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91.
The electrochemical and spectrophotometric characterization of the complex formed from samarium diiodide and 4 equiv of tripyrrolidinophosphoric acid triamide (TPPA) is presented. Kinetic studies indicate that the SmI(2)/TPPA complex possesses reactivity greater than the complex formed between samarium diiodide and 4 equiv of HMPA. Examples of the use of SmI(2)/TPPA in synthesis are presented. 相似文献
92.
Lieza M. Danan Zhihao Yu Peter J. Ludden Weitao Jia Kevin L. Moore Julie A. Leary 《Journal of the American Society for Mass Spectrometry》2010,21(9):1633-1642
Human tyrosylprotein sulfotransferases catalyze the transfer of a sulfuryl moiety from the universal sulfate donor PAPS to
the hydroxyl substituent of tyrosine residues in proteins and peptides to yield tyrosine sulfated products and PAP. Tyrosine
sulfation occurs in the trans-Golgi network, affecting an estimated 1% of the tyrosine residues in all secreted and membrane-bound
proteins in higher order eukaryotes. In this study, an effective LC-MS-based TPST kinetics assay was developed and utilized
to measure the kinetic properties of human TPST-2 and investigate its catalytic mechanism when G protein-coupled CC-chemokine
receptor 8 (CCR8) peptides were used as acceptor substrates. Through initial rate kinetics, product inhibition studies, and
radioactive-labeling experiments, our data strongly suggest a two-site ping-pong model for TPST-2 action. In this mechanistic
model, the enzyme allows independent binding of substrates to two distinct sites, and involves the formation of a sulfated
enzyme covalent intermediate. Some insights on the important amino acid residues at the catalytic site of TPST-2 and its covalent
intermediate are also presented. To our knowledge, this is the first detailed study of the reaction kinetics and mechanism
reported for human TPST-2 or any other Golgi-resident sulfotransferase. 相似文献
93.
Aline Staub Sylvain Giraud Martial Saugy Serge Rudaz Jean‐Luc Veuthey Julie Schappler 《Electrophoresis》2010,31(2):388-395
CE is a powerful analytical tool used to separate intact biomolecules such as proteins. The coupling of CE with TOF/MS produces a very promising method that can be used to detect and identify proteins in different matrices. This paper describes an efficient, rapid, and simple CE‐ESI‐TOF/MS procedure for the analysis of endogenous human growth hormone and recombinant human growth hormone without sample preparation. Operational factors were optimized using an experimental design, and the method was successfully applied to distinguish human growth hormone and recombinant human growth hormone in unknown samples. 相似文献
94.
Carl R. Kemnitz Prof. Joel L. Mackey Mark J. Loewen Julie L. Hargrove Joshua L. Lewis Whitney E. Hawkins Adam F. Nielsen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(23):6942-6949
The potential origins of stability in branched alkanes are investigated, paying close attention to two recent hypotheses: geminal steric repulsion and protobranching. All alkane isomers through C6H14 along with heptane and octane were investigated at the MPW1B95/6‐311++G(d,p) level. Their geminal steric repulsion, total steric repulsion, and orbital interactions were evaluated by using natural bond orbital analysis. All measures of steric repulsion fail to explain the stability of branched alkanes. The extra stability of branched alkanes and protobranching, in general, is tied to stabilizing geminal σ→σ* delocalization, particularly of the type that involves adjacent C? C bonds and, thus, preferentially stabilizes branched alkanes. This picture is corroborated by valence bond calculations that attribute the effect to additional ionic structures (e.g., CH3+ :CH2 :CH3? and CH3:? CH2: CH3+ for propane) that are not possible without protobranching. 相似文献
95.
Allegrand J Touboul D Schmitz-Afonso I Guérineau V Giuliani A Le Ven J Champy P Laprévote O 《Rapid communications in mass spectrometry : RCM》2010,24(24):3602-3608
Collision‐induced dissociation experiments of seven annonaceous acetogenins were carried out under high and low collision energy conditions. Each compound was studied as protonated or deprotonated and lithium‐ or sodium‐ cationized molecules, using ElectroSpray Ionisation (ESI) with a hybrid linear trap/orbitrap mass spectrometer (LTQ‐Orbitrap®). The same ion species were studied with a Matrix‐Assisted Laser Desorption Ionisation (MALDI) tandem mass spectrometer in a high collision energy regime (1 or 2 keV). Although each of the techniques showed some limitations in the detection of functional groups, unambiguous structural identification of the acetogenins was obtained. MALDI ToF‐ToF has the advantage over ESI‐based methods to provide mass spectra rich in informative fragments which allows the confirmation of some functional groups position. By contrast, ESI‐LTQ‐Orbitrap® analysis has the advantage over MALDI that the mass spectra are relatively simple with only fragments close to the functional groups. However, this technique needs to carry out experiments both in negative and positive ionization modes. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
96.
Christian P. Marocco Erik V. Davis Julie E. Finnell Phung-Hoang Nguyen Scott C. Mateer Ion Ghiviriga Clifford W. Padgett Brent D. Feske 《Tetrahedron: Asymmetry》2011,22(18-19):1784-1789
Fosfomycin is a gram positive and gram negative antibiotic that contains an asymmetric epoxide. An enzyme library was screened for its ability to reduce dimethyl(1-chloro-2-oxopropyl)phosphonate to the corresponding asymmetric chlorohydrin. Homology models were built in MOE, which were shown to accurately model the enzyme–substrate complex displaying the stereoselectivity that we observed. Two enzymes, YDR368w and YHR104w, were chosen for the scale up and synthesis of fosfomycin and its trans-(1S,2S)-diastereomer. 相似文献
97.
Julie Déserti 《Bulletin of the Brazilian Mathematical Society》2007,38(3):377-388
Résumé. Nous décrivons les sous-groupes nilpotents non virtuellement abéliens du groupe des transformations birationnelles du plan
projectif complexe: un tel groupe est d'ordre fini ou virtuellement métabélien.
相似文献
98.
In several applications, underestimation of functions has proven to be a helpful tool for global optimization. In protein–ligand
docking problems as well as in protein structure prediction, single convex quadratic underestimators have been used to approximate
the location of the global minimum point. While this approach has been successful for basin-shaped functions, it is not suitable
for energy functions with more than one distinct local minimum with a large magnitude. Such functions may contain several
basin-shaped components and, thus, cannot be underfitted by a single convex underestimator. In this paper, we propose using
an underestimator composed of several negative Gaussian functions. Such an underestimator can be computed by solving a nonlinear
programming problem, which minimizes the error between the data points and the underestimator in the L
1 norm. Numerical results for simulated and actual docking energy functions are presented. 相似文献
99.
Stephen MT Hoke Gaoyang Liang A Irina Mutiu Julie Genereaux Christopher J Brandl 《BMC biochemistry》2007,8(1):16
Background
Spt7 is an integral component of the multi-subunit SAGA complex that is required for the expression of ~10% of yeast genes. Two forms of Spt7 have been identified, the second of which is truncated at its C-terminus and found in the SAGA-like (SLIK) complex. 相似文献100.
Spitzer SM Liss JM Mattys SL 《The Journal of the Acoustical Society of America》2007,122(6):3678-3687
It has been posited that the role of prosody in lexical segmentation is elevated when the speech signal is degraded or unreliable. Using predictions from Cutler and Norris' [J. Exp. Psychol. Hum. Percept. Perform. 14, 113-121 (1988)] metrical segmentation strategy hypothesis as a framework, this investigation examined how individual suprasegmental and segmental cues to syllabic stress contribute differentially to the recognition of strong and weak syllables for the purpose of lexical segmentation. Syllabic contrastivity was reduced in resynthesized phrases by systematically (i) flattening the fundamental frequency (F0) contours, (ii) equalizing vowel durations, (iii) weakening strong vowels, (iv) combining the two suprasegmental cues, i.e., F0 and duration, and (v) combining the manipulation of all cues. Results indicated that, despite similar decrements in overall intelligibility, F0 flattening and the weakening of strong vowels had a greater impact on lexical segmentation than did equalizing vowel duration. Both combined-cue conditions resulted in greater decrements in intelligibility, but with no additional negative impact on lexical segmentation. The results support the notion of F0 variation and vowel quality as primary conduits for stress-based segmentation and suggest that the effectiveness of stress-based segmentation with degraded speech must be investigated relative to the suprasegmental and segmental impoverishments occasioned by each particular degradation. 相似文献