全文获取类型
收费全文 | 10600篇 |
免费 | 1517篇 |
国内免费 | 920篇 |
专业分类
化学 | 5779篇 |
晶体学 | 88篇 |
力学 | 504篇 |
综合类 | 36篇 |
数学 | 995篇 |
物理学 | 3173篇 |
无线电 | 2462篇 |
出版年
2024年 | 45篇 |
2023年 | 262篇 |
2022年 | 317篇 |
2021年 | 395篇 |
2020年 | 457篇 |
2019年 | 355篇 |
2018年 | 326篇 |
2017年 | 324篇 |
2016年 | 485篇 |
2015年 | 538篇 |
2014年 | 564篇 |
2013年 | 715篇 |
2012年 | 915篇 |
2011年 | 877篇 |
2010年 | 640篇 |
2009年 | 621篇 |
2008年 | 675篇 |
2007年 | 512篇 |
2006年 | 586篇 |
2005年 | 465篇 |
2004年 | 327篇 |
2003年 | 273篇 |
2002年 | 223篇 |
2001年 | 176篇 |
2000年 | 209篇 |
1999年 | 224篇 |
1998年 | 204篇 |
1997年 | 161篇 |
1996年 | 174篇 |
1995年 | 152篇 |
1994年 | 123篇 |
1993年 | 107篇 |
1992年 | 98篇 |
1991年 | 95篇 |
1990年 | 57篇 |
1989年 | 43篇 |
1988年 | 51篇 |
1987年 | 36篇 |
1986年 | 31篇 |
1985年 | 24篇 |
1984年 | 23篇 |
1983年 | 20篇 |
1982年 | 9篇 |
1981年 | 16篇 |
1980年 | 9篇 |
1977年 | 6篇 |
1976年 | 10篇 |
1975年 | 9篇 |
1973年 | 8篇 |
1972年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
131.
Two novel species, trichloromethanesulfenyl acetate, CCl(3)SOC(O)CH(3), and trichloromethanesulfenyl trifluoroacetate, CCl(3)SOC(O)CF(3), have been generated in situ by the heterogeneous reactions between trichloromethanesulfenyl chloride, CCl(3)SCl, and corresponding silver salts, silver acetate (AgOC(O)CH(3)) and silver trifluoroacetate (AgOC(O)CF(3)), respectively. Photoelectron spectroscopy and quantum chemical calculations are performed to investigate these two molecules, together with their precursor, CCl(3)SCl. Both of these two compounds may exist in the gas phase as a mixture of gauche and trans conformations. As for the dihedral angles delta(RSOR') of the gauche conformers, 107.0 degrees and 108.5 degrees are derived by theoretical calculations (at the B3LYP/6-311+G(3df) level) for CCl(3)SOC(O)CH(3) and CCl(3)SOC(O)CF(3), respectively. The first vertical ionization energies of CCl(3)SOC(O)CH(3) and CCl(3)SOC(O)CF(3), which have been determined by photoelectron spectroscopy, are 9.67 and 10.34 eV, respectively. According to the experimental results and theoretical analysis, the first ionization energy of these two molecules both come from the ionization of the lone pair electron of S atom. 相似文献
132.
Du S Kautz JA McGrath TD Stone FG 《Dalton transactions (Cambridge, England : 2003)》2005,(22):3672-3680
Treatment of 7-NH(2)Bu(t)-nido-7-CB(10)H(12) in tetrahydrofuran (THF) with LiBu(n)(3 equiv) and then [ReBr(CO)(3)(THF)(2)] gives the rhenacarborane dianion [1-NHBu(t)-2,2,2-(CO)(3)-closo-2,1-ReCB(10)H(10)](2-), isolated as the bis-[N(PPh(3))(2)](+) salt (4). Iodine oxidation of this Re(I) intermediate gives the Re(III) complex [1,2-mu-NHBu(t)-2,2,2-(CO)(3)-closo-2,1-ReCB(10)H(10)] 6 in which the carborane functions formally as an 8-electron (6pi+ 2sigma) donor. Reaction of with ligands L in the presence of Me(3)NO gives substituted products [1,2-mu-NHBu(t)-2,2-(CO)(2)-2-L-closo-2,1-ReCB(10)H(10)][L = PPh(3)(7a), CNXyl (7b; Xyl = C(6)H(3)Me(2)-2,6), or Bu(t)C triple bond CH (7c)]. Formation of complex 7c is unexpectedly accompanied by [1,2-mu-NHBu(t)-2,2-(CO)(2)-3,2-sigma:eta(2)-{C(=CHBu(t))-CH=CHBu(t)}-closo-2,1-ReCB(10)H(9)] 8a, in which an alkyne-derived dienyl group is bound to both the rhenium centre and to an adjacent boron vertex. Complex 8a is also obtained from 7c with Bu(t)C triple bond CH and Me(3)NO. The same reaction of 7c, using PhC triple bond CH or CNXyl instead of Bu(t)C triple bond CH, gives, respectively, [1,2-micro-NHBu(t)-2,2-(CO)(2)-3,2-sigma:eta(2)-{C(=CHBu(t))-CH=CHPh}-closo-2,1-ReCB(10)H(9)] 8b and [1,2-micro-NHBu(t)-2-Bu(t)C triple bond CH-2-CO-2-CNXyl-closo-2,1-ReCB(10)H(10)] 9. Addition of donors L to results in displacement from rhenium of the pendant dienyl moiety, yielding [1,2-mu-NHBu(t)-2,2-(CO)(2)-2-L-3-{C(=CHBu(t))-CH=CHBu(t)}-closo-2,1-ReCB(10)H(9)][L = PMe(3)(10a), CNBu(t)(10b)]. Single-crystal X-ray diffraction analyses have confirmed the novel structural features of compounds 6, 7c, 8b and 9. 相似文献
133.
Miao Du Zhi‐Hui Zhang Yan‐Ping You 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(9):o574-o576
Co‐crystallization of hemimellitic acid (benzene‐1,2,3‐tricarboxylic acid) dihydrate (H3HMA·2H2O) with 4,4′‐bipyridine (4,4′‐bpy) affords the 1:1 co‐crystal benzene‐1,2,3‐tricarboxylic acid–4,4′‐bipyridine (1/1), H3HMA·4,4′‐bpy or C9H6O6·C10H8N2. Strong O—H⋯O hydrogen bonds connect the acid molecules to form a one‐dimensional zigzag chain, around which the 4,4′‐bpy components are fixed as arms via O—H⋯N interactions, resulting in a ladder motif. Through weak C—H⋯O non‐covalent forces, the resulting acid layers are extended into a three‐dimensional pillar‐layered architecture supported by rod‐like 4,4′‐bpy components. The influence on hydrogen‐bonding models is also discussed, with the discovery of an unexpected interaction motif that does not follow the routine hydrogen‐bonded hierarchical rule in the construction of an acid–base co‐crystal. 相似文献
134.
Yanfang Shen Tianying Xiong Hao Du Huazi Jin Jianku Shang Ke Yang 《Journal of Sol-Gel Science and Technology》2009,50(1):98-102
P, N, and Mo ternary co-doped nano TiO2 photocatalysts ((P, N, Mo)-TiO2) were prepared by a single step sol–gel method, which show much enhanced photocatalytic activities over Mo-TiO2, (P, N)-TiO2, un-doped TiO2 and Degussa P25 under visible light irradiation. The degradation rate of 0.72Mo–P-TiO2 is as high as 65.3%, which is about 6.7 times of that of Degussa P25. Possible reasons for the improvement of photocatalytic
activities were analyzed. 相似文献
135.
136.
Hongwei Du Paul D. Hamilton Matthew A. Reilly Andr dAvignon Pramit Biswas Nathan Ravi 《Journal of colloid and interface science》2009,340(2):202-208
A series of highly water-soluble organo-silica nanoparticles, ranging from 2 to 10 nm in diameter, were synthesized by the cohydrolysis and copolycondensation reactions. ω-methoxy(polyethyleneoxy)propyltrimethoxysilane (PEG6-9) and hydroxymethyltriethoxysilane (HMTEOS) mixtures were catalyzed by sodium hydroxide in the presence of surfactant benzethonium chloride (BTC) with various ratios of PEG6-9/HMTEOS at room temperature. The synthesized organo-silica nanoparticles possess a core–shell structure with a core of organo-silica resulting from HMTEOS and a monolayer shell of PEG6-9. The chemo-physical characteristics of the particles were studied by gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectroscopy, 29Si nuclear magnetic resonance (NMR), dynamic light scattering (DLS), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The molecular weight and particle size of the particles increased with increasing HMTEOS molar ratios. The richest HMTEOS composition for the water-soluble particles was found to be HMTEOS:PEG6-9 = 80:20, where the particles had a 6 nm diameter core and a 0.8 nm thick shell. We propose that these water-soluble organo-silica nanoparticles will be suitable for biomedical applications. 相似文献
137.
Sun L Zhao R Zhang L Zhang T Xin W Lan X Huang C Du G 《Molecules (Basel, Switzerland)》2012,17(3):3333-3347
Proliferation and migration of vascular smooth muscle cells (VSMCs) are critical events in the initiation and development of restenosis upon percutaneous transluminal coronary angioplasty (PTCA). Polyphenols have been suggested to ameliorate post-angioplasty restenosis. Salvianolic A (SalA) is one of the most abundant polyphenols extracted from salvia. In this study, we investigated the effect of salvianolic A (SalA) on the migration and proliferation of VSMCs. We found a preferential interaction of SalA with cellular systems that rely on the PDGF signal, but not on the EGF and bFGF signal. SalA inhibits PDGF-BB induced VSMC proliferation and migration in the concentration range from 0.01 to 0.1 μM. The inhibition of SalA on VSMC proliferation is associated with cell cycle arrest. We also found that SalA inhibits the PDGFRβ-ERK1/2 signaling cascade activated by PDGF-BB in VSMCs. In addition, SalA does not influence the proliferation of endothelial cells, the synthesis of NO and eNOS protein expression. Our results suggest that SalA inhibits migration and proliferation of VSMCs induced by PDGF-BB via the inhibition of the PDGFRβ-ERK1/2 cascade, but that it does not constrain endothelial cell proliferation and nitric oxide biosynthesis. Thus, the present study suggests a novel adjunct pharmacological strategy to prevent angioplasty-related restenosis. 相似文献
138.
Liu W Cao W Liu W Du K Gong P 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2012,85(1):283-287
This study established a novel flow injection (FI) methodology for the determination of phenol in aqueous samples based on luminol chemiluminescence (CL) detection. The method was based on the inhibition that phenol caused on the hemin-catalysed chemiluminescence reaction between luminol and hydrogen peroxide in alkaline solution. Optimum conditions and possible mechanisms have been investigated. The linear range was 2.0×10(-9) to 4.0×10(-7)gmL(-1) for phenol. The proposed method is sensitive with a detection limit of 4.0×10(-10)gmL(-1). The relative standard deviation for 11 measurements was 2.3% for 1.0×10(-7)gmL(-1) phenol. The method was applied for the determination of phenol in waste water samples. The results obtained compared well with those by an official method. 相似文献
139.
The cyclization reactions of arylamines with 2-deoxy-D-ribose or glycals were reinvestigated in the current report. In the montmorillonite KSF- or InCl(3)-initiated reactions of 2-deoxy-D-ribose with arylamines, a pair of diastereomeric tetrahydro-2H-pyran-fused tetrahydroquinolines was obtained in a nearly 1:1 ratio where the structure of one diastereomer was incorrectly assigned in the literature. Meanwhile, the diastereoselectivity in InBr(3)-catalyzed cyclization of glycals with arylamines was also incorrectly reported previously. It was found that high diastereomeric selectivity was achieved only when a C5-substituted glycal was used; otherwise, a pair of diastereomers was obtained in moderate yield with 1:1 diastereomeric ratio. Furthermore, tetrahydrofuran-fused tetrahydroquinolines 5b and 5b' were also prepared successfully by using TBDPS-protected ribose as the glycal precursor and montmorillonite KSF as the activator. 相似文献
140.
Jia-Zheng Lu Yi-fan Du Bin Wu Jin-Wang Huang Jing Jiang 《Transition Metal Chemistry》2010,35(4):451-456
A fluorescein–porphyrin hybrid (Fl-PTPP) has been synthesized and characterized by UV/Vis, IR, 1H NMR, ES-MS and elemental analysis. The supramolecular self-assembly of Fl-PTPP with the copper(II) complex of 5-(p-amino-phenyl)-10,15,20-triphenylporphyrin, (CuAPTPP), by hydoxyl-amino type hydrogen bonding was studied using vapor pressure
osmometry (VPO) measurements, ES-MS, UV/Vis, 1H NMR and fluorescence spectroscopic titration. The data indicate formation of a (Fl-PTPP)–CuAPTPP supramolecular complex.
Fluorescence strengthening character was observed in a spectroscopic titration experiment for the Fl-PTPP/CuAPTPP system.
The association constant of the supramolecular complex was calculated from the fluorescence titration data, and found to be
less than that of a carboxyl–carboxyl type hydrogen-bonding system. 相似文献