全文获取类型
收费全文 | 36108篇 |
免费 | 7020篇 |
国内免费 | 5739篇 |
专业分类
化学 | 26823篇 |
晶体学 | 576篇 |
力学 | 2329篇 |
综合类 | 395篇 |
数学 | 4013篇 |
物理学 | 14731篇 |
出版年
2024年 | 107篇 |
2023年 | 658篇 |
2022年 | 1305篇 |
2021年 | 1364篇 |
2020年 | 1473篇 |
2019年 | 1530篇 |
2018年 | 1324篇 |
2017年 | 1362篇 |
2016年 | 1788篇 |
2015年 | 1978篇 |
2014年 | 2396篇 |
2013年 | 2988篇 |
2012年 | 3487篇 |
2011年 | 3522篇 |
2010年 | 2617篇 |
2009年 | 2678篇 |
2008年 | 2897篇 |
2007年 | 2406篇 |
2006年 | 2233篇 |
2005年 | 1800篇 |
2004年 | 1346篇 |
2003年 | 1129篇 |
2002年 | 1144篇 |
2001年 | 926篇 |
2000年 | 748篇 |
1999年 | 616篇 |
1998年 | 444篇 |
1997年 | 402篇 |
1996年 | 354篇 |
1995年 | 286篇 |
1994年 | 289篇 |
1993年 | 224篇 |
1992年 | 175篇 |
1991年 | 143篇 |
1990年 | 139篇 |
1989年 | 88篇 |
1988年 | 80篇 |
1987年 | 61篇 |
1986年 | 70篇 |
1985年 | 47篇 |
1984年 | 24篇 |
1983年 | 28篇 |
1982年 | 13篇 |
1981年 | 14篇 |
1980年 | 9篇 |
1979年 | 19篇 |
1978年 | 7篇 |
1977年 | 11篇 |
1957年 | 8篇 |
1925年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
941.
金属硫蛋白(Metallothioneins,简称MTs)是一类富含巯基和金属的低分子量蛋白质,广泛存在于哺乳动物中.MTs 通常含61个氨基酸,其中20个为半胱氨酸,不含芳香族氯基酸和组氨酸,因此在280nm 附近没有吸收峰.MTs 通常结合7个Cd 或zn,20个巯基全部去质子化并参与配位,从而形成牢固的结构域.有证据表明MTs 可能有储存Zn 和Cu 的作用,同时能减轻重金属对动物细胞的毒性,但其生理功能一直不很清楚.近几年的研究表明,MTs 能增强机体对电离辐射的耐受力、修复DNA 损伤,这可能与MTs 中含有丰富的巯基有关.体外实验测得k_(MT/OH)=10~(12)dm~3·mol~(-1)·s~(-1),k_(MT/O(?))=5×10~5dm~3·mol~(-1)·s~(-1),但其辐解机理尚不清楚.本工作利用脉冲辐解技术研究了免肝MT-I 稀水溶液辐解时的中间过程,并作了初步的解释. 相似文献
942.
The equation for the Helmholtz free energy for systems of small anisotropic molecules and ions is deduced by substituting the complete expression for various potential energies (including repulsive, dispersive, electrostatic, and induced energies) into the perturbation expansion. The equation is applied to pure water. The relative dielectric constant is set at unity. Based on the equal chemical potentials of equilibrated vapor and liquid phases, the molecular parameters of water are regressed from the densities of saturated vapor in the temperature range of 0 to 370°C. The ARD of regression is 1.16%. These parameters are used to predict the heat of vaporization and densities of saturated vapor and liquid phases of water in the same temperature range. The ARDs of prediction are 4.5% and 9.8%, respectively. The equation is used to correlate the osmotic coefficients of twelve 1:1 electrolyte solutions. The relative dielectric constant is set at unity. The parameters (Soft-sphere diameter and dispersive constant) of seven ions (Na+, K+, Rb+, Cs+, Cl–, Br–, and I–) are obtained. The total average absolute deviation between calculated and experimental values of the osmotic coefficient is 0.041. The parameters of ions can keep constant in different systems. 相似文献
943.
Herein, we report a novel amino acid based reaction system for CO2 capture and utilization (CCU) to produce formates in the presence of the naturally occurring amino acid l-lysine. Utilizing a specific ruthenium-based catalyst system, hydrogenation of absorbed carbon dioxide occurs with high activity and excellent productivity. Noteworthy, following the CCU concept, CO2 can be captured from ambient air in the form of carbamates and converted directly to formates in one-pot (TON > 50 000). This protocol opens new potential for transforming captured CO2 from ambient air to C1-related products.A novel amino acid based reaction system for CO2 capture and utilization (CCU) to produce formates is presented applying a ruthenium-based catalyst. Noteworthy, CO2 can be captured from ambient air and converted to formates in one-pot (TON > 50 000). 相似文献
944.
Structural tuning of coordination polymers by 4-connecting metal node and secondary building process
Due to variation in ligand's conformation, metal node's connecting geometry, and secondary building process by anions, bat-like, dumbell-like, diamondoid, or pillar-layer topologies are achieved. 相似文献
945.
Chao Chen Yu-Lin Yang Kun-Lin Huang Zhen-Hua Sun Wei Wang Zhuo Yi Yun-Ling Liu Wen-Qin Pang 《Polyhedron》2004,23(18):3033-3042
With a hydrothermal technique, a layered titanium phosphate with the formula Ti2(H2PO4)(HPO4)(PO4)2 · 0.5C6N2H16 (denoted TP-J2) has been prepared by treating the Ti/H3PO4/H2O/1-methylpiperazine system directly. The as-synthesized products were characterized by powder X-ray diffraction, CP-MAS solid-state 31P NMR spectroscopy, thermogravimetric and differential thermal analyses (TG-DTA). The structure was solved by single-crystal X-ray diffraction analysis and it presents an extended γ-phase intercalated with organic amine. Crystal data: triclinic, , a = 8.106 (2) Å, b = 8.197 (2) Å, c = 11.658 (2) Å. = 78.32 (3)°, β = 80.85 (3)°, γ = 77.90 (3)°, Z = 2. Additionally, the intercalation behavior of TP-J2 with n-alkyl monoamine (n = 2, 3, 4, 6, 8, 10 and 12) was investigated. Owing to the strong brønsted base, N,N′-dimethylpiperazine, resides in the interlayer, it presented unusual features of TP-J2 in contrast with that of γ-Tip. 相似文献
946.
[structure: see text] A synthetic strategy promising the establishment of a new star-shaped and linear polycyclic aromatic hydrocarbons (PAHs) family with distinct molecular topologies has been developed. The Sonogashira reaction between the iodide derivatives 2a-e and phenylacetylene catalyzed with Pd(0) affords 3a-e in high yields. The Diels-Alder and decarbonylation reactions between 3a-e and tetraphenylcyclophentadiene following the oxidation by FeCl(3) produce the star-shaped and linear PAHs 5a-e containing a five-membered ring. The structural analysis and the optical properties of all new compounds are performed by a combination of MALDI-TOF mass spectrometry, UV-vis, and fluorescence spectrometry. The electronic and photophysical properties are studied by orthogonal comparisons of the absorption and fluorescence spectra in THF solutions, which not only give insight into the interactions among aromatic submoieties in each molecule and the effects of meta-conjugation and para-conjugation on electronic delocalization, but also indicate effective conjugation length variations from oligophenylacetylenes 3a-e to oligophenylene dendrimers 4a-e and PAHs 5a-e. The star-shaped 5c exhibits the highest aggregation in excited states compared with the other four hexa-peri-hexabenzocoronene (HBC) derivatives. 相似文献
947.
Xujiao Ma Yajie Yang Rongchen Ma Yunfeng Zhang Xiaoqin Zou Shoujun Zhu Xin Ge Ye Yuan Wei Zhang Guangshan Zhu 《Chemical science》2020,11(44):12187
Despite their remarkable mechanical, optical, and electrical properties, inorganic particles and dynamic polymer assemblies encounter difficulties in their compatibility with regards to structural order and complexity. Here, covalent organic frameworks (COFs) constructed through reversible coupling reactions were exploited as dynamic porous polymers to prepare inorganic nanocrystal-polymer assemblies. Under an in situ growth process, carbon quantum dots (CDs) were gradually prepared in the COF cavity, with a narrow size distribution (2 ± 0.5 nm). The well-established assemblies achieve effective energy transfer from the inorganic to the organic part (efficiency > 80%), thus rendering a ∼130% increase in quantum yield compared with the pristine COF network. Notably, the hybrid material realizes a simple, selective, and sensitive diagnostic tool for urine copper, surpassing the detection limit of COF solid by 150 times. Beyond the scientific and fundamental interests, such hybrid assemblies are attractive from technological perspectives as well, for example, in energy storage, electronics, catalysis, and optics.Despite their remarkable mechanical, optical, and electrical properties, inorganic particles and dynamic polymer assemblies encounter difficulties in their compatibility with regards to structural order and complexity. 相似文献
948.
Determination of amino acids in a complex matrix without derivatization is advantageous, however, difficulties are found in both the detection and the separation of those compounds. In this study, a rapid and reliable LC-MS-MS method for the quantitation of underivatized amino acids in exocellular media was established. Injections were made directly after centrifugation of the samples, without further preparation. The separation of seven underivatized amino acids was achieved on a reversed-phase C18 column with pentadecafluorooctanoic acid as a volatile ion-pair reagent, and the specific detection of most amino acids was achieved by MS-MS of the specific transitions [M + H]+-->[M + H - 46]+. The calibration curves of all analytes were linear over the range of 1.0-1000 microg ml(-1) and the detection limits ranged from 0.1 to 5 ng ml(-1), with an injection volume of 20 microl. The inter-day and intra-day precisions ranged from 2.6 to 5.7% and 4.8 to 8.2%, respectively; the mean recoveries of the seven analytes were 81-104%, 91-107% and 93-101% respectively at the spiked level of 10, 40 and 200 microg ml(-1). A large number of fermentation samples were analysed using this method. The technique is simple, rapid, selective and sensitive, and shows potential for the high-throughput quantitation of amino acids from other biological matrices. 相似文献
949.
H.-J. Machulla A. Blocher M. Kuntzsch M. Piert R. Wei J.R. Grierson 《Journal of Radioanalytical and Nuclear Chemistry》2000,243(3):843-846
[18F]FLT (3-deoxy-3-[18F]fluorothymidine) turned out to be a tracer particularly suitable for PET imaging of tumor proliferation because of lacking degradation in vivo. To facilitate clinical studies with [18F]FLT, we investigated two new easily accessible precursors, 2,3-anhydrothymidine (AThy) and 5-O-(4,4-dimethoxytriphenylmethyl)-2,3-anhydrothymidine (DMTThy), using a common approach for introducing the label with nucleophilic [18F]fluoride. Radiochemical yields were determined in dependence on substrate concentration, reaction time and temperature. In the case of AThy (10 mg), best FLT yields were 5.3%±1.2 (130 °C, 30 min). Labeling of DMTThy (10 mg) gave 14.3%±3.3 at 160 °C within 10 minutes. Starting with an aqueous solution of 20 GBq [18F]fluoride the new method allows to produce 1.3 GBq [18F]FLT within 90 minutes ready for intravenous injection. The new labeling procedures allow [18F]FLT synthesis without lengthy preparation of the precursor and with high reproducibility mandatory for clinical application. 相似文献
950.
The reaction of electron-deficient cyclopropane derivatives, cis-1-methoxycarbonyl-2-aryl-6,6-dimethyl-5,7dioxospiro[2,5]octa-4,8-diones with benzoylmethylenetriphenylarsorane (2) and methoxycarbonylmethylenetriphenylarsorane (4) was found to form cis,trans-l-methoxycarbonyl-2-aryl-3-benzoyl-7,7-dimethyl-6,8-dioxospiro[3,5]nona-5,9-dione (3a-3e) and trans,cis,trans-5-[2‘-methoxycarbonyl-2‘-(triphenylarsoranylidene)acetyl]-6oxo-3-aryl-tetrahydro-pyran-2,4-dicarboxylic acid dimethyl esters (5a-5c) respectively with high stereoselectivity. The possible reaction mechanisms for the formation of the different products were also orooosed. 相似文献