全文获取类型
收费全文 | 1279篇 |
免费 | 43篇 |
国内免费 | 13篇 |
专业分类
化学 | 948篇 |
晶体学 | 5篇 |
力学 | 37篇 |
数学 | 133篇 |
物理学 | 212篇 |
出版年
2023年 | 12篇 |
2022年 | 6篇 |
2021年 | 8篇 |
2020年 | 24篇 |
2019年 | 19篇 |
2018年 | 16篇 |
2017年 | 9篇 |
2016年 | 43篇 |
2015年 | 28篇 |
2014年 | 24篇 |
2013年 | 43篇 |
2012年 | 65篇 |
2011年 | 92篇 |
2010年 | 50篇 |
2009年 | 38篇 |
2008年 | 76篇 |
2007年 | 73篇 |
2006年 | 76篇 |
2005年 | 73篇 |
2004年 | 54篇 |
2003年 | 54篇 |
2002年 | 37篇 |
2001年 | 18篇 |
2000年 | 16篇 |
1999年 | 9篇 |
1998年 | 10篇 |
1997年 | 9篇 |
1996年 | 24篇 |
1995年 | 16篇 |
1994年 | 20篇 |
1993年 | 13篇 |
1992年 | 19篇 |
1990年 | 12篇 |
1988年 | 11篇 |
1987年 | 13篇 |
1986年 | 6篇 |
1985年 | 16篇 |
1984年 | 11篇 |
1983年 | 12篇 |
1982年 | 11篇 |
1981年 | 8篇 |
1980年 | 12篇 |
1979年 | 8篇 |
1978年 | 8篇 |
1977年 | 10篇 |
1976年 | 13篇 |
1975年 | 10篇 |
1974年 | 14篇 |
1973年 | 7篇 |
1876年 | 7篇 |
排序方式: 共有1335条查询结果,搜索用时 78 毫秒
71.
72.
Rob. J. M. Hermans Henk M. Buck 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):255-265
Abstract An 1H NMR study of the conformation of the dioxaphosphorinane ring of a number of diastereoisomeric bicyclic saturated six-membered ring phosphites (3ab-10ab) has been performed. The dioxaphosphorinane ring of these phosphites is transannelated with a tetrahydrofuran, cyclopen-tane, tetrahydropyran or cyclohexane ring. The substituent on the phosphorus atom is a methoxy or phenoxy group. It is shown that the cis isomers 3a-10a prefer a chair conformation of the dioxaphosphorinane ring, independent of the substituent on the phosphorus atom and of the nature of the transannelated ring. In contrast, for the trans isomers 3b-10b a twist rather than a chair conformation of the dioxaphosphorinane ring is preferred. The fraction of the twist conformer in the trans isomers is mainly determined by the substituent on phosphorus. The size and composition of the transannelated ring are relatively unimportant in this respect. For both cis and trans isomers the preferred geometry is solvent-independent. The measured 3JPOCH couplings of the cis isomers 3a-10a are used to formulate an expression for the dependence of such couplings upon dihedral angles in bicyclic phosphites. 相似文献
73.
74.
Analyte–wall interaction is a significant problem in capillary electrophoresis (CE) as it may compromise separation efficiencies and migration time repeatability. In CE, self-assembled polyelectrolyte multilayer films of Polybrene (PB) and dextran sulfate (DS) or poly(vinylsulfonic acid) (PVS) have been used to coat the capillary inner wall and thereby prevent analyte adsorption. In this study, atomic force microscopy (AFM) was employed to investigate the layer thickness and surface morphology of monolayer (PB), bilayer, (PB-DS and PB-PVS), and trilayer (PB-DS-PB and PB-PVS-PB) coatings on glass surfaces. AFM nanoshaving experiments providing height distributions demonstrated that the coating procedures led to average layer thicknesses between 1 nm (PB) and 5 nm (PB-DS-PB), suggesting the individual polyelectrolytes adhere flat on the silica surface. Investigation of the surface morphology of the different coatings by AFM revealed that the PB coating does not completely cover the silica surface, whereas full coverage was observed for the trilayer coatings. The DS-containing coatings appeared on average 1 nm thicker than the corresponding PVS-containing coatings, which could be attributed to the molecular structure of the anionic polymers applied. Upon exposure to the basic protein cytochrome c, AFM measurements showed an increase of the layer thickness for bare (3.1 nm) and PB-DS-coated (4.6 nm) silica, indicating substantial protein adsorption. In contrast, a very small or no increase of the layer thickness was observed for the PB and PB-DS-PB coatings, demonstrating their effectiveness against protein adsorption. The AFM results are consistent with earlier obtained CE data obtained for proteins using the same polyelectrolyte coatings. 相似文献
75.
Rianne A.G. Harmsen Nourdin Ghalit Johan Kemmink Eefjan Breukink Rob M.J. Liskamp Dirk T.S. Rijkers 《Tetrahedron》2014
The bacteria-specific membrane component lipid II is essential for bacterial cell wall synthesis. A tricyclic nisin mimic was designed and synthesized in which both thioether moieties were mimicked by an alkane-bridge, as well as the introduction of a third conformational constraint consisting of a macrocyclic lactam-bridge between the N-terminus and the B-ring. The newly designed tricyclic AB-ring mimic was found to bind lipid II since it was able to inhibit nisin-induced membrane leakage in a dose-dependent manner. These results imply that the tricyclic AB-ring mimic may form a novel class of lead structures for the development of nisin-based peptide antibiotics. 相似文献
76.
Donglin He Chengxi Zhao Dr. Linjiang Chen Dr. Marc A. Little Dr. Samantha Y. Chong Rob Clowes Katherine McKie Mark G. Roper Graeme M. Day Dr. Ming Liu Prof. Andrew I. Cooper 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(41):10589-10594
Ethyl acetate is an important chemical raw material and solvent. It is also a key volatile organic compound in the brewing industry and a marker for lung cancer. Materials that are highly selective toward ethyl acetate are needed for its separation and detection. Here, we report a trianglimine macrocycle ( TAMC ) that selectively adsorbs ethyl acetate by forming a solvate. Crystal structure prediction showed this to be the lowest energy solvate structure available. This solvate leaves a metastable, “templated” cavity after solvent removal. Adsorption and breakthrough experiments confirmed that TAMC has adequate adsorption kinetics to separate ethyl acetate from azeotropic mixtures with ethanol, which is a challenging and energy-intensive industrial separation. 相似文献
77.
Palladium‐Catalyzed Synthesis of Ammonium Sulfinates from Aryl Halides and a Sulfur Dioxide Surrogate: A Gas‐ and Reductant‐Free Process 下载免费PDF全文
Edward J. Emmett Dr. Barry R. Hayter Prof. Michael C. Willis 《Angewandte Chemie (International ed. in English)》2014,53(38):10204-10208
Sulfonyl‐derived functional groups populate a broad range of useful molecules and materials, and despite a variety of preparative methods being available, processes which introduce the most basic sulfonyl building block, sulfur dioxide, using catalytic methods, are rare. Described herein is a simple reaction system consisting of the sulfur dioxide surrogate DABSO, triethylamine, and a palladium(0) catalyst for effective convertion of a broad range of aryl and heteroaryl halides into the corresponding ammonium sulfinates. Key features of this gas‐ and reductant‐free reaction include the low loadings of palladium (1 mol %) and ligand (1.5 mol %) which can be employed, and the use of isopropyl alcohol as both a solvent and formal reductant. The ammonium sulfinate products are converted in situ into a variety of sulfonyl‐containing functional groups, including sulfones, sulfonyl chlorides, and sulfonamides. 相似文献
78.
Effect of Protic Ionic Liquid and Surfactant Structure on Partitioning of Polyoxyethylene Non‐ionic Surfactants 下载免费PDF全文
Inga L. Topolnicki Dr. Paul A. FitzGerald Prof. Rob Atkin Prof. Gregory G. Warr 《Chemphyschem》2014,15(12):2485-2489
The partitioning constants and Gibbs free energies of transfer of poly(oxyethylene) n‐alkyl ethers between dodecane and the protic ionic liquids (ILs) ethylammonium nitrate (EAN) and propylammonium nitrate (PAN) are determined. EAN and PAN have a sponge‐like nanostructure that consists of interpenetrating charged and apolar domains. This study reveals that the ILs solvate the hydrophobic and hydrophilic parts of the amphiphiles differently. The ethoxy groups are dissolved in the polar region of both ILs by means of hydrogen bonds. The environment is remarkably water‐like and, as in water, the solubility of the ethoxy groups in EAN decreases on warming, which underscores the critical role of the IL hydrogen‐bond network for solubility. In contrast, amphiphile alkyl chains are not preferentially solvated by the charged or uncharged regions of the ILs. Rather, they experience an average IL composition and, as a result, partitioning from dodecane into the IL increases as the cation alkyl chain is lengthened from ethyl to propyl, because the IL apolar volume fraction increases. Together, these results show that surfactant dissolution in ILs is related to structural compatibility between the head or tail group and the IL nanostructure. Thus, these partitioning studies reveal parameters for the effective molecular design of surfactants in ILs. 相似文献
79.
Ritashree Pal Sean C. O'Brien Prof. Michael C. Willis 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(51):11710-11714
We show that readily available α-amidoaldehydes are effective substrates for intermolecular Rh-catalyzed alkyne hydroacylation reactions. The catalyst [Rh(dppe)(C6H5F)][BArF4] provides good reactivity, and allows a broad range of aldehydes and alkynes to be used as substrates, delivering α-amidoketone products. High yields and high levels of regioselectivity are achieved. The use of α-amidoaldehydes as substrates establishes that 1,4-dicarbonyl motifs can be used as controlling groups in Rh-catalyzed hydroacylation reactions. 相似文献
80.
Benjamin D. Egleston Konstantin V. Luzyanin Michael C. Brand Rob Clowes Michael E. Briggs Rebecca L. Greenaway Andrew I. Cooper 《Angewandte Chemie (International ed. in English)》2020,59(19):7362-7366
Control of pore window size is the standard approach for tuning gas selectivity in porous solids. Here, we present the first example where this is translated into a molecular porous liquid formed from organic cage molecules. Reduction of the cage window size by chemical synthesis switches the selectivity from Xe‐selective to CH4‐selective, which is understood using 129Xe, 1H, and pulsed‐field gradient NMR spectroscopy. 相似文献