaneosly. The number of binding sites is shown to be dependent on the nature of the quencher. 相似文献
74.
[structure: see text] The first syntheses of the adducts formed in the reactions of o-quinone metabolites of carcinogenic polycyclic aromatic hydrocarbons (BPQ and BAQ) at 2'-deoxyadenosine and 2'-deoxyguanosine sites in DNA are reported. These syntheses entail Pd-catalyzed coupling of protected amine derivatives of catechols with suitably protected halopurine analogues of 2'-deoxyribonucleosides. 相似文献
75.
This study aims to clarify the effects of carbon activation type and physical form on the extent of adsorption capacity and
desorption capacity of a bi-solute mixture of phenol and 2-chlorophenol (2-CP). For this purpose, two different PACs; thermally
activated Norit SA4 and chemically activated Norit CA1, and their granular countertypes with similar physical characteristics,
thermally activated Norit PKDA and chemically activated Norit CAgran, were used. The thermally activated carbons were better
adsorbers for phenol and 2-CP compared with chemically activated carbons, but adsorption was more reversible in the latter
case. 2-CP was adsorbed preferentially by each type of activated carbon, but adsorption of phenol was strongly suppressed
in the presence of 2-CP. The simplified ideal adsorbed solution (SIAS) model underestimated the 2-CP loadings and overestimated
the phenol loadings. However, the improved and modified forms of the SIAS model could better predict the competitive adsorption.
The type of carbon activation was decisive in the application of these models. For each activated carbon type, phenol was
desorbed more readily in the bi-solute case, but desorption of 2-CP was less compared with single-solute. This was attributed
to higher energies of 2-CP adsorption. 相似文献
76.
Yvan Giroud Pierre-Alain Carrupt Alessandra Pagliara Bernard Testa Ronald G. Dickinson 《Helvetica chimica acta》1998,81(2):330-341
In this study, we compared the lipophilicity of O-glucuronides and their aglycones. Distribution coefficients (log D) and P values of neutral species (log P) were determined by centrifugal partition chromatography (CPC) in octanol/buffer systems. Two-phase potentiometry was also used to measure the log P value of some lipophilic solutes. The experimentally determined global influence of glucuronidation on lipophilicity, obtained as the difference (decrement) log P(glucuronide) ? log P(aglycone), was found to be ?1.30 ± 0.16 (n = 4) for glucuronides of alcohols (methyl, menthyl, neomenthyl, and chloramphenicol O-glucuronide). The mean decrement was ?2.06 ± 0.31 (n = 9) for glucuronides of phenols (phenyl, p-nitrophenyl, 1-naphthyl, 6-bromo-2-naphthyl, 4-methylumbelliferyl, 3-coumarinyl, phenolphthalein, 4′-benzophenonyl O-glucuronide, and diflunisal phenolic glucuronide). For the acylglucuronide of diflunisal and its rearrangement isomers, the mean decrement was ?1.80 ± 0.08 (n = 4; range ?1.7 to ?1.9). Differences in through-bond proximity effects as parametrized in the CLOGP algorithm seem to account for much of this difference. Conformational factors may also play a role, although it appears modest and unassessable for the glucuronides investigated here. The results imply that in vivo glucuronidation should have a stronger influence on the excretion of phenols than on that of alcohols. 相似文献
77.
Potassium Iodide as a Chemical Actinometer for 254 nm Radiation: Use of lodate as an Electron Scavenger 总被引:2,自引:0,他引:2
Ronald O. Rahn 《Photochemistry and photobiology》1997,66(4):450-455
Abstract— A solution of 0.6 M iodide and 0.1 M iodate in 0.01 M borate buffer (pH 9.25) can be used as a chemical actinometer to measure the incident fluence from a low-pressure mercury lamp that puts out more than 85% of its energy at 254 nm. The actinometric solution is optically opaque to light below 290 nm and is optically transparent to wavelengths greater than 330 nm. Hence, the solution absorbs all of the germicidal wavelengths but little if any of the ambient light normally present in the laboratory. Iodate acts as an electron scavenger and prevents the back reaction of the free electron with the iodine atom following UV excitation of KI. Irradiation results in the linear formation of triiodide, which is quantitated by measuring its absorbance at 352 nm. The quantum yield for this system is approximately 0.75 0.03 at 20.7Ao C or approximately three times greater than that obtained previously using nitrous oxide as an electron scavenger. A model is proposed to account for this difference. A precise expression to account for the concentration and temperature dependence of the quantum yield is given by pH = 0.75(1 + 0.23[C - 0.577])(1 + 0.02[T - 20.7]) where C is the concentration of iodide and T is the temperature. The concentration of iodide can be obtained from the absorbance at 300 nm prior to irradiation using 1.061 MJ cm−1 as the molar extinction coefficient. This actinometric system meets the quality criteria established by the International Union of Pure and Applied Chemistry with the caveat that it is designed to measure only germicidal radiation (i.e. wavelengths less than 290 nm). 相似文献
78.
Ronald L. Cerny Kenneth B. Tomer Michael L. Gross 《Journal of mass spectrometry : JMS》1986,21(10):655-660
Combining desorption ionization with tandem mass spectrometry overcomes the disadvantage of limited fragmentation accompanying desorption and permits mixtures of closely related substances to be investigated directly. These features of the combination are illustrated by completing the structure-proof of a minor component of an ornithine-containing lipid mixture isolated from Thiobacillus thiooxidans. The minor component is a homolog of the major constituent and differs from the principal component owing to the presence of a double bond in lieu of a cyclopropyl ring in one of the constituent fatty acids. Another feature of the combined method is the potentially complementary nature of collision-activated dissociation spectra of protonated and cationized biomolecules. This is illustrated by the differences in the collision-activated dissociations of the [M + Na]+ of sucrose, desorbed by field desorption, and [M + H]+, desorbed by fast atom bombardment. A third illustration is the application of field desorption and tandem mass spectrometry to an organometallic compound. The combined approach allows the ligands to be identified and the relative ligand binding energies to be approximated. 相似文献
79.
Serganov A Yuan YR Pikovskaya O Polonskaia A Malinina L Phan AT Hobartner C Micura R Breaker RR Patel DJ 《Chemistry & biology》2004,11(12):1729-1741
Metabolite-sensing mRNAs, or "riboswitches," specifically interact with small ligands and direct expression of the genes involved in their metabolism. Riboswitches contain sensing "aptamer" modules, capable of ligand-induced structural changes, and downstream regions, harboring expression-controlling elements. We report the crystal structures of the add A-riboswitch and xpt G-riboswitch aptamer modules that distinguish between bound adenine and guanine with exquisite specificity and modulate expression of two different sets of genes. The riboswitches form tuning fork-like architectures, in which the prongs are held in parallel through hairpin loop interactions, and the internal bubble zippers up to form the purine binding pocket. The bound purines are held by hydrogen bonding interactions involving conserved nucleotides along their entire periphery. Recognition specificity is associated with Watson-Crick pairing of the encapsulated adenine and guanine ligands with uridine and cytosine, respectively. 相似文献
80.
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