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41.
Kimmel KL Weaver JD Lee M Ellman JA 《Journal of the American Chemical Society》2012,134(22):9058-9061
The highly enantioselective protonation of nitronates formed upon the addition of α-substituted Meldrum's acids to terminally unsubstituted nitroalkenes is described. This work represents the first enantioselective catalytic addition of any type of nucleophile to this class of nitroalkenes. Moreover, for the successful implementation of this method, a new type of N-sulfinyl urea catalyst with chirality residing only at the sulfinyl group was developed, thereby enabling the incorporation of a diverse range of achiral diamine motifs. Finally, the Meldrum's acid addition products were readily converted to pharmaceutically relevant 3,5-disubstituted pyrrolidinones in high yield. 相似文献
42.
Kulkarni A DeFrees K Hyun SH Thompson DH 《Journal of the American Chemical Society》2012,134(18):7596-7599
A novel siRNA delivery vector has been developed, based on the self-assembly of monosubstituted cationic β-CD derivatives with a poly(vinyl alcohol)MW27kD (PVA) main-chain polymer bearing poly(ethylene glycol)MW2000 (PEG) and acid-labile cholesterol-modified (Chol) grafts through an acid-sensitive benzylidene acetal linkage. These components were investigated for their ability to form nanoparticles with siRNA using two different assembly schemes, involving either precomplexation of the pendant Chol-PVA-PEG polymer with the cationic β-CD derivatives before siRNA condensation or siRNA condensation with the cationic β-CD derivatives prior to addition of Chol-PVA-PEG to engage host:guest complexation. The pendant polymer:amino-β-CD:siRNA complexes were shown to form nanoparticles in the size range of 120-170 nm, with a slightly negative zeta potential. Cell viability studies in CHO-GFP cells shows that these materials have 10(3)-fold lower cytotoxicities than 25 kD bPEI, while maintaining gene-silencing efficiencies that are comparable to those of benchmark transfection reagents such as bPEI and Lipofectamine 2000. These results suggest that the degradable Chol-PVA-PEG polymer is able to self-assemble in the presence of siRNA and cationic-β-CD to form nanoparticles that are an effective and low-toxicity vehicle for delivering siRNA cargo to target cells. 相似文献
43.
Sayonara Maria Calado Gonçalves Glória Najara Silva Ivan da Rocha Pitta Moacyr Jesus Barreto de Melo Rêgo Simone Cristina Baggio Gnoato 《Natural product research》2020,34(12):1702-1711
AbstractBetulin (BE) is a pentacyclic triterpenes, obtained from natural sources and with several biological activities described, such as anti-tumoral and anti-inflammatory activities. The BE esterification at hydroxyl group (C-3 and C-28) resulted in five new ester derivatives with different numbers of carbons or halogens (chlorine and fluorine). Among these BE derivatives, two (2a e 2c) were able to significantly decrease IFN-g (*p?=?0.0391; **p?=?0.0156) and 2c modulated the expression of COX-2 better than Dexamethasone (DEXA). Regarding to cytotoxic assay, the best results were obtained for BE without modifications, with emphasis on tumoral cell lines Raji and MCF-7. The derivatives 2a and 2c showed immunomodulation activity (for the cytokines IFN-g). The presence of chorine in BE seems to be important for the ability of modulate COX-2 expression, since the ester chloride derivative 2c at 100?μM is more powerful inhibitor of COX-2 than DEXA. 相似文献
44.
Holly D. Bendorf Kyle E. Ruhl Andrew J. Shurer Jennie B. Shaffer Tess O. Duffin Theresa L. LaBarte Michelle L. Maddock Oscar W. Wheeler 《Tetrahedron letters》2012,53(10):1275-1277
Medium-ring heterocycles are prepared via an amine-directed, rhodium(I)-catalyzed intramolecular hydroacylation. The presence of an allyl substituent on the amine accelerates the reaction and increases product yields. 相似文献
45.
46.
A key bottleneck in the profiling of lipids is the multistep derivatization required prior to gas chromatography (GC) analysis. A single in-vial lipid derivatization and analysis may significantly minimize sample loss and improve analytical sensitivity. A cotton fiber-supported poly(glycidylmethacrylate-co-ethylene glycol dimethacrylate) polymer microbrush microreactor loaded with Candida antarctica lipase B was developed for the facile conversion of triacylglycerols into fatty acid ethyl ester derivatives for gas chromatograph–mass spectrometry (GC–MS) analysis. The polymer microbrush microreactor was fabricated in effort to provide efficient, simplified, cost effective, and high-throughput GC–MS determination of triacylglycerols. The polymer microbrush microreactor was used as an in-vial triacylglycerol transesterification platform, with economical sample consumption of less than or equal to 100?µL and significant reduction of reagents. To evaluate the polymer microbrush microreactor performance for lipids, a triolein standard and camelina oil triacylglycerols were quantitatively transformed into ethyl oleate and fatty acid ethyl esters, respectively, following a 3?h reaction time. The lipase-loaded cotton fiber-supported poly(glycidylmethacrylate-co-ethylene glycol dimethacrylate) polymer microbrush microreactors were reusable for up to five times for quantitative transesterification with minimal loss of lipase activity. 相似文献
47.
Cobalt compounds supported on 2-, 3-, and 4-aminopyridine-modified silica surfaces, named Sil2Co, Sil3Co, and Sil4Co, respectively, were used to catalyze the decomposition of hydrogen peroxide on ethanolic solutions at 293, 298, and 303 K. The calculated k values (x10(-4) s(-1)) for Sil2Co, Sil3Co, and Sil4Co are 0.65, 1.24, and 4.78 (293 K); 1.23, 1.87, and 6.33 (298 K); and 1.80, 2.80, and 10.30 (303 K), respectively. All obtained results evidence that such decomposition is a first-order reaction. Zinc-, nickel-, and copper-supported compounds were also tested, but exhibited a very low catalytic activity. By using the k values at 298 and 303 K, and employing the equation ln (k1/k2) = E(a)/R(1/T2-1/T1), the activation energy values for the considered reaction were Sil2Co = 57.20, Sil3Co = 60.60, and Sil4Co = 73.10 kJ mol(-1), respectively. The low values calculated for E(a) are in agreement with a free-radical mechanism. 相似文献
48.
Direct square-wave voltammetry (SWV) and square-wave cathodic stripping voltammetry (SWCSV) at hanging mercury drop electrodes have been developed for determination of the psychoactive 1,4-benzodiazepine compounds clonazepam, bromazepam, midazolam, diazepam, medazepam, and flurazepam over a wide range of concentrations. Analysis was performed with better precision, lower detection limits, and much more rapidly than by previously reported voltammetric techniques.The applicability of both procedures is discussed. The methods were applied to the analysis of commercially available tablets with minimum sample manipulation. The accuracy of the results was accessed by comparison with those obtained by use of the methods described in official pharmacopoeias. A critical comparison with those procedures is also presented. 相似文献
49.
50.
C.E.T. Gonçalves da Silva 《Solid State Communications》1979,30(5):283-287
The magnetic properties of an intermediate valence compound are discussed within a single-ion framework. The effects of configuration mixing, crystalline electric fields, and external magnetic fields are included in the hamiltonian. The method incorporates in one single consistent approach both coherent (quantum) and incoherent (thermal) fluctuations. Numerical evaluation of the susceptibility and field dependent magnetization with parameters appropriate for TmSe yields results in good agreement with experiment. 相似文献