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排序方式: 共有218条查询结果,搜索用时 15 毫秒
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32.
Carina I. Jette Z. Jaron Tong Ryan G. Hadt Brian M. Stoltz 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(5):2049-2054
Herein, we report a Cu-catalyzed enantioselective allylic alkylation using a γ-butyrolactone-derived silyl ketene acetal. Critical to the development of this work was the identification of a novel mono-picolinamide ligand with the appropriate steric and electronic properties to afford the desired products in high yield (up to 96 %) and high ee (up to 95 %). Aryl, aliphatic, and unsubstituted allylic chlorides bearing a broad range of functionality are well-tolerated. Spectroscopic studies reveal that a CuI species is likely the active catalyst, and DFT calculations suggest ligand sterics play an important role in determining Cu coordination and thus catalyst geometry. 相似文献
33.
Absolute Configuration of Pharmaceutical Research Compounds Determined by X‐ray Powder Diffraction
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M. Sc. Carina Schlesinger M. Sc. Lukas Tapmeyer Dr. Silke D. Gumbert Dr. Dragica Prill Dr. Michael Bolte Prof. Dr. Martin U. Schmidt Dr. Christoph Saal 《Angewandte Chemie (International ed. in English)》2018,57(29):9150-9153
The absolute configuration of active pharmaceutical ingredients (APIs) was determined by generating salts of the active pharmaceutical ingredient (API) with counterions of known chirality, and determining the crystal structures by X‐ray powder diffraction. This approach avoids the (often tedious) growth of single crystals, and is successful with very limited quantities of material (less than 1 mg). The feasibility of the method is demonstrated on five examples, and its limitations are discussed as well. 相似文献
34.
Novel unsaturated ethers were synthesised in good yields starting from sucrose,using a two-step mild and efficient procedure based on the Gassman method, which consists in forming a vinyl group by the elimination of ethanol from mixed acetals with trimethylsilyl trifluoromethanesulfonate in the presence of alkyl amines. Mixed acetals are readily obtained from the corresponding alcohols and ethyl vinyl ether, using an acidic catalyst. Conventional etherification involving a primary halide was also examined. The monomers thus obtained were successfully polymerised by a free radical mechanism,yielding unbranched linear and soluble polymers with pending sucrose moieties, and some of their physical properties were determined. 相似文献
35.
Bäcktorp C Börje A Nilsson JL Karlberg AT Norrby PO Nyman G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(31):9549-9554
Pathways for formation of previously observed autoxidation products of ethoxylated surfactants have been studied by DFT (B3LYP). In addition to the established radical-chain reaction, several mechanistic possibilities for intramolecular fragmentation of the intermediate radicals have been characterized concerning reaction barriers and energies of transition states. The results can rationalize the formation of previously observed autoxidation products, including several, which have been implicated as strongly allergenic. 相似文献
36.
Keck GE Kraft MB Truong AP Li W Sanchez CC Kedei N Lewin NE Blumberg PM 《Journal of the American Chemical Society》2008,130(21):6660-6661
Highly potent bryostatin analogues which contain the complete bryostatin core structure have been synthesized using a pyran annulation approach as a key strategic element. The A ring pyran was assembled using a pyran annulation reaction between a C1-C8 hydroxy allylsilane and an aldehyde comprising C9-C13. This pyran was transformed to a new hydroxy allylsilane and then coupled with a preformed C ring aldehyde subunit in a second pyran annulation, with concomitant formation of the B ring. This tricyclic intermediate was elaborated to bryostatin analogues which displayed nanomolar to subnanomolar affinity for PKC, but displayed properties indistinguishable from a phorbol ester in a proliferation/attachment assay. 相似文献
37.
Sertchook H Elimelech H Makarov C Khalfin R Cohen Y Shuster M Babonneau F Avnir D 《Journal of the American Chemical Society》2007,129(1):98-108
Polyethylene (PE) and silica are perhaps the simplest and most common organic and inorganic polymers, respectively. We describe, for the first time, a physically interpenetrating nanocomposite between these two elementary polymers. While polymer-silica composites are well known, the nanometric physical blending of PE and silica has remained a challenge. A method for the preparation of such materials, which is based on the entrapment of dissolved PE in a polymerizing tetraethoxysilane (TEOS) system, has been developed. Specifically, the preparation of submicron particles of low-density PE@silica and high-density PE@silica is detailed, which is based on carrying out a silica sol-gel polycondensation process within emulsion droplets of TEOS dissolved PE, at elevated temperatures. The key to the successful preparation of this new composite has been the identification of a surfactant, PE-b-PEG, that is capable of stabilizing the emulsion and promoting the dissolution of the PE. A mechanism for the formation of the particles as well as their inner structure are proposed, based on a large battery of analyses, including transmission electron microscopy (TEM) and scanning electron microscopies (SEM), surface area and porosity analyses, various thermal analyses including thermal gravimetric analysis (TGA/DTA) and differential scanning calorimetry (DSC) measurements, small-angle X-ray scattering (SAXS) measurements and solid-state NMR spectroscopy. 相似文献
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39.
Effective Behavior Near Clogging in Upscaled Equations for Non-isothermal Reactive Porous Media Flow
For a non-isothermal reactive flow process, effective properties such as permeability and heat conductivity change as the underlying pore structure evolves. We investigate changes of the effective properties for a two-dimensional periodic porous medium as the grain geometry changes. We consider specific grain shapes and study the evolution by solving the cell problems numerically for an upscaled model derived in Bringedal et al. (Transp Porous Media 114(2):371–393, 2016. doi: 10.1007/s11242-015-0530-9). In particular, we focus on the limit behavior near clogging. The effective heat conductivities are compared to common porosity-weighted volume averaging approximations, and we find that geometric averages perform better than arithmetic and harmonic for isotropic media, while the optimal choice for anisotropic media depends on the degree and direction of the anisotropy. An approximate analytical expression is found to perform well for the isotropic effective heat conductivity. The permeability is compared to some commonly used approaches focusing on the limiting behavior near clogging, where a fitted power law is found to behave reasonably well. The resulting macroscale equations are tested on a case where the geochemical reactions cause pore clogging and a corresponding change in the flow and transport behavior at Darcy scale. As pores clog the flow paths shift away, while heat conduction increases in regions with lower porosity. 相似文献
40.
Carina Schönherr Sounia Touchene Gaston Wilser Regine Peschka-Süss Giancarlo Francese 《Journal of chromatography. A》2009,1216(5):781-786
In recent decades the use of liposomal preparations as drug delivery systems has become very attractive in pharmaceutical development. Therefore, thorough characterization and quantification of the lipids which form liposomes is wished from both investigators and regulatory authorities when the application in humans is being considered. In this study a new HPLC method for the detection of lipids in liposomal formulations was established using corona charged aerosol detection (CAD) which has the advantage to be independent of the chemical properties of the analytes. The superiority of this method over UV detection was demonstrated. Compared to UV detection no absorption effects of the organic solvent in the mobile phase interfering with the lipid signals were observed with CAD. CAD showed good linearity (R2 > 0.990) for all liposomal compounds. The acceptance criteria for precision including repeatability were met. The average recovery for each of the excipients of the liposomal formulation was in the range of 90.0–110%. 相似文献