全文获取类型
收费全文 | 4108篇 |
免费 | 560篇 |
国内免费 | 423篇 |
专业分类
化学 | 2896篇 |
晶体学 | 33篇 |
力学 | 183篇 |
综合类 | 50篇 |
数学 | 638篇 |
物理学 | 1291篇 |
出版年
2024年 | 12篇 |
2023年 | 79篇 |
2022年 | 135篇 |
2021年 | 131篇 |
2020年 | 145篇 |
2019年 | 160篇 |
2018年 | 153篇 |
2017年 | 125篇 |
2016年 | 202篇 |
2015年 | 189篇 |
2014年 | 261篇 |
2013年 | 295篇 |
2012年 | 332篇 |
2011年 | 320篇 |
2010年 | 235篇 |
2009年 | 219篇 |
2008年 | 263篇 |
2007年 | 214篇 |
2006年 | 213篇 |
2005年 | 172篇 |
2004年 | 141篇 |
2003年 | 127篇 |
2002年 | 147篇 |
2001年 | 127篇 |
2000年 | 74篇 |
1999年 | 70篇 |
1998年 | 63篇 |
1997年 | 45篇 |
1996年 | 40篇 |
1995年 | 47篇 |
1994年 | 53篇 |
1993年 | 35篇 |
1992年 | 36篇 |
1991年 | 45篇 |
1990年 | 31篇 |
1989年 | 16篇 |
1988年 | 15篇 |
1987年 | 14篇 |
1986年 | 9篇 |
1985年 | 17篇 |
1984年 | 8篇 |
1983年 | 6篇 |
1982年 | 7篇 |
1981年 | 8篇 |
1980年 | 6篇 |
1979年 | 6篇 |
1978年 | 5篇 |
1977年 | 5篇 |
1971年 | 5篇 |
1962年 | 3篇 |
排序方式: 共有5091条查询结果,搜索用时 358 毫秒
111.
A.J. Leusink G. An Koten J.W. Marsman J.G. Noltes 《Journal of organometallic chemistry》1973,55(2):419-425
Bis{2-[(dimethylamino)methyl]phenyl}silverlithium has been prepared and characterized. Molecular weight determinations, and 13C NMR and 1H NMR spectra reveal that the compound exists (in benzene) as a tetranuclear mixed metal cluster containing aryl groups bridging the silver and lithium atoms. Silver-proton, silver-carbon and lithium-carbon couplings have been observed in the NMR spectra of this compound. 相似文献
112.
AnLIU ZhongMeiZOU LiZhenXU ShiLinYANG 《中国化学快报》2003,14(11):1144-1145
A new compound, subglain B, was isolated from the stems of Uvaria tonkinensis var.subglabra and its structure was identified as 1S, 2R, 3S, 6R-1-benzoyloxymethylene-1,2-dihydroxy-3-benzoyloxy-6-chlorocyclohex-4-ene (1), by spectral evidences. 相似文献
113.
Aggregation of sodium 1-(n-alkyl)naphthalene-4-sulfonates in aqueous solution: micellization and microenvironment characteristics 总被引:2,自引:0,他引:2
Tan XL Zhang L Zhao S Li W Ye JP Yu JY An JY 《Langmuir : the ACS journal of surfaces and colloids》2004,20(17):7010-7014
In aqueous solution, the micellization and microenvironment characteristics of the micelle assemblies of three anionic surfactants, sodium 1-(n-alkyl)naphthalene-4-sulfonates (SANS), have been investigated by steady-state fluorescence and time-resolved fluorescence decay techniques using pyrene, Ru(bpy)3(2+), and 1,6-diphenyl-1,3,5-hexatriene as fluorescence probes. The critical micelle concentrations (cmc's), effective carbon atom numbers (neff's), hydrophilic-lipophilic balances (HLBs), mean micelle aggregation numbers, micropolarities, and microviscosities of these surfactant micelles have been determined. The logarithmic cmc of the alkylnaphthalene sulfonates decreases linearly with an increase in the neff. The logarithmic aggregation number of the alkylnaphthalene sulfonates increases linearly with an increase in the neff. However, in contrast to the alkylsufonates and the alkylbenzene sulfonates, the aggregation for these alkylnaphthalene sulfonate molecules is less sensitive to the increase in the neff. The micropolarity of these alkylnaphthalene sulfonate micelles is less sensitive to the increase in the alkyl chain length and is lower than that of sodium dodecyl sulfate (SDS). The microviscosity of these alkylnaphthalene sulfonate micelles increases with an increase in the alkyl chain length and is lower than those of nonionic surfactants and zwitterionic surfactants. These results suggest that naphthyl rings have a notable effect on the micellization of SANS. 相似文献
114.
Three unusual compounds based on polyoxometalate building blocks, [(H2O)5Na2(C6NO2H4)(C6NO2H5)3Ag2][Ag2IMo6O24(H2O)4] x 6.25H2O (1), [(H2O)4Na2(C6NO2H5)6Ag3][IMo6O24] x 6H2O (2), and (C6NO2H6)2[(C6NO2H5)2Ag][Cr(OH)6Mo6O18] x 4H2O (3), have been synthesized and characterized by elemental analysis; IR, XPS, and ESR spectroscopy; TG analysis; and single-crystal X-ray diffraction. Compound 1 is constructed from the cationic two-dimensional (2D) coordination polymer sheets which are constituted of [(H2O)5Na2(C6NO2H4)(C6NO2H5)3Ag2]3+ and anionic [Ag2IMo6O24(H2O)4]3- chains as pillars, forming a three-dimensional (3D) supramolecular framework via weak Ag-O interactions. Compound 2 is composed of the well-defined [IMo6O24]5- building blocks, which are linked through trinuclear Ag-pyridine-3-carboxylic acid, [(C6NO2H5)6Ag3]3+, fragments into a one-dimensional (1D) hybrid chain; adjacent chains are further connected by sodium cations to yield a novel 2D network. Compound 3 has a 1D chainlike structure constructed from [Cr(OH)6Mo6O18]3- building blocks and Ag-pyridine-4-carboxylic acid coordination units. The crystal data for these compounds are the following: 1, triclinic, P1, a = 13.280(3) A, b = 13.641(3) A, c = 16.356(3) A, alpha = 89.68(3) degrees, beta = 88.31(3) degrees, gamma = 75.87(3) degrees, Z = 2; 2, triclinic, P1, a = 11.978(2) A, b = 12.008(2) A, c = 13.607(3) A, alpha = 116.14(3) degrees, beta = 108.85(3) degrees, gamma = 93.86(3) degrees, Z = 1; 3, triclinic, P1, a = 10.458(2) A, b = 10.644(2) A, c = 12.295(3) A, alpha = 97.40(3) degrees, beta = 112.38(3) degrees, gamma = 113.59(3) degrees, Z = 1. 相似文献
115.
Hee-Yoon LeeMihyun An 《Tetrahedron letters》2003,44(14):2775-2778
α,β-Unsaturated ketones and aldehydes were selectively reduced to the corresponding saturated carbonyl compounds by Co2(CO)8-H2O system. The current reducing system also offered a chemoselective reduction of less substituted unsaturated carbonyl groups. 相似文献
116.
A new dual‐amplification strategy of electrochemical signaling from antigen–antibody interactions was proposed via backfilling gold nanoparticles on (3‐mercaptopropyl) trimethoxysilane sol‐gel (MPTS) functionalized interface. The MPTS was employed not only as a building block for the electrode surface modification but also as a matrix for ligand functionalization with first amplification. The second signal amplification strategy introduced in this study was based on the backfilling immobilization of nanogold particles to the immunosensor surface. Several coupling techniques, such as with nanogold but not MPTS or with MPTS but not nanogold, were investigated for the determination of carcinoembryonic antigen (CEA) as a model, and a very good result was obtained with nanogold and MPTS coupling immunosensor. With the noncompetitive format, the formation of the antigen–antibody complex by a simple one‐step immunoreaction between the immobilized anti‐CEA and CEA in sample solution introduced membrane potential change before and after the antigen–antibody interaction. Under optimal conditions, the proposed immunosensor exhibited a good electrochemical behavior to CEA in a dynamic concentration range of 4.4 to 85.7 ng/mL with a detection limit of 1.2 ng/mL (at 3 δ). Moreover, the precision, reproducibility and stability of the as‐prepared immunosensor were acceptable. Importantly, the proposed methodology would be valuable for diagnosis and monitoring of carcinoma and its metastasis. 相似文献
117.
Gold nanotubule membranes were prepared by using electroless deposition of gold within the pores and surfaces of polycarbonate track-etched membranes.And the gold nanotubule membrane was used as an electrode for determination of uric acid in urine samples for the first time.In Britton-Robinson buffer of pH 4.56,uric acid exhibited well-defined differential pulse voltammograms.And the interference between coexistent ascorbic acid and uric acid was overcome owing to the attractive ability of the gold nanotubule electrode to yield a large anodic peak difference ca.0.404 V(vs.SCE).The proposed method was then applied to the determination of uric acid in urine without any pretreatment. 相似文献
118.
Xiaofeng Wu Jong Min An Jizhen Shang Eugene Huh Sujie Qi Eunhye Lee Haidong Li Gyoungmi Kim Huimin Ma Myung Sook Oh Dokyoung Kim Juyoung Yoon 《Chemical science》2020,11(41):11285
Acetylcholinesterase (AChE) is an extremely critical hydrolase tightly associated with neurological diseases. Currently, developing specific substrates for imaging AChE activity still remains a great challenge due to the interference from butyrylcholinesterase (BChE) and carboxylesterase (CE). Herein, we propose an approach to designing specific substrates for AChE detection by combining dimethylcarbamate choline with a self-immolative scaffold. The representative P10 can effectively eliminate the interference from CE and BChE. The high specificity of P10 has been proved via imaging AChE activity in cells. Moreover, P10 can also be used to successfully map AChE activity in different regions of a normal mouse brain, which may provide important data for AChE evaluation in clinical studies. Such a rational and effective approach can also provide a solid basis for designing probes with different properties to study AChE in biosystems and another way to design specific substrates for other enzymes.In this work, a new approach was developed for designing the representative P10 with high selectivity and sensitivity for imaging AChE activity in the cells and normal mouse brain. 相似文献
119.
Oligomers of l-lactic acid and citric acid (PLCA) were synthesized by reacting lactic acid with citric acid in the presence of stannous chloride. The chemical compositions of these multicarboxylated oligomers were verified by FT-IR and 1H-NMR spectroscopy. The thermal characteristics of the oligomers, such as glass transition temperature Tg, melting temperature Tm and melting enthalpy, were confirmed by DSC. The crystallinity of the oligomers were determined by DSC and WXRD. Meanwhile, the acid-base surface characteristics of PLCA have been determined by contact angle. The results implicated that these oligomers may be used to entrap the cospecies on PLLA surface in tissue engineering. 相似文献
120.
Starting from shikimic acid, the total synthesis of zeylenone was studied. The product was proved to be the (+)antipode of zeylenone through analysis and comparison of their respective spectra (including NMR, MS, IR and CD) and optical data. The absolute configuration of the natural product was thus determined to be (1S,2S,3R). 相似文献