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41.
Marino ST Stachurska-Buczek D Huggins DA Krywult BM Sheehan CS Nguyen T Choi N Parsons JG Griffiths PG James IW Bray AM White JM Boyce RS 《Molecules (Basel, Switzerland)》2004,9(6):405-426
In the past decade there has been a significant growth in the sales of pharmaceutical drugs worldwide, but more importantly there has been a dramatic growth in the sales of single enantiomer drugs. The pharmaceutical industry has a rising demand for chiral intermediates and research reagents because of the continuing imperative to improve drug efficacy. This in turn impacts on researchers involved in preclinical discovery work. Besides traditional chiral pool and resolution of racemates as sources of chiral building blocks, many new synthetic methods including a great variety of catalytic reactions have been developed which facilitate the production of complex chiral drug candidates for clinical trials. The most ambitious technique is to synthesise homochiral compounds from non-chiral starting materials using chiral metal catalysts and related chemistry. Examples of the synthesis of chiral building blocks from achiral materials utilizing asymmetric hydrogenation and asymmetric epoxidation are presented. 相似文献
42.
Dellinger DJ Sheehan DM Christensen NK Lindberg JG Caruthers MH 《Journal of the American Chemical Society》2003,125(4):940-950
Phosphonoacetate and thiophosphonoacetate oligodeoxynucleotides were prepared via a solid-phase synthesis strategy. Under Reformatsky reaction conditions, novel esterified acetic acid phosphinodiamidites were synthesized and condensed with appropriately protected 5'-O-(4, 4'-dimethoxytrityl)-2'-deoxynucleosides to yield 3'-O-phosphinoamidite reactive monomers. These synthons when activated with tetrazole were used with an automated DNA synthesizer to prepare phosphonoacetic acid modified internucleotide linkages on controlled pore glass. The phosphinoacetate coupling products were quantitatively oxidized at each step with (1S)-(+)-(10-camphorsulfonyl)oxaziridine or 3H-1,2-benzodithiol-3-one-1,1-dioxide to produce mixed sequence phosphonoacetate and thiophosphonoacetate oligodeoxynucleotides with an average per cycle coupling efficiency of greater than 97%. Completely deprotected, modified oligodeoxynucleotides were purified by reverse-phase HPLC and characterized by ion exchange HPLC, (31)P NMR, and MALDI/TOF mass spectroscopy. Both analogues were stable toward hydrolysis with snake venom phosphodiesterase and stimulated RNase H1 activity. 相似文献
43.
The synthesis of a new bicyclic system has been reported. Three substituted 5,6-dihydro-1,3-oxazines have been condensed to a fused β-lactam ring system by use of phthaloylglycyl chloride. The resulting phthalimido compounds were dephthaloylated to the corresponding oxygen analogs of cepham (2). 相似文献
44.
2-Amino-3-(o-bromobenzyloxy)pyridine ( 1 ) and ethyl acetoacetate gave 9-(o-bromobenzyl-oxy)-2-methyl-4H-pyrido[1,2-α]pyrimidin-4-one ( 2 ) in 2% yield. When 1 and methyl β-amino-crotonate ( 3 ) were reacted, benzyl ether cleavage occurred and the products were 9-hydroxy-2-methyl-4H-pyrido[1,2-α]pyrimidin-4-one ( 4 ) and its ammonium salt ( 5 ). These observations led to an alternative synthesis in which 2-amino-3-pyridinol ( 6 ) and either 3 or methyl acetoacetate, ( 8 ) in diethylbenzene at 185° gave 4 in 86 and 87% yields, respectively, and the anion of 4 and o-bromobenzyl bromide gave 2 in 61% yield. Even in diethylbenzene at 185°, 1 and 8 gave only trace amounts of 2 . Thus, o-bromobenzylation of the 3-hydroxyl group in 6 markedly decreased the reactivity of the amino group in 6 toward reactions with acetoacetic esters. 相似文献
45.
pH-biased isoelectric trapping was used to separate proteins from egg white at the preparative level (80 mg), into discrete protein fractions based on isoelectric point. The problems of isoelectric precipitation that are common for the separation of complex protein mixtures under isoelectric conditions were mitigated by using single-component isoelectric buffers within the sample separation compartments. This combined with the mild process conditions of the Gradiflow unit that was modified for binary isoelectric trapping separations, ensured that biological activity was maintained. This was verified by measurement of the trypsin protease inhibitory activity of the extract and separated fractions. Furthermore, the high resolving power of this system under preparative conditions was demonstrated by separation of three protein isoforms using isoelectric membranes with differences of 0.025 pH units from each other. 相似文献
46.
Sheehan SM Parsons BF Zhou J Garand E Yen TA Moore DT Neumark DM 《The Journal of chemical physics》2008,128(3):034301
Anion photoelectron spectroscopy of C3H- and C3D- is performed using both field-free time-of-flight and slow electron velocity-map imaging. We observe and assign transitions originating from linear/bent (l-C3H) and cyclic (c-C3H) anionic isomers to the corresponding neutral ground states and low-lying excited states. Transitions within the cyclic and linear manifolds are distinguished by their photoelectron angular distributions and their intensity dependence on the neutral precursor. Using calculated values for the energetics of the neutral isomers [Ochsenfeld et al., J. Chem. Phys. 106, 4141 (1997)], which predict c-C3H to lie 74 meV lower than l-C3H, the experimental results establish c-C3H- as the anionic ground state and place it 229 meV below l-C3H-. Electron affinities of 1.999+/-0.003 and 1.997+/-0.005 eV are determined for C3H and C3D from the X 2B2<--X 1A1 photodetachment transition of c-C3H. Term energies for several low-lying states of c-C3H and l-C3H are also determined. Franck-Condon simulations are used to make vibrational assignments for the bands involving c-C3H. Simulations of the l-C3H bands were more complicated owing to large amplitude bending motion and, in the case of the neutral A 2Pi state, strong Renner-Teller coupling. 相似文献
47.
48.
We investigate the values of t(n), the maximum number of edges in a graph with n vertices and not containing a four-cycle. Techniques for finding these are developed and the values of t(n) for all n up to 21 are obtained. All the corresponding extremal graphs are found. 相似文献
49.
A rapid gas chromatographic method for the determination of underivatized theophylline in whole blood is described. Theophylline is extracted from acidified blood and chromatographed directly using cyheptamide as an internal standard. Concentrations of the drug down to 2 mug/ml in blood could be determined with recoveries ranging from 90 to 110%. 相似文献
50.
Christopher Jennison Nuala Sheehan 《Journal of computational and graphical statistics》2013,22(4):296-318
Abstract We investigate the basic form of the genetic algorithm as an optimization technique. Its failure to maximize a simple function of a string of 50 binary variables prompts a closer study of Holland's “schema theorem” and we find the implications of this result to be much weaker than are often claimed. Further theoretical results and exact calculations for simple problems provide an understanding of how the genetic algorithm works and why it failed in our original application. We show that the algorithm can be fine tuned to succeed in that problem but only by introducing features that could cause serious difficulties in harder problems. 相似文献