全文获取类型
收费全文 | 19312篇 |
免费 | 3340篇 |
国内免费 | 2316篇 |
专业分类
化学 | 13617篇 |
晶体学 | 179篇 |
力学 | 1112篇 |
综合类 | 119篇 |
数学 | 2742篇 |
物理学 | 7199篇 |
出版年
2024年 | 58篇 |
2023年 | 416篇 |
2022年 | 556篇 |
2021年 | 660篇 |
2020年 | 852篇 |
2019年 | 773篇 |
2018年 | 677篇 |
2017年 | 628篇 |
2016年 | 971篇 |
2015年 | 919篇 |
2014年 | 1061篇 |
2013年 | 1432篇 |
2012年 | 1677篇 |
2011年 | 1766篇 |
2010年 | 1234篇 |
2009年 | 1103篇 |
2008年 | 1252篇 |
2007年 | 1104篇 |
2006年 | 980篇 |
2005年 | 885篇 |
2004年 | 706篇 |
2003年 | 617篇 |
2002年 | 685篇 |
2001年 | 543篇 |
2000年 | 443篇 |
1999年 | 430篇 |
1998年 | 346篇 |
1997年 | 311篇 |
1996年 | 331篇 |
1995年 | 291篇 |
1994年 | 232篇 |
1993年 | 163篇 |
1992年 | 165篇 |
1991年 | 158篇 |
1990年 | 123篇 |
1989年 | 94篇 |
1988年 | 54篇 |
1987年 | 56篇 |
1986年 | 71篇 |
1985年 | 47篇 |
1984年 | 32篇 |
1983年 | 26篇 |
1982年 | 15篇 |
1981年 | 11篇 |
1980年 | 4篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1969年 | 1篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 537 毫秒
961.
Three oxovanadium complexes, namely [VO(NOSAA)(bpy)] (1) (NOSAA = 2-hydroxy-5-nitrosalicylidene anthranilic acid, bpy = 2,2′-bipyridyl), [VO(NOSAA)(4,4′-dimebpy)] (2) (4,4′-dimebpy = 4,4′-dimethyl-2,2′- bipyridyl), and [VO(NOSAA)(phen)] (3) (phen = 1,10-phenanthroline), have been prepared and characterized. The binding modes and strengths of these complexes with calf thymus DNA (CT-DNA) were studied using various techniques. The chemical nuclease activities and photocleavage reactions of the complexes were also tested. All three complexes interact with CT-DNA through intercalative modes, and complex 3 possesses the largest binding affinity. All three complexes can efficiently cleave pBR322 DNA upon irradiation or under physiological conditions in the presence of H2O2, and complex 3 has the best cleaving ability. In vitro experimental results showed that the three complexes are cytotoxic against myeloma (Ag8.653) and gliomas (U251) cell lines and complex 3 again showed the highest efficacy. 相似文献
962.
Yuming Guo Feifei Wang Jie Zhang Lin Yang Xiaoman Shi Qilong Fang Xiaoming Ma 《Research on Chemical Intermediates》2013,39(6):2407-2415
Using three different amino acids (AAs) as organic matrices, including the highly nonpolar hydrophobic l-valine, the positively charged l-arginine and the less polar uncharged l-serine, calcium carbonate (CaCO3) with different morphologies and polymorphs were synthesized by a facile gas diffusion reaction based on biomimetic strategy. Compared with the control cubic calcite obtained in the absence of AAs, the product from l-valine was cubic calcite aggregates assembled by nano-platelets. The product from l-arginine was spherical vaterite aggregates assembled by spherical nanoparticles. The product from l-serine was the mixture of cubic calcite and spherical vaterite. The structures and properties of the side chains of the AAs exerted the significant effects on the nucleation and growth of the CaCO3. The formation mechanisms of the CaCO3 in the presence of AAs are preliminarily discussed. The results suggest that the polymorphs and morphologies of the inorganic nanomaterials might be easily adjusted through the careful selection of the organic matrices. 相似文献
963.
Qumei Jin Fengyu Qu Jingjie Jiang Yan Dong Wei Guo Huiming Lin 《Journal of Sol-Gel Science and Technology》2013,66(3):466-471
A novel dual-drug delivery system based on mesoporous-macroporous silica/polyelectrolytes-SBA-15 has been synthesized. The structure and composition of these materials were characterized by powder X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and N2 adsorption–desorption measurements. In this system, water-soluble metformin hydrochloride and fat-soluble ibuprofen were used as model drugs to study the controlled release behavior. The pH-controlled release of individual drugs was obtained by the primary release of metformin hydrochloride from polyelectrolytes-SBA-15 in acid condition and the predominant release of ibuprofen from MMC in alkaline environment. The results show that the polyelectrolytes-SBA-15/mesoporous-macroporous silica can be used as dual-drug release system and the individual drug can be controlled release with the change of pH value of the environment. 相似文献
964.
Yanan Hao Xiaohui Wang Hui Zhang Limin Guo Longtu Li 《Journal of Sol-Gel Science and Technology》2013,67(1):182-187
Ultrafine tetragonal BaTiO3 nanocrystals have been prepared by a sol–gel based method. By adjusting the volume ratio of H2O/DEG (diethylene glycol) in the solutions, hydrolysis rate of tetra-n-butyl titanate was strongly inhibited and the particle size could be controlled as small as 4–8 nm. The powder X-ray diffraction and transmission electron microscopy characterizations exhibit that the nanocrystals are spherical and well crystallized. The Raman spectrum shows the products are composed of the orthorhombic phase and tetragonal phase. The Fourier transform infrared spectrum revealed that a surface modification layer was formed around the BaTiO3 nanocrystals, which can prevent them from aggregation and help to form a stable, high solid content sol. 相似文献
965.
Xingzhong Guo Wenyan Li Hui Yang Kazuyoshi Kanamori Yang Zhu Kazuki Nakanishi 《Journal of Sol-Gel Science and Technology》2013,67(2):406-413
An in situ two-step processing using an initial acid catalysis step accompanied by an epoxide-mediated condensation step in the presence of ammonium chloride (NH4Cl) is reported, and macroporous cocontinuous methylsilsesquioxane (MSQ) monoliths have been successfully prepared by this processing. We explain the hydrolysis, gelation behavior and phase separation of MTMS(methyltrimethoxysilane)-MeOH(methanol)-HCl-PO(propylene oxide) system and the in situ effect of NH4Cl, and examine the macroporous morphology and pore structures of MSQ monoliths obtained under different conditions. Macroporous MSQ monolith under optimized conditions possesses a narrow macropore size distribution between 3 to 10 μm, surface area as high as 366 m2·g?1 and minimal shrinkage of only 1 %. 相似文献
966.
967.
Shuwen Li Zhengping Dong Honglei Yang Shujing Guo Galian Gou Ren Ren Zhejun Zhu Prof. Jun Jin Jiantai Ma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(7):2384-2391
A new catalyst consisting of ionic liquid (IL)‐functionalized carbon nanotubes (CNTs) obtained through 1,3‐dipolar cycloaddition support‐enhanced electrocatalytic Pd nanoparticles (Pd@IL(Cl?)‐CNTs) was successfully fabricated and applied in direct ethanol alkaline fuel cells. The morphology, structure, component and stability of Pd@IL(Cl?)‐CNTs were systematic characterized by transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM), Raman spectra, thermogravimetric analysis (TGA) and X‐ray diffraction (XRD). The new catalyst exhibited higher electrocatalytic activity, better tolerance and electrochemical stability than the Pd nanoparticles (NPs) immobilized on CNTs (Pd@CNTs), which was ascribed to the effects of the IL, larger electrochemically active surface area (ECSA), and greater processing performance. Cyclic voltammograms (CVs) at various scan rates illustrated that the oxidation behaviors of ethanol at all electrodes were controlled by diffusion processes. The investigation of the different counteranions demonstrated that the performance of the IL‐CNTs hybrid material was profoundly influenced by the subtly varied structures of the IL moiety. All the results indicated that the Pd@IL(Cl?)‐CNTs catalyst is an efficient anode catalyst, which has potential applications in direct ethanol fuel cells and the strategy of IL functionalization of CNTs could be available to prepare other carbonaceous carrier supports to enhance the dispersivity, stability, and catalytic performance of metal NPs as well. 相似文献
968.
Gadolinium(III)‐Hydroxy Ladders Trapped in Succinate Frameworks with Optimized Magnetocaloric Effect
Yan‐Cong Chen Fu‐Sheng Guo Prof. Dr. Yan‐Zhen Zheng Jun‐Liang Liu Ji‐Dong Leng Róbert Tarasenko Prof. Dr. Martin Orendáč Dr. Jan Prokleška Prof. Dr. Vladimír Sechovský Prof. Dr. Ming‐Liang Tong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13504-13510
Two kinds of inorganic gadolinium(III)‐hydroxy “ladders”, [2×n] and [3×n], were successfully trapped in succinate (suc) coordination polymers, [Gd2(OH)2(suc)2(H2O)]n ? 2n H2O ( 1 ) and [Gd6(OH)8(suc)5(H2O)2]n ? 4n H2O ( 2 ), respectively. Such coordination polymers could be regarded as alternating inorganic–organic hybrid materials with relatively high density. Magnetic and heat capacity studies reveal a large cryogenic magnetocaloric effect (MCE) in both compounds, namely (ΔH=70 kG) 42.8 J kg?1 K?1 for complex 1 and 48.0 J kg?1 K?1 for complex 2 . The effect of the high density is evident, which gives very large volumetric MCEs up to 120 and 144 mJ cm?3 K?1 for complexes 1 and 2 , respectively. 相似文献
969.
Dr. Meiling Guo Prof. Dr. Zhaochi Feng Dr. Jan P. Hofmann Prof. Dr. Bert M. Weckhuysen Dr. Fengtao Fan Prof. Dr. Can Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(42):14200-14204
Microporous vanadosilicates with octahedral VO6 and tetrahedral SiO4 units, better known as AM‐6, have been hydrothermally synthesized with different morphologies by controlling the Na/K molar ratio of the initial gel mixtures. The morphology of the AM‐6 materials changed from bulky cube to nanofiber aggregates as the Na/K molar ratio decreased from 1.9 to 0.2. Raman spectroscopy revealed that the VO3? intermediate species plays an important role in the formation of the nanofiber morphology. The orientation of ‐V‐O‐V‐ chains in nanofiber aggregates was examined by confocal polarized micro‐Raman spectroscopy. It was found that these aggregates are assemblies of short ‐V‐O‐V‐ chains perpendicular to the axis of nanofibers. The obtained AM‐6 nanofibers greatly increase the exposed proportion of V? O terminals, and thus improve the catalytic performance. 相似文献
970.
Yu‐Sheng Su Dr. Yongzhu Fu Dr. Bingkun Guo Dr. Sheng Dai Prof. Arumugam Manthiram 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(26):8621-8626
The cathodic reactions in Li–S batteries can be divided into two steps. Firstly, elemental sulfur is transformed into long‐chain polysulfides (S8?Li2S4), which are highly soluble in the electrolyte. Next, long‐chain polysulfides undergo nucleation reaction and convert into solid‐state Li2S2 and Li2S (Li2S4?Li2S) by slow processes. As a result, the second‐step of the electrochemical reaction hinders the high‐rate application of Li–S batteries. In this report, the kinetics of the sulfur/long‐chain‐polysulfide redox couple (theoretical capacity=419 mA h g?1) are experimentally demonstrated to be very fast in the Li–S system. A Li–S cell with a blended carbon interlayer retains excellent cycle stability and possesses a high percentage of active material utilization over 250 cycles at high C rates. The meso‐/micropores in the interlayer are responsible for accommodating the shuttling polysulfides and offering sufficient electrolyte accessibility. Therefore, utilizing the sulfur/long‐chain polysulfide redox couple with an efficient interlayer configuration in Li–S batteries may be a promising choice for high‐power applications. 相似文献