全文获取类型
收费全文 | 13298篇 |
免费 | 2557篇 |
国内免费 | 2014篇 |
专业分类
化学 | 10229篇 |
晶体学 | 215篇 |
力学 | 697篇 |
综合类 | 174篇 |
数学 | 1392篇 |
物理学 | 5162篇 |
出版年
2024年 | 35篇 |
2023年 | 239篇 |
2022年 | 394篇 |
2021年 | 485篇 |
2020年 | 630篇 |
2019年 | 678篇 |
2018年 | 533篇 |
2017年 | 493篇 |
2016年 | 709篇 |
2015年 | 723篇 |
2014年 | 868篇 |
2013年 | 1053篇 |
2012年 | 1269篇 |
2011年 | 1252篇 |
2010年 | 939篇 |
2009年 | 855篇 |
2008年 | 938篇 |
2007年 | 896篇 |
2006年 | 748篇 |
2005年 | 622篇 |
2004年 | 483篇 |
2003年 | 388篇 |
2002年 | 467篇 |
2001年 | 417篇 |
2000年 | 254篇 |
1999年 | 323篇 |
1998年 | 215篇 |
1997年 | 163篇 |
1996年 | 148篇 |
1995年 | 106篇 |
1994年 | 105篇 |
1993年 | 91篇 |
1992年 | 72篇 |
1991年 | 61篇 |
1990年 | 58篇 |
1989年 | 39篇 |
1988年 | 28篇 |
1987年 | 24篇 |
1986年 | 15篇 |
1985年 | 9篇 |
1984年 | 11篇 |
1983年 | 13篇 |
1982年 | 4篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1975年 | 1篇 |
1959年 | 3篇 |
1936年 | 1篇 |
1909年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
131.
由于乙醇最有可能成为直接甲醇燃料电池(DMFC)的替代燃料,因此近年来。对乙醇的电化学氧化及直接乙醇燃料电池的研究已引起人们的很大兴趣。甲醇毒性较大并且易透过Nafion膜进入阴极造成阴极的混合电位而影响DMFC的阴极性能.这是制约DMFC走向实用化的主要问题之一。因此人们在致力于研究直接甲醇燃料电池的同时.也寻求其它的小分子醇作为甲醇的替代燃料。乙醇是除甲醇以外最简单的醇.它来源广泛.无毒,是可再生和环保型能源.并且也有较高的能量密度和反应活性。但是乙醇在电极上的完全氧化因涉及到C-C键的断裂要比甲醇困难.阳极反应动力学过程也比较缓慢。到目前为止铂基催化剂仍然是乙醇氧化最好的催化剂.虽然也有使用非铂催化剂研究乙醇的电氧化,但催化活性远不如铂基催化剂高。 相似文献
132.
133.
An efficient Pd‐catalyzed three‐component coupling reaction of allyl carboxylates, norbornenes and diboronates is described, which allows efficient assembly of C(sp3)—C(sp3) and C(sp3)—B bonds in a single process. Moreover, this approach shows advantages of good chemo‐ and regioselectivity, as well as good substrates suitability. 相似文献
134.
We report microscopic observations and a structural determination of actin granules self-assembled in concentrated solutions of actin filaments (F-actin). Optical microscopy shows reproducible formation of numerous and stable granules of densely packed F-actin of variable sizes on the order of 10 microm. These granules coexist with a uniform network of F-actin of a lower concentration. The microscopic segregation of F-actin into two distinct states is assisted by an actin cross-linking protein, alpha-actinin. The rapid on and off rates and temperature sensitivity of the alpha-actinin/F-actin interaction facilitate the formation of multi-micrometer-sized granules of well-defined shapes. Additional physical factors such as the excluded volume effect and the minimization of surface energy act in concert with the specific molecular interactions to define the intriguing granular formation. Both the biochemical specificity of alpha-actinin and the thermodynamics of phase transitions are required for understanding such large scale self-assembly. 相似文献
135.
The adsorptive and electrochemical behaviors of medecamycin were investigated on a glassy carbon electrode (GCE) pretreated by anodic oxidation at +1.8 V for 5 min in 0.025 mol l–1 NH3-NH4Cl (pH 8.6) solution. An adsorptive stripping voltammetric method for the determination of medecamycin at the pretreated glassy carbon electrode has been developed. Medecamycin was accumulated in NH3-NH4Cl buffer (pH 9.0) at a potential of –0.7 V (vs. saturated calomel electrode (SCE)) for a certain time, and then determined by second-order differential anodic stripping voltammetry. The second-order differential anodic stripping peak current at +0.72 V was proportional to the concentration of medecamycin in the range 2.0 g ml–1 to 50.0 g ml–1. The detection limit (three times the signal-to-noise) was 1.0 g ml–1 and the relative standard deviation of the results was 3.28% for eight successive determinations of 10.0 g ml–1 medecamycin. This method has been applied to the direct determination of medecamycin in commercial tablets and spiked urine samples with satisfactory results. 相似文献
136.
Fan Caiyun Jia Hongmei Deuther-Conrad Winnie Brust Peter Steinbach J?rg Liu Boli 《中国科学B辑(英文版)》2006,49(2):169-176
A novel 99mTc labeled complex, [N-[2-((2-oxo-2-(4-(3-phenylpropyl)piperazin-1-yl)ethyl) (2-mercaptoethyl)amino)acetyl]-2-aminoethanethiolato]Technetium(V)
oxide (PPPE-MAMA’-99mTcO) ([
99m
Tc]-2) has been designed and prepared based on the integrated approach. The corresponding rhenium complex (PPPE-MAMA’-ReO)(Re-2) has been prepared and characterized. In vitro competition binding assays show moderate affinity of Re-2 towards σ1 and σ2 receptors with K
i values of 8.67 ± 0.07 and 5.71 ± 1.88 μmol, respectively. Planar images obtained at 0.5 h, 4 h, 20 h after i.v. injection
indicate the accumulation of [
99m
Tc]-2 in MCF-7 human breast tumor bearing mice at 20 h. Furthermore, the accumulation of [
99m
Tc]-2 has been inhibited at 20 h after co-injection of [
99m
Tc]-2 plus haloperidol (1 mg/kg). Biodistribution studies of [
99m
Tc]-2 display an in vivo tumor uptake of 0.14% ± 0.01% ID/g at 24 h post i.v. injection with a tumor/muscle ratio of 6.02 ± 0.87. The above results
suggest that [
99m
Tc]-2, derived from a previously published lead compound, retains certain tumor uptake and affinity for σ receptors. [
99m
Tc]-2 may be used as a basis for further structural modifications to develop tumor imaging agents with high affinity for σ receptors. 相似文献
137.
138.
A nickel catalyst was nodeled with ligand L^2,[NH=CH-CH=CH-0]^-,which should have potential use as a syndiotactic plyolefin catalyst,and the reaction mechanism was studied by theoretical calculations using the density functinal method at the B3LYP/LANL2MB level.The mechanism involves the formation of the intermediate [NiL^2Me]^ ,in which the metal occupies a T-shaped geometry.This intermediate has two possible structures with the methyl group trans either to the oxygen or to the nitrogen atom of L^2.The results show that both structures can lead to the desired product via similar reaction paths,A and B.Thus,the polymerization could be considered as taking place either with the alkyl group occupying the position trans to the Ni-0 or trans to the Ni-N bond in the catalyst.The polymerization process thus favors the catalysis of syndiotactic polyolefins.The syndiotactic synthesis effects could also be enhanced by varations in the ligand substituents.From energy considerations,we can conclude that it is more favorable for the methyl ttrans-O position to form a complex than to occupy the trans-N position.From bond length considerations,it is also more favoured for ethene to occupy the trans-O position than to occupy the trans-N position. 相似文献
139.
A simple, sensitive and selective method has been developed for the determination of protein using resonance light scattering (RLS) technique. The method is based on the interaction of protein and arsenazo-DBC-Al(3+) in the pH range of 5.0-7.0, which causes a substantial enhancement of the resonance scattering signal of arsenazo-DBC-Al(3+) in the wavelength range of 300-550 nm with the maximum RLS platform at 405-420 nm. With this method, 2.50-50.00 mug ml(-1) of bovine serum albumin (BSA) and 2.50-60.00 mug ml(-1) of human serum albumin (HSA) can be determined, and the detection limits, calculated three times the standard deviation (S.D.) of six blank measurements, for BSA and HSA were 123.4 and 89.6 ng ml(-1), respectively. Moreover, the method is free from interference from many amino acids and metal ions. The method, with high sensitivity, selectivity and reproducibility, was satisfactorily applied to the determination of total protein in human serum samples. Mechanism studies indicated that arsenazo-DBC-Al(3+) could bind to BSA depending mainly on electrostatic forces, which results in enhanced RLS in the arsenazo-DBC-Al(3+)-protein system. 相似文献
140.
An easily prepared and highly efficient monodentate phosphoramidite ligand derived from BINOL, (S)-2,2'-O,O-(1,1'-binaphthyl)-dioxo-N,N-diethylphospholidine, was examined in the hydrogenation of both enamides and alpha-dehydroamino acid derivatives. The catalyst provided remarkably high enantioselectivities (up to 99.6% ee for enamides and >99.9% ee for alpha-dehydroamino acid derivatives). 相似文献