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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
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A Rethwilm G Baunach K O Netzer B Maurer B Borisch V ter Meulen 《Nucleic acids research》1990,18(4):733-738
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Eighteen heifers and 120 cows which were descendants of a presumed 1/29 carrier Simmental bull were karotyped. Nine heifers (50%) and 48 cows (40%) were found to be heterozygous for the 1/29 translocation (59, XX, t(1q;29q)). The other animals were chromosomally normal (i.e., 60, XX) or not karotyped. The 48 1/29 cows were compared with 72 chromosomally normal cows with regards to days to first conception, calving interval, percentage of calves conceived, percentage of calves weaned and production efficiency (% calved conceived × % calved weaned). Nine carrier heifers were compared to the nine noncarrier heifers as to pregnancy status. Carrier, noncarrier and nonkarotyped relatives were compared to each other and to contemporary females with regard to pregnancy status at their initial exposure to males. The percentage of calves conceived (calving efficiency) in the 72 noncarrier and the 48 females heterozygous for the 1/29 translocation were 81.5 and 74.8%, respectively (P<0.07). Although days to first conception was longer and percentage of calves weaned and production efficiency were lower in the female heterozygous for the 1/29 translocation, the differences were not statistically different (P>0.10) from the noncarriers. Pregnancy rate was 44.4 and 66.7% (P>0.10) for nine carrier and nine noncarrier heifers, respectively. The pregnancy rate of carrier (65.4%), noncarrier (73.2%) and nonkarotyped (77.8%) relatives of this sire at their mating as yearlings, did not differ (P>0.10). The pregnancy rate as yearlings of carrier females (65.4%) and contemporary heifers (79.8%) did differ (P<0.05). Comparing the pregnancy rate as yearlings of all descendants (72.0%) of the Simmental sire to contemporary heifers (79.8%), a significant decrease (P<0.05) was found indicating that fertility of this sire may have been lower than other sires or that other factors beside the translocation affected fertility. 相似文献
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E J Gibbs M C Maurer J H Zhang W M Reiff D T Hill M Malicka-Blaszkiewicz R E McKinnie H Q Liu R F Pasternack 《Journal of inorganic biochemistry》1988,32(1):39-65
Studies of the solution properties of gold(III)tetrakis(4-N-methylpyridyl) porphine and its DNA binding characteristics have been conducted utilizing uv/vis absorption spectroscopy, circular dichroism (CD), Mossbauer spectroscopy, and temperature-jump relaxation techniques. These studies indicate that over the concentration range considered this water soluble gold(III) porphyrin does not aggregate, binds axial ligands only weakly with a preference for soft Lewis bases, and is capable of intercalation into nucleic acids of appropriate base pair content. The interaction of this and several other porphyrins with the synthetic polynucleotide poly(dA-dC).poly(dT-dG) has been studied. Spectroscopic signatures for intercalation were found for those derivatives not having axial ligands. Intercalation into chromatin in vitro can also occur with those porphyrins and metalloporphyrins which do not have axial ligands. Finally, studies utilizing microinjection techniques indicate that once within the cell, tetrakis(4-N-methylpyridyl)porphine tends to localize in the nucleus. 相似文献
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K Leung K E Kim R A Maurer T D Landefeld 《Molecular endocrinology (Baltimore, Md.)》1988,2(3):272-276
Cyclic changes in the production of the pituitary gonadotrophic hormones, LH and FSH are essential events in the maintenance of the reproductive system of female mammals. While studies have examined changes in the secretion of LH and FSH during the estrous cycle and demonstrated the importance of these hormones in regulation of ovarian development and gametogenesis, considerably less is known concerning the regulation of the biosynthesis of these hormones. Although initial studies have examined changes in LH subunit mRNA concentrations during the rat and ovine estrous cycles, no information concerning the physiological regulation of FSH beta mRNA concentrations has been available. In the present study we have examined the relationship between pituitary concentrations of LH and FSH subunit mRNAs and the serum concentrations of these gonadotropins. The results demonstrate a very different pattern of change for FSH beta subunit mRNA than that observed for alpha and LH beta subunit mRNAs. In fact, FSH beta mRNA concentration decline substantially during the preovulatory period, reaching minimal values at a time when alpha and LH beta mRNA levels are near maximal. Furthermore, this decline in FSH beta mRNA amounts occurs when serum FSH concentrations are maximal. Thus, FSH beta mRNA concentrations follow a very different pattern than that of serum FSH. In contrast, LH beta mRNA and serum LH concentrations tend to increase at the same time. These findings provide evidence that concentrations of LH beta and FSH beta mRNAs are likely regulated by different mechanisms. 相似文献
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L Selleri J H Eubanks M Giovannini G G Hermanson A Romo M Djabali S Maurer D L McElligott M W Smith G A Evans 《Genomics》1992,14(2):536-541
"Chimeric" yeast artificial chromosomes (YACs) are clones containing two or more noncontiguous segments of DNA and represent the most common artifact found in total genomic YAC libraries currently used for large-scale genome mapping. These YACs create spurious mapping information that complicates the construction of YAC contigs and leads to erroneous maps during chromosome walks. The presence of these artifactual clones necessitates laborious and time-consuming characterization of each isolated YAC clone, either by comparison of the physical map of the YAC with the corresponding source genomic DNA, or by demonstrating discrepant chromosomal origins for the two ends of the YAC by hybridization or polymerase chain reaction (PCR). Here, we describe a rapid and sensitive method for the assessment of YAC colinearity by fluorescence in situ suppression hybridization (FISSH) by utilizing fluorescein-12-dUTP for labeling YAC clones. We have analyzed 51 YACs and found that 43% (22 out of 51) are chimeric and significantly larger (302 kb) than colinear ones (228 kb). One of the 51 YAC clones (2%) examined contains portions of three chromosomes and 2 (4%) seem to map to a chromosome different than that of the identifying STS. FISSH analysis offers a straightforward visualization of the entire YAC insert on the chromosomes and can be used to examine many YACs simultaneously in few days. 相似文献
10.
S M Van Patten P Howard D A Walsh R A Maurer 《Molecular endocrinology (Baltimore, Md.)》1992,6(12):2114-2122
The inhibitor protein (PKI) of the cAMP-dependent protein kinase was first characterized from rabbit skeletal muscle. More recently a form of PKI was isolated and cloned from rat testis which shares relatively limited amino acid sequence with the rabbit skeletal muscle form. We have now isolated a cDNA from rat brain which encodes a protein corresponding to the rabbit skeletal muscle PKI. This establishes the presence of the "skeletal muscle" and "testis" proteins in the same species and therefore that they clearly represent distinct isoforms. We have also demonstrated that the isoform from testis, like the skeletal muscle isoform, is specific for the cAMP-dependent protein kinase and that it is able to inhibit this enzyme when expressed in cultured JEG-3 cells. Both forms contain the five specific amino acid recognition determinants which have been shown to be required for high affinity binding to the protein kinase catalytic site, although there is some noted lack of conservation of codons used for these residues. Overall, the two rat isoforms are only 41% identical at the amino acid level and 46% at the level of coding nucleotides. We propose that the rabbit skeletal muscle and rat testis forms be designated PKI alpha and PKI beta, respectively. Using Northern blot analysis, we have examined the tissue distribution of the two forms in the rat and their relative expression during development. In the adult rat, mRNA of the PKI alpha species is highest in muscle (both skeletal and cardiac) and brain (cortex and cerebellum).(ABSTRACT TRUNCATED AT 250 WORDS) 相似文献