全文获取类型
收费全文 | 65545篇 |
免费 | 9634篇 |
国内免费 | 7304篇 |
专业分类
化学 | 45577篇 |
晶体学 | 860篇 |
力学 | 3845篇 |
综合类 | 515篇 |
数学 | 7893篇 |
物理学 | 23793篇 |
出版年
2024年 | 207篇 |
2023年 | 1181篇 |
2022年 | 2018篇 |
2021年 | 2165篇 |
2020年 | 2317篇 |
2019年 | 2239篇 |
2018年 | 1983篇 |
2017年 | 1891篇 |
2016年 | 2813篇 |
2015年 | 2826篇 |
2014年 | 3409篇 |
2013年 | 4514篇 |
2012年 | 5401篇 |
2011年 | 5718篇 |
2010年 | 3969篇 |
2009年 | 3911篇 |
2008年 | 4299篇 |
2007年 | 3883篇 |
2006年 | 3614篇 |
2005年 | 2965篇 |
2004年 | 2362篇 |
2003年 | 1977篇 |
2002年 | 1875篇 |
2001年 | 1548篇 |
2000年 | 1454篇 |
1999年 | 1366篇 |
1998年 | 1192篇 |
1997年 | 1092篇 |
1996年 | 1134篇 |
1995年 | 982篇 |
1994年 | 884篇 |
1993年 | 754篇 |
1992年 | 731篇 |
1991年 | 597篇 |
1990年 | 519篇 |
1989年 | 426篇 |
1988年 | 359篇 |
1987年 | 299篇 |
1986年 | 291篇 |
1985年 | 300篇 |
1984年 | 204篇 |
1983年 | 133篇 |
1982年 | 129篇 |
1981年 | 88篇 |
1980年 | 67篇 |
1979年 | 68篇 |
1978年 | 40篇 |
1976年 | 37篇 |
1974年 | 40篇 |
1973年 | 45篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
141.
Xu X Zhao J Jiang D Kong J Liu B Deng J 《Analytical and bioanalytical chemistry》2002,374(7-8):1261-1266
A novel hydrogen peroxide biosensor was developed based on the immobilization of horseradish peroxidase (HRP) in a TiO(2) sol-gel matrix on an electropolymerized phenazine methosulfate (PMS) modified electrode surface. Such membranes are of interest due to their high surface area, biological compatibility, and ease of fabrication. HRP entrapped in the TiO(2) matix was stable and retained its activity to a large extent. Cyclic voltammetry and amperometric measurements were employed to demonstrate the feasibility of electron transfer between immobilized HRP and the glassy carbon electrode via electropolymerized PMS. The influence of various experimental parameters such as operating potential, pH, temperature, and stability was investigated for optimum analytical performance. The biosensor provided a wide linear calibration range from 4.0x10(-6) M to 1.0x10(-3) M, with a detection limit of 8.0x10(-7) M at a signal-to-noise ratio of 3. The sensor retained 80% of its original activity after two months of operation. 相似文献
142.
The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence. 相似文献
143.
O. de la Iglesia M. Pedernera R. Mallada Z. Lin J. Rocha J. Coronas J. Santamaría 《Journal of membrane science》2006,280(1-2):867-875
MCM-48 membranes have been prepared on alumina supports of different pore sizes. A battery of characterization techniques has been used to study the physical properties and the quality of the membranes prepared. The highest quality membranes were prepared on supports with pore size of up to 60 nm. The MCM-48 membranes were tested in the separation of gas phase mixtures and a cyclohexane/O2 selectivity higher than 270 was obtained. The selective separation of organic compounds from inert components is a result of the cooperative effects of capillary condensation in MCM-48 pores and of the specific interactions of the permeating compounds and the membrane material. 相似文献
144.
To explore the properties of cyclodextrins (CDs) as an optical sensing phase, the behavior of immobilized CD in interaction with analytes was studied in this work. CDs having different cavity sizes were immobilized onto the surface of infrared (IR) internal reflection-sensing element (IRE) to kinetically monitor the behavior of CD in interaction with analytes. Several aromatic compounds having various molecular sizes and functional groups were used to characterize the interaction mechanism. A two-layer modification method was proposed in this work, which utilized a thin hydrophobic film (polyvinyl benzyl chloride) to stick on the IRE and to covalently bond to the CDs through an ethylene diamine linker. The synthesized CD phases exhibited high stability in aqueous solution. To analyze the behavior during the formation of complexes between the guest molecules and the CD phases, we modeled the interaction behavior and treated the kinetic data with the theoretical equations developed in this work. The results indicate that the behavior of the interaction between guest molecules and CDs was explained by considering the formation of two types of complexes: adsorbed complexes and inclusion complexes. The formation of the inclusion complexes was relatively fast, the time required to reach equilibrium could be shorter than a few minutes. The adsorbed complexes were also observed, but their rate of formation was relatively slow; equilibrium could be reached at times greater than 60 min. Based on the signals observed under equilibrium conditions, the concentration of inclusion complexes was approximately three times than that of the adsorbed complexes. 相似文献
145.
Xiao Wen Hu Zhi Min Zheng Cai Hong Xu 《中国化学快报》2007,18(11):1351-1352
Three new 1,3-bis(phenylethynyl)disilazanes were synthesized from the reaction of 1,3-dichlorodisilazanes with (phenylethy- nyl)lithium,and characterized by infrared (IR) spectra,nuclear magnetic resonance (NMR) and mass spectrometry (MS). 相似文献
146.
LiLi Liu WanHong Ma WenJing Song ChunCheng Chen Jun Lin JinCai Zhao XinHua Qian ShiBo Zhang 《中国科学:化学(英文版)》2007,50(6):770-775
This study investigated the visible-light catalysis mediated by zeolite NaY on the oxidation of dyes with H2O2. The results demonstrated that zeolite NaY acts as a sink for the electron from the photo-excited dye in the heterogeneous catalysis. Furthermore, the electron can effectively activate H2O2 to produce ·OH radical that is a powerful oxidant for the oxidation of dye at room temperature. The effects of the framework topology, Si/Al ratio, and exchangeable cation of the zeolite on the oxidation of various dyes were also shown. 相似文献
147.
148.
Protein-ligand interactions may lead to the formation of multiple molecular complexes in dynamic exchange, affecting the kinetic and thermodynamic characteristics of the binding equilibrium. We followed the dissociation kinetics of the transient and specific complex of an antithrombotic peptide N-acetyl-Asp(55)-Phe-Glu-Glu-Ile-Pro(60)-Glu-Glu-Tyr-Leu-Gln(65) with human prothrombin by use of (15)N NMR relaxation dispersion spectroscopy of the peptide. Every one of the five (15)N-labeled adjacent residues of the peptide exhibited apparently different kinetic exchange and relaxation behaviors, which were especially evident at different concentrations of prothrombin. Binding-induced (15)N relaxation dispersion of residues Phe(56), Glu(57), Glu(58), and Ile(59) can be fitted phenomenologically to a two-site on-and-off exchange mechanism with physically feasible relaxation and kinetic parameters obtained for residues Phe(56), Glu(58), and Ile(59), independent of the prothrombin concentration. The apparent kinetic parameters of Glu(57) show some dependence on the concentration of prothrombin and the extracted transverse relaxation rate for Glu(57) in the bound state was severalfold higher than that expected for a protein-peptide complex with a size of approximately 72 kDa. In addition, the equilibrium population of the bound peptide obtained for Glu(57) was inconsistent with those for Phe(56), Glu(58), and Ile(59) and with the prothrombin/peptide ratios used in the experiments. These discrepancies can be explained by the presence of two conformations for the peptide-protein complex exchanging at a rate of approximately 100 s(-)(1). In all, our study shows that fast dissociation of protein-peptide complexes can be studied quantitatively using peptide (15)N NMR relaxation dispersion measurements without a precise knowledge of the peptide and protein concentrations. In addition, protein titration was found to improve the accuracy of quantitative analysis and may make it possible to determine the rate of conformational changes within the protein-peptide complex. 相似文献
149.
Hulin Li Boyan Zhang Lin Ma Liliu Wu James Q. Chambers 《Transition Metal Chemistry》1995,20(6):552-556
Summary The spectrochemical, electrochemical and electrocatalytic properties of Co[15]aneN4 ([15]aneN4 = 1,4,8,12-tetraazacyclopentadecane) have been investigated. The results show that, in aqueous solution, this compound mainly exists as three species whose axial coordination positions are occupied by water and/or hydroxy ligands; it is marginal whether other substrates such as Cl– and NO
inf3
sup–
interact with the central ion in acid-base solutions. The approximate Pourbaix diagram of CoIII/II[15]ane N4 was determined. There is an electrochemically-induced isomerization between two trans conformational isomers of the Co[15]aneN4 complexes in acid and netural solutions. The Co[15]aneN4 complex has electrocatalytic properties for reduction of nitrate and nitrite only in strong alkaline solution. 相似文献
150.