全文获取类型
收费全文 | 41856篇 |
免费 | 7838篇 |
国内免费 | 6977篇 |
专业分类
化学 | 31936篇 |
晶体学 | 670篇 |
力学 | 2638篇 |
综合类 | 523篇 |
数学 | 4822篇 |
物理学 | 16082篇 |
出版年
2024年 | 85篇 |
2023年 | 715篇 |
2022年 | 1141篇 |
2021年 | 1423篇 |
2020年 | 1695篇 |
2019年 | 1736篇 |
2018年 | 1525篇 |
2017年 | 1516篇 |
2016年 | 2024篇 |
2015年 | 2218篇 |
2014年 | 2727篇 |
2013年 | 3391篇 |
2012年 | 3957篇 |
2011年 | 4106篇 |
2010年 | 3107篇 |
2009年 | 3153篇 |
2008年 | 3398篇 |
2007年 | 2826篇 |
2006年 | 2631篇 |
2005年 | 2163篇 |
2004年 | 1712篇 |
2003年 | 1409篇 |
2002年 | 1492篇 |
2001年 | 1208篇 |
2000年 | 979篇 |
1999年 | 781篇 |
1998年 | 545篇 |
1997年 | 462篇 |
1996年 | 427篇 |
1995年 | 348篇 |
1994年 | 324篇 |
1993年 | 258篇 |
1992年 | 205篇 |
1991年 | 171篇 |
1990年 | 164篇 |
1989年 | 98篇 |
1988年 | 95篇 |
1987年 | 73篇 |
1986年 | 76篇 |
1985年 | 51篇 |
1984年 | 26篇 |
1983年 | 29篇 |
1982年 | 15篇 |
1981年 | 16篇 |
1980年 | 10篇 |
1979年 | 20篇 |
1977年 | 11篇 |
1957年 | 9篇 |
1936年 | 7篇 |
1925年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 343 毫秒
991.
Poly(p-phenylenevinylene)s with amines and pentafluorophenyl esters on side chains were synthesized and assembled on solid substrates by sequential layer-by-layer (LBL) deposition. This approach enables the creation of robust multilayer thin films via in-situ covalent coupling reactions between successive layers. The buildup of the multilayers was followed by UV/vis absorption spectroscopy and ellipsometry. The observed complex assembly behavior suggests that both covalent and hydrogen-bonding interactions are involved in the formation of multilayer films. The organized structure and surface morphology of resultant multilayers were investigated by reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. This covalent LBL method was further applied to generate conjugated polymer micropatterns using microstamped self-assembled monolayers as templates. 相似文献
992.
Hsu MH Hu WS Lin JJ Hsu YJ Wei DH Yang CW Chang CS Tao YT 《Langmuir : the ACS journal of surfaces and colloids》2004,20(9):3641-3647
The structure of self-assembled monolayers ofp-terphenyl-4-carboxylic acid and the mixed monolayers of this acid with n-hexadecanoic acid on silver surface were studied by reflection-IR spectroscopy, near-edge X-ray absorption fine structure (NEXAFS) measurement, X-ray photoemission electron microscopy (X-PEEM), and atomic force microscopy. Exposure of the p-terphenyl-4-carboxylate monolayer to H2S vapor resulted in reorganization of the film structure into clusters of the corresponding free acids, in tens of nanometer dimension. Exposure of the mixed monolayer to H2S resulted in reorganization of the mixed monolayer film into phase-separated clusters of respective component molecules. The saturated aliphatic acid formed clusters of submicrometer size, whereas the p-terphenyl-4-carboxylic acid formed clusters of tens of nanometer size, presumably due to different surface mobility and/or intermolecular interaction of the two types of molecule. Restoration of the monolayer film from the clusters, driven by the reaction between the free acid molecules and the basic surface sites, proceeded at different speeds for the two types of molecules. The saturated acid monolayer was restored much faster than the p-terphenyl-4-carboxylic acid monolayer. A domain-separated monolayer in several micrometers scale was obtained. The process was imaged by tapping mode atomic force microscopy. 相似文献
993.
Jin-long Wu Zhen-ya Zeng Lan-hua Wei Ling-zhi Meng Ting-xian Yang 《Tetrahedron》2004,60(19):4309-4314
Three new neutral receptors (1, 2 and 3) containing thiourea and amide groups were synthesized by simple steps in good yields. The binding properties for anions of 1, 2 and 3 were examined by UV-vis, fluorescence, and 1H NMR spectroscopy. Receptors 1, 2 and 3 all had a better adipate anion selectivity by comparison with other dicarboxylate anions. The association constants of 1, 2 and 3 with adipate were higher as compared to other anions (malonate, succinate, glutarate). In particular, a distinct color change was observed from light yellow to orange-red upon addition of adipate to the solution of 1 in DMSO. The UV-vis and fluorescence data indicate that a 1:1 stoichiometry complex is formed between compound 1, 2 or 3 and dicarboxylate anions through hydrogen bonding interactions. 相似文献
994.
聚苯乙烯磺酸掺杂聚苯胺的合成 总被引:7,自引:1,他引:7
以苯胺(An)为单体,过硫酸铵(APS)为氧化剂,在聚苯乙烯磺酸(PSSA)的水溶液中,合成了可完全溶于水的PSSA掺杂PAn。研究了An浓度,PSSA浓度,APS浓度,APS的滴加时间,反应时间及温度对An聚合反应及其产物的水溶性,导电性及特性粘度[η]的影响。结果表明:在比较宽的实验条件下,都可以合成出具有良好导电性的可溶于水的PSSA掺杂PAn;其中当An:PSSA:APS的摩尔比为1.7:2.5:1,APS溶液的滴加时间为3h,反应时间为1h,反应温度为14℃时,得到的掺杂PAn导电率最高达0.156S/cm。 相似文献
995.
Monitoring the removal of carbonate from alkali metal hydroxide (MOH, M = K, Na) solutions with calcium oxide (CaO) was studied using a newly developed method for the determination of trace amounts of total carbonate (TC) in alkaline solutions based on a flow injection (FI) technique coupled with a gas diffusion system. The optimized conditions of the FI system were as follows: the flow rate of each carrier, reaction solution (H2SO4) and receptor solution (Cresol Red, pH 8.9) was 0.25 ml min(-1), the sample size was 0.1 ml and the concentration of H2SO4 in the reaction solution was 0.09 M. The limit of detection of TC by the proposed method was 4 x 10(-7) M. The removal efficiency of carbonate was affected by the amount of CaO added, the shaking time of the solutions and the concentration of MOH. For 1 M NaOH and KOH solution, the removal efficiency of carbonate was about 99% and the concentration of residual carbonate was 4 x 10(-5) and 1.2 X 10(-4) M, respectively, when the amount of CaO added was 2 g l(-1) and the shaking time was 16 h. 相似文献
996.
Amphiphilic copolymers of 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS) with dihydrocholesteryl acrylate (pDHCHAt) or tert-octyl acrylamide (ptOAm) as comonomers were synthesized, characterized and used as new polymeric pseudostationary phases in electrokinetic chromatography. High-efficiency separations with theoretical plates around 500,000 to 870,000/m were achieved. Linear solvation energy relationships analysis of 20 solutes was performed to investigate the retention mechanism. Polycyclic aromatic hydrocarbons (PAHs) were separated under 30% v/v acetonitrile. The separation of nine aromatic model solutes by pDHCHAt showed significantly different selectivity from that of sodium dodecyl sulfate. Although only minor difference in selectivity was found for small aromatic compounds on pDHCHAt and poly(AMPS-lauryl acrylate), significantly different retention mechanism was found for PAHs and n-dodecanophenone comparing both copolymers. Significant chemical selectivity difference was found for selected small aromatic compounds on ptOAm and poly(AMPS-stearyl acrylamide). 相似文献
997.
Wenxuan Jiang Wei Wei Tinglian Yuan Shasha Liu Ben Niu Hui Wang Wei Wang 《Chemical science》2021,12(24):8556
The inevitable microstructural defects, including cracks, grain boundaries and cavities, make a portion of the material inaccessible to electrons and ions, becoming the incentives for electrochemically inactive zones in single entity. Herein, we introduced dark field microscopy to study the variation of scattering spectrum and optical mass centroid (OMC) of single Prussian blue nanoparticles during electrochemical reaction. The “dark zone” embedded in a single electroactive nanoparticle resulted in the incomplete reaction, and consequently led to the misalignment of OMC for different electrochemical intermediate states. We further revealed the dark zones such as lattice defects in the same entity, which were externally manifested as the fixed pathway for OMC for the migration of potassium ions. This method opens up enormous potentiality to optically access the heterogeneous intraparticle dark zones, with implications for evaluating the crystallinity and electrochemical recyclability of single electroactive nano-objects.The schematic of single cubic-shaped Prussian blue (PB) mesocrystals formed by the oriented aggregation of small nanocrystals. The dark-field images of single PB nanoparticle at PB and Prussian white (PW) states, respectively. 相似文献
998.
ZuPeiLIANG YaQingFENG ShuXianMENG ZhiYanLIANG 《中国化学快报》2005,16(1):135-138
Urease was immobilized onto the glutaraldehyde cross-linked chitosan beads that were prepared under microwave irradiation. The activity and the yield of activity of immobilized urease was 10.83 U/g B and 47.7%, respectively. The conditions of urease immobilization were optimized. The properties of the immobilized urease were investigated and compared with that of the free enzyme. 相似文献
999.
Yang W Wilkins AL Ye Y Liu ZR Li SY Urbauer JL Hellinga HW Kearney A van der Merwe PA Yang JJ 《Journal of the American Chemical Society》2005,127(7):2085-2093
Ca2+, "a signal of life and death", controls numerous cellular processes through interactions with proteins. An effective approach to understanding the role of Ca2+ is the design of a Ca2+-binding protein with predicted structural and functional properties. To design de novo Ca2+-binding sites in proteins is challenging due to the high coordination numbers and the incorporation of charged ligand residues, in addition to Ca2+-induced conformational change. Here, we demonstrate the successful design of a Ca2+-binding site in the non-Ca2+-binding cell adhesion protein CD2. This designed protein, Ca.CD2, exhibits selectivity for Ca2+ versus other di- and monovalent cations. In addition, La3+ (Kd 5.0 microM) and Tb3+ (Kd 6.6 microM) bind to the designed protein somewhat more tightly than does Ca2+ (Kd 1.4 mM). More interestingly, Ca.CD2 retains the native ability to associate with the natural target molecule. The solution structure reveals that Ca.CD2 binds Ca2+ at the intended site with the designed arrangement, which validates our general strategy for designing de novo Ca2+-binding proteins. The structural information also provides a close view of structural determinants that are necessary for a functional protein to accommodate the metal-binding site. This first success in designing Ca2+-binding proteins with desired structural and functional properties opens a new avenue in unveiling key determinants to Ca2+ binding, the mechanism of Ca2+ signaling, and Ca2+-dependent cell adhesion, while avoiding the complexities of the global conformational changes and cooperativity in natural Ca2+-binding proteins. It also represents a major achievement toward designing functional proteins controlled by Ca2+ binding. 相似文献
1000.
Qing Z Wen-Chen Z Xiao-Xuan W Yang M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):769-772
From the high-order perturbation formulas of EPR parameters (zero-field splitting D, g factors gparallel, gperpendicular and hyperfine structure constants Aparallel, Aperpendicular) based on the two spin-orbit coupling parameter model for 3d3 ions in trigonal symmetry, the EPR parameters of Cr3+ and V2+ ions in HfS2 crystals are calculated. From the calculations, it is found that the local trigonal distortion angle theta of impurity center in HfS2:Cr3+ is smaller than that in HfS2:V2+. The dominant cause of the small zero-field splitting |D| and g-anisotropy |Deltag|=|gparallel-gperpendicular| in HfS2:Cr3+ (compound to HfS2:V2+) is due to the small local trigonal distortion angle theta rather than to the small impurity-ligand distance R in HfS2:Cr3+. 相似文献