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81.
Helen E. Blackwell Lucy Prez Robert A. Stavenger John A. Tallarico Elaine Cope Eatough Michael A. Foley Stuart L. Schreiber 《Chemistry & biology》2001,8(12):1776-1182
BACKGROUND: In chemical genetics, small molecules instead of genetic mutations are used to modulate the functions of proteins rapidly and conditionally, thereby allowing many biological processes to be explored. This approach requires the identification of compounds that regulate pathways and bind to proteins with high specificity. Structurally complex and diverse small molecules can be prepared using diversity-oriented synthesis, and the split-pool strategy allows their spatial segregation on individual polymer beads, but typically in quantities that limit their usefulness. RESULTS: We report full details of the first phase of our platform development, including the synthesis of a high-capacity solid-phase bead/linker system, the development of a reliable library encoding strategy, and the design of compound decoding methods both from macrobeads and stock solutions. This phase was validated by the analysis of an enantioselective, diversity-oriented synthesis resulting in an encoded 4320-member library of structurally complex dihydropyrancarboxamides. CONCLUSIONS: An efficient and accessible approach to split-pool, diversity-oriented synthesis using high-capacity macrobeads as individual microreactors has been developed. Each macrobead contains sufficient compound to generate a stock solution amenable to many biological assays, and reliable library encoding allows for rapid compound structure elucidation post-synthesis. This 'one-bead, one-stock solution' strategy is a central element of a technology platform aimed at advancing chemical genetics. 相似文献
82.
83.
光活性[1]1-联萘酚(BINOL)的不对称合成 总被引:3,自引:1,他引:2
由于 1 ,1 -联萘酚 ( BINOL)可作为手性配体或手性催化剂的前体 ,在不对称合成反应中具有广泛的应用 [1,2 ] ,所以如何得到光学纯的 BINOL的研究吸引了许多化学家的注意 .制备光学活性的 BINOL的方法较多 ,但一般效果较好的是用拆分的方法[3,4] .通过 2 -萘酚不对称氧化偶联直接得到 BINOL的方法也有许多报道 [5 ,6 ] ,但结果都不理想 .近来 ,Kocovsky等 [7]用鹰爪金碱作为手性诱导试剂 ,在Cu Cl2 存在下 ,2 -萘酚偶联得 BINOL,其 ee值为 1 0 0 % ,但产率只有 1 4% ,且由于鹰爪金碱价格昂贵 ,限制了该法的应用 .在此基础上 ,我… 相似文献
84.
交通流非参数回归模型 总被引:7,自引:0,他引:7
交通流宏观参数流量、速度和占有率在交通工程和管理中具有非常重要的作用 ,对这三者关系的刻划反映了道路本身特性和交通流的规律。到目前为止 ,基本上采用线性或非线性的参数模型来描述 ,此类模型在应用中具有一定的局限性 ,并交通变量时间序列进行预测 ,数据拟合表明 ,选择适当的核函数或邻近数以及窗宽 ,可以达到比较满意的效果 相似文献
85.
The effects of gamma irradiation on the microbiological, physical and sensory qualities of diced tomatoes 总被引:1,自引:0,他引:1
Anuradha Prakash Jacqueline Manley Suresh DeCosta Fred Caporaso Denise Foley 《Radiation Physics and Chemistry》2002,63(3-6):387-390
Diced Roma tomatoes were treated with gamma irradiation and evaluated for changes in microbial, physical, chemical and sensory properties. Dosages for Trial 1 were 0.0, 0.39, 0.56 and 1.82 kGy and in Trial 2, 0.0, 0.50, 1.24 and 3.70 kGy. Irradiation at 3.70 kGy resulted in no aerobic populations through day 12 and significantly fewer colonies through day 15 whereas yeast and mold populations experienced a 2 log reduction through day 12. Color, titratable acidity, and °Brix were not significantly affected by irradiation. Tissue firmness decreased with increasing dose but not with storage time. Treatment with 3.7 kGy decreased firmness by 50% and 20% with 0.5 kGy, however, the reduced firmness induced by 0.50 kGy was undetected by a 9 member trained sensory panel. A significant (p0.05) inverse correlation between changes in texture and water-soluble pectin (WSP) was determined while total pectin remained relatively constant and oxalate soluble pectin content decreased slightly with irradiation dose. The significant inverse correlation between the loss of firmness and WSP indicates that the changes in WSP play an important role in the tissue softening of tomatoes, This study indicates that irradiation at 0.5 kGy can reduce microbial counts substantially to improve microbial shelf life without adverse effects on sensory qualities. 相似文献
86.
Aoife M. Foley Declan P. Gavin Rebecca E. Deasy Sinéad E. Milner Thomas S. Moody Kevin S. Eccles Simon E. Lawrence Anita R. Maguire 《Tetrahedron》2018,74(13):1435-1443
Efforts to combine the intramolecular nitroaldol reaction with lipase-catalysed resolution of the resulting nitroaldol adduct in a one-pot dynamic kinetic resolution (DKR) are described. Significant challenges were encountered in the combination of the two systems. trans-2-Methyl-2-nitrocyclohexyl acetate (±)-3b was isolated in excellent enantiopurity (>98% ee) via a sequential DKR sequence where the lipase-mediated resolution and base-mediated interconversion of 2-methyl-2-nitrocyclohexanol 2 were effected alternately, demonstrating the feasibility of this approach initially. Further work showed, for the first time, evidence that a DKR-type system is possible for 2. Reaction engineering allowed the design of a sequential one-pot reaction system which furnished the products with excellent enantioselectivity, and good diastereoselectivity. 相似文献
87.
In a previous publication (Pascoe, R., Foley, J. P., Analyst 2002, 127, 710-714), a novel chiral microemulsion based on 1.0% w/v dodecoxycarbonylvaline (DDCV), 0.50% v/v ethyl acetate and 1.2% v/v 1-butanol, was shown to provide rapid enantiomeric separations of various pharmaceutical compounds. The two deficiencies noted with this method were that the peak shapes obtained were asymmetric and the efficiencies were lower than those previously obtained using DDCV micelles (Peterson, A. G., Ahuja, E. S., Foley, J. P., J. Chromatogr. B 1996, 683, 15-28). This study examines the use of three alternative low-interfacial-tension oils (methyl acetate, methyl propionate, and methyl formate), in combination with DDCV, to characterize their effect on the elution range, efficiency, resolution, and enantioselectivity of various pharmaceutical enantiomers. The oils were evaluated in both the same volume percentage and the same molar concentration as ethyl acetate in the original DDCV microemulsion system. Including ethyl acetate, a total of seven microemulsion systems were examined. For the compounds that were separated, average enantioselectivities ranged from 1.09 to 1.28, with corresponding efficiencies of 14,000-20,000. While some interesting differences were observed, ethyl acetate still proved to be the most advantageous in terms of enantioselectivity, resolution, and elution range. 相似文献
88.
分别采用全多孔型硅胶基键合强阴离子交换柱与氨丙基键合硅胶柱,在低波长 200 nm 处检测,分离测定了磷霉素 探讨了流动相条件,如p H 值、离子强度等对磷霉素保留及分离选择性的影响,优化分离条件,建立了一种测定磷霉素的高效液相色谱新方法方法简便、快速 相似文献
89.
90.
Beatriz Veleirinho Manuel F. Rei J. A. Lopes‐DA‐Silva 《Journal of Polymer Science.Polymer Physics》2008,46(5):460-471
This study describes the preparation and characterization of nanofibrous mats obtained by electrospinning poly(ethylene terephthalate) (PET) solutions in trifluoroacetic acid/dichloromethane (TFA/DCM). Special attention was paid to the effect of polymer concentration and solvent properties on the morphology, structure, and mechanical and thermal properties of the electrospun nonwovens. The results show that the spinnable concentration of PET solution in TFA/DCM solvents is above 10 wt %. Mats have nanofibrous morphology with fibers having an average diameter in the range of 200–700 nm (depending on polymer concentration and solvent composition) and an interconnected pore structure. Higher solution concentration favors the formation of uniform fibers without beads and with higher diameter. Morphology and fiber assembly changed with the solvent properties. Solvent mixtures rich in TFA, i.e., those with higher dielectric constant and lower surface tension, originated fibers with small diameter. However, due to the lower volatility, those solvent mixtures also produced more branched and crosslinking fibers, with less morphologic uniformity. Mechanical properties (Young's modulus, ultimate strength, and elongation at break) and thermal properties (glass transition, crystallization, and melting) have been studied for the PET electrospun nanomats and compared with those of the original polymer. Solvent effect on fiber crystallinity was not significant, but a complex effect was observed on the mechanical properties of the electrospun mats, as a consequence of the different structural organization of the fibers within the mat network. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 460–471, 2008 相似文献