全文获取类型
收费全文 | 6397篇 |
免费 | 1086篇 |
国内免费 | 798篇 |
专业分类
化学 | 4348篇 |
晶体学 | 46篇 |
力学 | 467篇 |
综合类 | 39篇 |
数学 | 789篇 |
物理学 | 2592篇 |
出版年
2024年 | 16篇 |
2023年 | 137篇 |
2022年 | 207篇 |
2021年 | 194篇 |
2020年 | 228篇 |
2019年 | 253篇 |
2018年 | 189篇 |
2017年 | 189篇 |
2016年 | 284篇 |
2015年 | 312篇 |
2014年 | 309篇 |
2013年 | 372篇 |
2012年 | 554篇 |
2011年 | 602篇 |
2010年 | 405篇 |
2009年 | 324篇 |
2008年 | 427篇 |
2007年 | 379篇 |
2006年 | 366篇 |
2005年 | 340篇 |
2004年 | 290篇 |
2003年 | 206篇 |
2002年 | 191篇 |
2001年 | 150篇 |
2000年 | 115篇 |
1999年 | 153篇 |
1998年 | 115篇 |
1997年 | 126篇 |
1996年 | 131篇 |
1995年 | 124篇 |
1994年 | 87篇 |
1993年 | 69篇 |
1992年 | 58篇 |
1991年 | 65篇 |
1990年 | 68篇 |
1989年 | 54篇 |
1988年 | 41篇 |
1987年 | 32篇 |
1986年 | 38篇 |
1985年 | 28篇 |
1984年 | 15篇 |
1983年 | 9篇 |
1982年 | 11篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 2篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1957年 | 3篇 |
排序方式: 共有8281条查询结果,搜索用时 15 毫秒
111.
Lian HZ Kang YF Bi SP Yasin A Shao DL Chen YJ Dai LM Tian LC 《Analytical and bioanalytical chemistry》2003,376(4):542-548
A reversed-phase high-performance liquid chromatographic method with fluorescence detection for the determination of labile monomeric aluminium has been developed through pre-column complexation using morin as the analytical reagent. The highly fluorescent aluminium-morin complex (excitation wavelength 418 nm, emission wavelength 490 nm) was separated on a Spherisorb ODS 2 column with an eluent consisting of 30% methanol and 70% water (pH 1.0 with perchloric acid). The most remarkable point of this protocol was that only the most toxic aluminium species, that is, free aqua-aluminium ion and its monomeric hydroxo complex ions, selectively respond among various aluminium complexes. This strategy has been successfully applied to direct fractionation of the toxic aluminium in natural waters and biological samples without any pretreatment. 相似文献
112.
线性非理想条件下液相色谱柱末端峰形规律 总被引:2,自引:1,他引:2
色谱流出曲线的二阶中心矩μ2和三阶中心矩μ3以及描述峰形非对称程度的偏态系数∑k=μ3/μ1.52是反映色谱峰形的重要参数。从液相色谱过程动力学方程出发,运用电子计算机证明了在线性非理想条件下高效液相色谱体系中不同保留值组分在柱末端峰形的分布基本一致的结论。 相似文献
113.
Alternating adsorption of poly(acrylic acid) and a polyethylenimine-Pd(II) complex on alumina and subsequent reduction of Pd(II) by NaBH4 yield catalytic Pd nanoparticles embedded in multilayer polyelectrolyte films. The polyelectrolytes limit aggregation of the particles and impart catalytic selectivity in the hydrogenation of alpha-substituted unsaturated alcohols by restricting access to catalytic sites. Hydrogenation of allyl alcohol by encapsulated Pd(0) nanoparticles can occur as much as 24-fold faster than hydrogenation of 3-methyl-1-penten-3-ol. Additionally, the nanoparticle/polyelectrolyte system suppresses unwanted substrate isomerization, when compared to a commercial palladium catalyst. Selective diffusion through poly(acrylic acid)/polyethlyenimine membranes suggests that hydrogenation selectivities are due to different rates of diffusion to nanoparticle catalysts. First-order kinetics are also consistent with a diffusion-limited mechanism. Further exploitation of the versatility of polyelectrolyte films should increase selectivity in hydrogenation as well as other reactions. 相似文献
114.
Hydrogen abstraction reaction, H C2H4 --H2 C2H2 was studied by using A initio SCF method. Ge-ometries were fully optimized at SCF level and energies were computed at STO-3G basis set for reactants and transition state. Vibrational analysis was performed thereupon. Finally, the rate constant calculations were carried out at different temperatures for all range of reaction temperature according to Eyring's sbwlute reaction rate theory. The calculated activation energy is 12. 68 kcal/mol, lower than observed value (H. S kcal/mol) by 1. 82 kcal/mol only. The agreement of the calculated rate constants with the experiments is satisfactory. 相似文献
115.
A simple and effective chemically modified carbon paste electrode (CMCPE) for the simultaneous determination of lead(II) and cadmium(II) was developed in this work. The electrode was prepared by the addition of diacetyldioxime into a carbon paste mixture. Pb2+ and Cd2+ were preconcentrated on the surface of the modified electrode by complexing with diacetyldioxime and reduced at a negative potential (−1.10 V). Then the reduced products were oxidized by differential pulse stripping. The fact that two stripping peaks appeared on the voltammograms at the potentials of −0.65 V (Cd2+) and −0.91 V (Pb2+) demonstrates the possibility of simultaneous determination of Pb2+ and Cd2+. Under the optimized working conditions, calibration graphs were linear in the concentration ranges of 1.0×10−7-1.5×10−5 mol l−1 (Pb2+) and 2.5×10−7-2.5×10−5 mol l−1 (Cd2+), respectively. For 5 min preconcentration, detection limits of 1×10−8 mol l−1 (Pb2+) and 4×10−8 mol l−1 (Cd2+) were obtained at the signal noise ratio (SNR) of 3. To evaluate the reproducibility of the newly developed electrode, the measurements of 5×10−7 mol l−1 Pb2+ and Cd2+ were parallel carried out for six times at different electrodes and the relative standard deviations were 2.9% (Pb2+) and 3.2% (Cd2+), respectively. Interferences by some metals were investigated. Only Ni2+ and Hg2+ apparently affected the peak currents of Pb2+ and Cd2+. The diacetyldioxime modified carbon paste electrode was applied to the determination of Pb2+ and Cd2+ in water samples. The results indicate that this electrode is sensitive and effective for the simultaneous determination of Pb2+ and Cd2+. 相似文献
116.
Multilayer poly(vinyl alcohol)-adsorbed coating on poly(dimethylsiloxane) microfluidic chips for biopolymer separation 总被引:1,自引:0,他引:1
A poly(dimethylsiloxane) (PDMS) microfluidic chip surface was modified by multilayer-adsorbed and heat-immobilized poly(vinyl alcohol) (PVA) after oxygen plasma treatment. The reflection absorption infrared spectrum (RAIRS) showed that 88% hydrolyzed PVA adsorbed more strongly than 100% hydrolyzed one on the oxygen plasma-pretreated PDMS surface, and they all had little adsorption on original PDMS surface. Repeating the coating procedure three times was found to produce the most robust and effective coating. PVA coating converted the original PDMS surface from a hydrophobic one into a hydrophilic surface, and suppressed electroosmotic flow (EOF) in the range of pH 3-11. More than 1,000,000 plates/m and baseline resolution were obtained for separation of fluorescently labeled basic proteins (lysozyme, ribonuclease B). Fluorescently labeled acidic proteins (bovine serum albumin, beta-lactoglobulin) and fragments of dsDNA phiX174 RF/HaeIII were also separated satisfactorily in the three-layer 88% PVA-coated PDMS microchip. Good separation of basic proteins was obtained for about 70 consecutive runs. 相似文献
117.
Hui‐Bo Zhou Wen Dong Mao Liang Dai‐Zheng Liao Zong‐Hui Jiang Shi‐Ping Yan Peng Cheng 《无机化学与普通化学杂志》2004,630(4):498-500
A three‐dimensional cyano‐bridged copper(II) complex, [Cu(dien)Ag(CN)2]2[Ag2(CN)3][Ag(CN)2] ( 1 ) (dien = diethylenetriamine), has been prepared and characterized by X‐ray crystallography. Complex 1 crystallized in the monoclinic space group P21/n with a = 6.988(2), b = 17.615(6), c = 12.564(4) Å, β = 90.790(5)°. The crystal consists of cis‐[Cu(dien)]2+ units bridged by [Ag(CN)2]— to form a zig‐zag chain. The Ag atoms of the free and bridging [Ag(CN)2]— link together to form additional infinite zig‐zag chains with short Ag···Ag distances. The presence of Ag···Ag interactions effectively increases the dimensionality from a 1‐D chain to a 3‐D coordination polymer. 相似文献
118.
Hayashi T Dejima H Matsuo T Sato H Murata D Hisaeda Y 《Journal of the American Chemical Society》2002,124(38):11226-11227
Myoglobin will be a good scaffold for engineering a function into proteins. To modulate the physiological function of myoglobin, almost all approaches have been demonstrated by site-directed mutagenesis, however, there are few studies which show a significant improvement in the function. In contrast, we focused on the replacement of heme in the protein with an artificial prosthetic group. Recently, we prepared a novel myoglobin reconstituted with an iron porphycene as a structural isomer of mesoheme. The bluish colored reconstituted myoglobin is relatively stable and the deoxymyoglobin reversibly binds ligands. Interestingly, the O2 affinity of the reconstituted myoglobin, 1.1 x 109 M-1, is a significant 1,400-fold higher than that of the native myoglobin. Furthermore, the unfavorable autoxidation kinetics show 7-fold decrease in rate for the reconstituted myoglobin relative to the native myoglobin, indicating the stable oxy-form against autoxidation. The net results come from the slow dissociation of the O2 ligand in the reconstituted myoglobin, koff = 0.11 s-1, because of the formation of strong hydrogen bond between His64 and negatively charged dioxygen. The present study indicates that the replacement of native heme with an artificially created prosthetic group will give us a unique function into a hemoprotein. 相似文献
119.
Dai JC Wu XT Fu ZY Cui CP Hu SM Du WX Wu LM Zhang HH Sun RQ 《Inorganic chemistry》2002,41(6):1391-1396
Three novel complexes, Cd3tma2*13H2O (1), Cd3tma2*dabco*2H2O (2), and Cd3Htma3*8H2O (3) (tma = trimesate), of cadmium(II)-trimesate coordination polymers are obtained from hydrothermal reaction. 1 (C18H32O25Cd3) crystallizes in the monoclinic C2/c space group [a = 18.985(2) A, b = 7.3872(6) A, c = 20.432(2) A, = 97.1660(10), and Z = 4]. 2 (C24H22N2O14Cd3) crystallizes in the monoclinic P2(1)/c space group [a = 10.1323(2) A, b = 19.5669(5) A, c = 13.15880(10) A, = 108.9810(10), and Z = 4]. 3 (C27H28O26Cd3) belongs to the trigonal P31c space group [a = 15.7547(3) A, b = 15.7547(3) A, c = 7.93160(10) A, and Z = 2]. The Cd(II) centers in the three complexes are bridged by tma ligands in the coordination fashion of unidentate, bridging unidentate, bidentate, chelating bis-bidentate, chelating/bridging bis-bidentate, or chelating/bridging bidentate to form the T-shaped molecular bilayer motif for 1, chicken-wire-like motif for 2, and honeycomb-like porous structure for 3, respectively, in which the T-shaped molecular bilayer motif and chicken-wire-like motif are further interlinked in interdigitating or alternating fashion to construct the different coordination architectures. These three complexes exhibit strong fluorescent emission bands at 355 nm (lambda(ex) = 220 nm) for 1, 437 nm (lambda(ex) = 365 nm) for 2, and 353 nm (lambda(ex) = 218 nm) for 3 in the solid state at room temperature. 相似文献
120.
Dialkoxydichlorosilanes ((RO)2SiCl2, R = alkyl) react almost completely with interlayer silanol groups in a layered silicate octosilicate to create a new crystalline silicate structure consisting of new five-membered rings arranged regularly on both sides of the silicate layers. The introduction of dialkoxysilyl groups to the interlamellar region of layered silicates with regular reaction sites provides a new methodology for the design and construction of novel crystalline silicate frameworks by a soft chemical route. 相似文献