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991.
Since their introduction in 1992 by Fréchet and Svec[1], monolithic supports as stationary phases in high performance liquid chromatography (HPLC) and capillary electrochromatography (CEC) have gained significant interest due to a number of unique properties. Their ease of preparation, high reproducibility, versatile surface chemistry and fast mass transport are advantageous in a variety of applications[2-4]. Separations in diverse chromatographic modes have been performed in either HPLC or CEC, showing their strong point for high-speed separations of biological and synthetic molecules[5-12]. Although a number of papers have been reported on the application of monolithic supports as chiral stationary phases in CEC and pressure-assisted capillary electrochromatography (p-CEC)[13-19], few reports have so far been published on chiral monolithic stationary phases for liquid chromatography[20]. 相似文献
992.
993.
994.
Hi Taing Jacob G. Rothera Justin F. Binder Charles L. B. Macdonald 《Liquid crystals》2018,45(8):1147-1154
Conformationally flexible cores that generate large free volume when stacked and have an insufficient number of side-chains for filling the lateral space around each core have been proposed as design criteria for discotic liquid crystals that display nematic rather than columnar mesophases. Presented here are 1,3,5-triazines substituted with three thiophene carboxylate ester groups that fulfil these design criteria. Nine derivatives with linear, branched, and chiral ester chains were synthesised and their mesomorphism was studied by polarised optical microscopy, differential scanning calorimetry, and powder x-ray diffraction. Triazines with linear propyl to octyl chains display monotropic nematic discotic mesophases that crystallise within hours or days or when mechanically agitated. Packing structures for the nematic phases are proposed based on the single crystal structure of the ethyl ester. Their unusually slow nucleation and crystal growth can be attributed to the large number of possible low energy conformations that arise from the conformationally flexible core. Incorporation of racemic and chiral branched chains expectedly lowers the melting points of these derivatives but, unexpectedly, enhances nucleation and crystal growth well above the temperature ranges of their hypothetical nematic phases. Chiral nematic discotic mesophases were obtained for binary mixtures of derivatives with chiral branched and linear chains. 相似文献
995.
996.
过渡金属催化卡宾对O-H键的不对称插入反应是合成手性醇及其衍生物的直接方法.近年来,人们发展了多种手性催化剂实现了重氮酯衍生的金属卡宾对醇、酚、羧酸甚至水的O-H键的高对映选择性插入反应,但是重氮酮作为卡宾前体的不对称O-H键插入反应鲜有成功的例子.以非手性双铑络合物和手性螺环磷酸组成的协同催化体系,首次实现了α-重氮酮对醇的O-H键的不对称插入反应,获得了较高的收率和高达95%ee的对映选择性.反应为手性α-烷氧基酮这类重要手性化合物提供了高效的合成方法.还通过密度泛函理论计算,对反应机理进行了初步研究,发现水很可能参与了手性磷酸促进的烯醇中间体质子转移过程. 相似文献
997.
Mizuho Sugiuchi Dr. Yukatsu Shichibu Prof. Katsuaki Konishi 《Angewandte Chemie (International ed. in English)》2018,57(26):7855-7859
2,3‐bis(diphenylphosphino)butane enantiomers (chiraphos, L) used as chiral auxiliaries results in the preferential formation of an unprecedented Au24 framework with inherent chirality. The crystal structure of [Au24L6Cl4]2+ ( 1 ) has a square antiprism‐like octagold core twinned by two helicene‐like hexagold motifs, where the inherent chirality is associated with the helical arrangement. The clusters carrying (R,R)‐ and (S,S)‐ diphosphines had right‐ and left‐handed strands, respectively. Circular dichroism spectra showed peaks in the visible to near‐IR region, some of which did not coincide with absorption bands, suggesting the enantiomeric Au24 frameworks possess unique chiroptical properties. The Au24 frameworks were thermally robust, which could be attributed to the superatomic concept (18 e? system) and the steric constraint effects of the bridging ligand units. 相似文献
998.
Vladimír Nosek Dr. Jiří Míšek 《Angewandte Chemie (International ed. in English)》2018,57(31):9849-9852
The highly enantioselective enzyme methionine sulfoxide reductase A was combined with an oxaziridine‐type oxidant in a biphasic setup for the deracemization of chiral sulfoxides. Remarkably, high ee values were observed with a wide range of substrates, thus providing a practical route for the synthesis of enantiomerically pure sulfoxides. 相似文献
999.
Enantio‐ and Diastereoselective Synthesis of Chiral Allenes by Palladium‐Catalyzed Asymmetric [3+2] Cycloaddition Reactions
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Prof. Dr. Barry M. Trost Dr. Daniel Zell Dr. Christoph Hohn Dr. Guillaume Mata Autumn Maruniak 《Angewandte Chemie (International ed. in English)》2018,57(39):12916-12920
A protocol for the asymmetric synthesis of highly substituted chiral allenes with control of point and axial chirality has been developed. A palladium‐catalyzed [3+2] cycloaddition using readily available racemic allenes gives access to densely functionalized chiral allenes with excellent yields and functional group tolerance. The catalytic asymmetric protocol utilizes a broad range of allenyl TMM (trimethylenemethane) donors to form cyclopentanes, pyrrolidines, and spirocycles with very good control of regio‐, enantio‐, and diastereoselectivity. The chiral allene moiety is shown to be a valuable functional group for rapid elaboration towards complex targets. 相似文献
1000.
《Journal of mass spectrometry : JMS》2018,53(8):693-699
In this work, the use of MALDI traveling wave ion mobility spectrometry‐mass spectrometry (MALDI‐TWIMS‐MS) for stereoselective structural analysis of direct cleavage and identification of 2‐substituted piperidines obtained through solid‐phase asymmetric synthesis by using heterogeneous 8‐phenylmenthyl‐based chiral auxiliary resins. A strategy for gas‐phase chiral and structural characterization of small molecular weight molecules by using MALDI‐IMS‐MS technique is discussed. Because both MALDI and IMS do not directly offer chiral resolution, an easy methodology by adding a chiral phase is described to carry out in situ online ion/molecule complexation with different chiral analytes inside the mass spectrometer. Piperidine enantiomers were resolved, and separation obtained shows dependence of surface areas. To corroborate this assumption and elucidate the separation mechanism to accomplish an analytical technique by which fast determination of the chirality of molecules may be determined for a wide range organic compound applications, it was performed DFT calculations to determine the cross‐sectional areas of proton‐bound dimer complexes. Drift times are affected by cross‐sectional areas, correlating bigger times with bigger molecular volumes during the ion mobility experiments of proton‐bound dimer complexes. 相似文献