全文获取类型
收费全文 | 12074篇 |
免费 | 154篇 |
国内免费 | 66篇 |
专业分类
化学 | 5303篇 |
晶体学 | 21篇 |
力学 | 695篇 |
综合类 | 5篇 |
数学 | 4025篇 |
物理学 | 2245篇 |
出版年
2024年 | 78篇 |
2023年 | 687篇 |
2022年 | 423篇 |
2021年 | 425篇 |
2020年 | 1471篇 |
2019年 | 1085篇 |
2018年 | 939篇 |
2017年 | 764篇 |
2016年 | 761篇 |
2015年 | 595篇 |
2014年 | 763篇 |
2013年 | 2887篇 |
2012年 | 530篇 |
2011年 | 69篇 |
2010年 | 70篇 |
2009年 | 69篇 |
2008年 | 84篇 |
2007年 | 76篇 |
2006年 | 57篇 |
2005年 | 112篇 |
2004年 | 101篇 |
2003年 | 58篇 |
2002年 | 33篇 |
2001年 | 29篇 |
2000年 | 17篇 |
1999年 | 16篇 |
1998年 | 18篇 |
1997年 | 7篇 |
1996年 | 9篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1989年 | 1篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 10篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1978年 | 6篇 |
1977年 | 6篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 3篇 |
1973年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
51.
52.
《Chemphyschem》2006,7(9):1980-1984
The photophysical properties of three dendrimers containing a p‐terphenyl core with appended sulfonimide branches of different size and n‐octyl chains have been investigated in dichloromethane solution. In the dendrimer absorption spectra contributions from both the branches and the core are clearly identified. The fluorescence spectra show only the characteristic fluorescence of the terphenyl unit. Energy transfer from the appended chromophoric groups to the core does not occur. In the dendrimers, the terphenyl core exhibits a very high fluorescence quantum yield (ca. 0.75) and a short emission lifetime (0.8 ns). These properties allowed investigations of the fluorescence depolarization caused by rotation of the dendrimers. The dendrimers show a very high steady‐state anisotropy in dichloromethane solution at room temperature (0.24 for the largest one), compared to that of the parent terphenyl under the same experimental conditions (<0.01) and in rigid matrix (0.33). Both the n‐octyl chains and the sulfonimide branches play important roles to slow down the molecular rotation. 相似文献
53.
A new reaction of organolithium compounds with phosphonium salts is described; reaction of t-butyllithium with dibenzylaminophosphonium or tetraphenylphosphonium bromides takes place through addition of the t-butyl group on a benzene ring at the position para to the phosphorus atom, the ylid formed reacts in a characteristic Wittig reaction with p-tolylaldehyde. 相似文献
54.
Allyloxy bisbenzo 16-crown-5 trimethoxysilane was first used as precursor to prepare the sol-gel-derived bisbenzo crown ether/hydroxyl-terminated silicone oil (OH-TSO) SPME coating. The coating procedure involving sol solution composition and conditioning process was presented. Compared with commercial SPME stationary phases, the new coatings showed higher extraction efficiency and therefore could provide higher sensitivity for organphosphorous pesticides (OPs). Limits of detection (LODs) were in the range of 0.003-1.0 ng/g for these OPs in food samples (honey, juice, orange and pakchoi). The optimal extraction conditions of the new coatings to OPs in these samples were investigated by adjusting extraction time, salt addition, extraction temperature, and dilution ratios of samples with distilled water by using SPME coupled with gas chromatography (GC)-flame photometric detection (FPD). The method was applied to determine the concentrations of OPs in real samples. 相似文献
55.
《Arabian Journal of Chemistry》2020,13(5):5277-5283
The new title two-dimensional hetero-tetra nuclear Cu3–Na coordination polymer {[NaCu3Cl(cpiap)2(H2O)3]n·6nH2O} (1) consists of crystallographically two-independent copper(II) centers, each bridged by a sodium cation through carboxylate-oxygen of the deprotonated H3cpiap ligand (H3cpiap = 2-(carboxyphenyl)iminoaceticpropanoic acid) to CuII (2) and CuII (2−) cations, and through water molecules to CuII (1) cation. CuII (2) and CuII (1) cations are bridged by carboxylate-oxygen atoms of the ligand in a syn-anti mode which, alternate regularly within the chain being bridged by a tetra coordinated sodium cation. Each CuII (2) and CuII (2−) cation in (1) is in an octahedral environment formed by four carboxylate-oxygens from two cpiap3− ligands, one nitrogen atom and a bridging chloride atom. CuII (1) cation is in a square pyramidal environment formed by three water molecules and two carboxylate-oxygens from two cpiap3− ligands. The ligand acts simultaneously as monodentate and tridentate toward CuII (1) and CuII (2) cations respectively. The lattice water molecules involved in OH···O hydrogen bonding are situated in the void spaces between layers. The zigzag chains, which run along the b-axes further construct three-dimensional metal-organic framework via hydrogen bonding and weak face-to-face π-π interactions. Weak CH···O interactions are also present. 相似文献
56.
57.
58.
Cu(phen)2+2和Cu(bpy)2+2与6-巯基嘌呤、腺嘌呤相互作用的研究 总被引:9,自引:0,他引:9
在pH为7.0的磷酸盐缓冲溶液中,用荧光光谱、紫外光谱、电化学及紫外光谱电化学等方法研究了铜配合物与6-巯基嘌呤、腺嘌呤的相互作用.结果表明,Cu(phen)2+2和Cu(bpy)2+2与6-巯基嘌呤、腺嘌呤发生了相互作用,但作用程度不同.根据荧光光谱实验数据计算出Cu(phen)2+2和Cu(bpy)2+2与6-巯基嘌呤、腺嘌呤的配位比均为1∶1;它们与6-巯基嘌呤作用的配位常数分别为2.23×104L/mol和6.11×104L/mol;与腺嘌呤作用的配位常数分别为1.95×104L/mol和5.12×104L/mol.电化学实验也获得了相近的结果.这为解释Cu(phen)2+2和Cu(bpy)2+2与DNA的作用机理及作用部位提供了有益的信息 相似文献
59.
A novel methodology in on-line pyrolysis-gas chromatography (Py-GC) for the fast analysis of fatty acids in vegetable oils with minimal sample treatment and the use of non-toxic reagents is described. Pyrolysis at 500 degrees C for 10 s of sub-microgram quantity of vegetable oil dissolved in dimethyl carbonate (DMC) and in the presence of nanopowder titanium silicon oxide resulted in the production of fatty acid methyl esters (FAMEs) as unique products. Pyrolysis performed by means of a resistively heated filament pyrolyser interfaced to a GC-MS apparatus enabled the direct analysis of evolved FAMEs. The DMC/Py-GC-MS analysis was tested on soybean, coconut, linseed, walnut and olive oil and the results compared to the classical BF(3)-methanol as reference methodology. The DMC method exhibited a lower precision and was biased towards lower levels of polyunsaturated fatty acids (PUFA) in comparison to the BF(3)-methanol method, but was more advantageous in terms of reduced sample treatment, waste generation and risk factors of employed chemicals. 相似文献
60.
A novel hybrid optimization method called quantum stochastic tunneling has been recently introduced. Here, we report its implementation within a new docking program called EasyDock and a validation with the CCDC/Astex data set of ligand-protein complexes using the PLP score to represent the ligand-protein potential energy surface and ScreenScore to score the ligand-protein binding energies. When taking the top energy-ranked ligand binding mode pose, we were able to predict the correct crystallographic ligand binding mode in up to 75% of the cases. By using this novel optimization method run times for typical docking simulations are significantly shortened. 相似文献