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1.
D. Allen Clabo Jr. Hamilton D. Dickson Toby L. Nelson 《Journal of molecular modeling》2000,6(2):341-348
Semiempirical and ab initio theoretical methods have been used to investigate molecular structures of the chalcogen-substituted carboxylic acid isomers RC(=O)XH (chalcogenol acid) and RC(=X)OH (chalcogenon acid). A recent experimental report suggests that the chalcogenon isomers, although less stable at room temperature, predominate at low temperature in polar solvents and that there is only a small barrier to isomerization between the isomers. Theoretical calculations have been used to locate minimum energy structures of chalcogen-substituted carboxylic acid isomers and to calculate energy differences between pairs of isomers. Carboxylic acids are well known to dimerize, especially in the gas phase and in non-polar solvents. We have, therefore, also calculated energies of dimerization of the chalcogen-substituted acids by optimizing the geometries of the symmetric dimers. We note that the PM3 level of theory is only qualitatively correct for sulfur- and selenium-containing species but fails even qualitatively for the tellurium-containing compounds. Ab initio results confirm the experimental observations and provide good estimates of both isomerization and dimerization energies. We conclude that for many functional groups with tautomers RC(=X)YH and RC(=Y)XH, the more acidic tautomer is the one with the acid proton on the smaller, more electronegative atom, although in many cases this may not be the more stable tautomer.Electronic Supplementary Material available. 相似文献
2.
Roselyne Rousseaux-Prvost Ren-Pierre Engelhardt Jean Rousseaux Danile Wouters-Tyrou Pierre Sautire 《Molecular reproduction and development》1988,19(3):277-290
The changes in basic nuclear proteins throughout cuttle-fish spermiogenesis were investigated both by immunocytochemical procedures and by isolation of late spermatid nuclei (by virtue of their resistance to sonication). Antibodies were raised in rabbits to a protein, named protein T, isolated from testis chromatin. The anti-protein T immune serum was found to recognize protein T and not histones from the testis. Immunoperoxidase staining of sections or of smears of testis with anti-protein T antibodies showed that protein T appears in the nuclei of round spermatids, is abundant in elongating spermatid nuclei, but cannot be detected in elongated spermatids. Nuclei from these elongated spermatids were isolated by sonication treatment of testis cells. A protein, named protein Sp, with the characteristic mobility of a protamine, was isolated from elongated spermatid nuclei. This protein has the same mobility as the protamine present in mature spermatozoa. Taken together, the results indicate that in cuttle-fish, nuclear protein transitions involve the replacement of histones by a spermatid-specific protein (protein T), which is replaced at the end of elongation of the nucleus by a protamine (protein Sp). Thus, spermiogenesis of the cuttle-fish (and perhaps of other cephalopods), shows two basic nuclear protein transitions, which are similar to the transitions observed in higher vertebrates such as mammals. 相似文献
3.
Marc Haumont Jacques Magdalou Jean-Claude Ziegler Roselyne Bidault Jean-Pascal Siest Gérard Siest 《Applied microbiology and biotechnology》1991,35(4):440-446
Summary The production of glucuronides from drugs by immobilized microsomal uridine diphosphate (UDP)-glucuronosyltransferase has been investigated. Of all the immobilization methods used (covalent binding, adsorption by ionic or hydrophobic interactions), only entrapment of microsomes into alginate beads in the presence of polyethyleneimine was effective in producing high glucuronidation rates, thus leading to the formation of large amounts of metabolites. The performance of the bioreactor was optimized with the drug 3-azido-3-deoxythymidine (AZT), active against the human immunodeficiency virus, as a model substrate of UDP-glucuronosyltransferase. Calcium (12 mm) could optimally improve the stability of microsomes entrapped in alginate beads. Upon immobilization, enzyme activation occurred, leading to a fivefold increase in specific activity. The determination of apparent K
m and V
max revealed that AZT was a better substrate for the immobilized enzyme than free microsomes. The AZT-glucuronide production obtained after 6 h was threefold higher than that observed with free microsomes. This bioreactor was also efficient in production of glucuronides from structurally different compounds such as bilirubin, 4-nitrophenol, clofibric acid, pirprofen, dextrorphan or morphine, the corresponding glucuronide of which possesses pharmacological or toxicological interest.
Offprint requests to: J. Magdalou 相似文献
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To investigate the physical and kinetic properties of sperm carnitine acetyltransferase, the enzyme was purified from bovine spermatozoa and heart muscle. Carnitine acetyltransferase was purified 580-fold from ejaculated bovine spermatozoa to a specific activity of 85 units/mg protein (95% homogeneity). Sperm carnitine acetyltransferase was characterized as a single polypeptide of Mr 62,000 and pI 8.2. Heart carnitine acetyltransferase was purified 650-fold by the same procedure to a final specific activity of 71 units/mg protein. The kinetic properties of purified bovine sperm carnitine acetyltransferase were consistent with the proposed function of this enzyme in acetylcarnitine pool formation. Product inhibition by either acetyl-l-carnitine or CoASH was not sufficient to predict significant in vivo inhibition of acetyl transfer. At high concentrations of l-carnitine, bovine sperm and heart carnitine acetyltransferases were most active with propionyl- and butyryl-CoA substrates, although octanoyl-, iso-butyryl-, and iso-valeryl-CoA were acceptable substrates. Binding of one substrate was enhanced by the presence of the second substrate. Carnitine analogs that have significance in reproduction, such as phosphorylcholine and taurine, did not inhibit carnitine acetyltransferase. Bovine sperm and heart carnitine acetyltransferases were indistinguishable on the basis of purification behavior, pI, pH optima, kinetic properties, acyl-CoA specificity, and sensitivity to sulfhydryl reagents and divalent cations; thus there was no indication that bovine sperm carnitine acetyltransferase is a sperm-specific isozyme. 相似文献
6.
This study describes the sequential alternation of compaction and decompaction in the chromosomes of the Chinese hamster oocyte from diakinesis to metaphase II. A series of micrographs show that the compact metaphase I chromosomes become greatly extended as they enter and pass through anaphase I. Once polarized, the presumptive oocyte chromosomes become exceedingly compact and form a tightly packed mass, each chromosome assuming contours to accomodate dovetailing with its neighbors, while the chromosomes consigned to the polar body remain extended and show signs of the incipient deterioration. Prior to ovulation, the chromosomes of the mass separate and begin to decompact, in part at least, by the previously postulated mechanism of uncoiling. Following ovulation, the chromosomes are greatly extended and, as the metaphase II complement, remain in that state until the advent of fertilization. — Evidence that the compaction patterns are ordered and chromosome specific is presented by observation of the two smallest chromosomes of the complement. At telophase I those chromosomes are markedly different in size and arm ratio; at metaphase II the differences are less pronounced and at mitotic metaphase the two smallest chromosome pairs are so similar in morphology as to be indistinguishable. It is proposed, therefore, that those two chromosomes differ in their fundamental morphology as revealed at the exceedingly compact state of telophase I oocyte chromosomes. Their subsequently established resemblance at mitotic metaphase may be due to allocycly on the part of one or both, resulting in two chromosomes of apparantly similar length and arm ratio.Supported by grants from the Institute of Child Health and Development of the National Institutes of Health, 5 RO1 HDO4846 and the Damon Runyan Foundation, DRG-907.Supported in part by CA-08748 from the Cancer Institute of the National Institutes of Health. 相似文献
7.
Toby A. Ferguson John Vozenilek Christopher M. West 《Development, growth & differentiation》1994,36(6):597-604
As a result of transfecting Dictyostelium discoideum with an actin 6/ lac Z fusion transgene, strain HW80 was created which expresses the β-galactosidase gene product uniformly throughout development. When mixed with an excess of unmarked wild-type cells, however, HW80 cells selectively migrate to the positions of anterior-like cells surrounding the prespore cell mass, and differentiate as if they were anterior-like cells. As the proportion of HW80 cells is increased, they also sort to positions adjacent to anterior-like cells and some differentiate as prespore cells. Thus sorting of HW80 cells toward the opposite ends of the prespore cell zone supersedes how they differentiate, suggesting that position influences whether cells differentiate as anterior-like or prespore cells. 相似文献
8.
Studies indicate that low birthweight (LBW) children display reduced deciduous tooth size but there is little information about permanent tooth size. It has also been shown that dental fluctuating asymmetry (FA) increases in response to various environmental influences, but the relationship between birthweight and FA remains unclear. The aim of this study was to compare tooth size and asymmetry, according to birthweight, in the deciduous and permanent dentitions of a sample of Australian twins. The study sample comprised 436 twins, classified into 2 groups: normal birthweight (NBW > 2500 g) and low birthweight (LBW < or = 2500 g). For each individual it was generally possible to measure maximum mesiodistal crown diameters of both deciduous and permanent central incisors from serial dental models. Correlations were calculated between tooth-size variables and birthweight; subsequently comparisons of tooth size and FA were made between the LBW and NBW samples using Student's t tests. Small positive correlations (around .1) were noted between birthweight and tooth-size variables. There was no evidence of tooth-size reduction in the LBW male sample, but the LBW females displayed tooth-size reduction of approximately 2-3% for both deciduous and permanent incisors, compared to the NBW females. There was no evidence of increased FA in the LBW individuals of either sex. These findings indicate that developing teeth are generally well-protected from developmental disturbances during prenatal and perinatal periods. Further research is needed to clarify the biological basis of an apparently true but weak association between tooth size and birthweight. 相似文献
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10.
Antonio P. Linares Stuart H. Cohen Elliot Goldstein Alan D. K. Kelley Toby K. Eisenstein 《The Western journal of medicine》1984,141(2):203-205
Salmonella thompson, a common pathogen of poultry, has received scant attention as a cause of human gastroenteritis. At least 45 persons were infected with S thompson in Sacramento, California, after eating at a chicken restaurant and 38 became symptomatic. Ten required admission to hospital, and all were treated with antibiotics and improved. In 19 cases cultures of stool specimens for S thompson over a 60-day period showed slower but statistically insignificant differences in salmonellal elimination in 7 patients who received antibiotics when compared with 12 who were untreated. We report this outbreak to increase awareness of the virulence and prevalence of gastroenteritis due to S thompson. 相似文献