全文获取类型
收费全文 | 83575篇 |
免费 | 492篇 |
国内免费 | 418篇 |
专业分类
化学 | 28418篇 |
晶体学 | 839篇 |
力学 | 6837篇 |
数学 | 32513篇 |
物理学 | 15878篇 |
出版年
2022年 | 41篇 |
2021年 | 49篇 |
2020年 | 76篇 |
2019年 | 95篇 |
2018年 | 10475篇 |
2017年 | 10284篇 |
2016年 | 6165篇 |
2015年 | 940篇 |
2014年 | 399篇 |
2013年 | 568篇 |
2012年 | 4116篇 |
2011年 | 10894篇 |
2010年 | 5817篇 |
2009年 | 6200篇 |
2008年 | 6933篇 |
2007年 | 9138篇 |
2006年 | 637篇 |
2005年 | 1714篇 |
2004年 | 1903篇 |
2003年 | 2264篇 |
2002年 | 1275篇 |
2001年 | 327篇 |
2000年 | 352篇 |
1999年 | 221篇 |
1998年 | 267篇 |
1997年 | 197篇 |
1996年 | 274篇 |
1995年 | 175篇 |
1994年 | 132篇 |
1993年 | 135篇 |
1992年 | 93篇 |
1991年 | 109篇 |
1990年 | 87篇 |
1989年 | 93篇 |
1988年 | 91篇 |
1987年 | 86篇 |
1986年 | 87篇 |
1985年 | 98篇 |
1984年 | 94篇 |
1983年 | 83篇 |
1982年 | 87篇 |
1981年 | 85篇 |
1980年 | 90篇 |
1979年 | 85篇 |
1978年 | 83篇 |
1977年 | 58篇 |
1976年 | 53篇 |
1973年 | 41篇 |
1914年 | 45篇 |
1909年 | 41篇 |
排序方式: 共有10000条查询结果,搜索用时 187 毫秒
991.
Hood BL Lucas DA Kim G Chan KC Blonder J Issaq HJ Veenstra TD Conrads TP Pollet I Karsan A 《Journal of the American Society for Mass Spectrometry》2005,16(8):1221-1230
With advancements in the analytical technologies and methodologies in proteomics, there is great interest in biomarker discovery in biofluids such as serum and plasma. Current hypotheses suggest that the low molecular weight (LMW) serum proteome possesses an archive of clipped and cleaved protein fragments that may provide insight into disease development. Though these biofluids represent attractive samples from which new and more accurate disease biomarkers may be found, the intrinsic person-to-person variability in these samples complicates their discovery. Mice are one of the most extensively used animal models for studying human disease because they represent a highly controllable experimental model system. In this study, the LMW serum proteome was compared between xenografted tumor-bearing mice and control mice by differential labeling utilizing trypsin-mediated incorporation of the stable isotope of oxygen, 18O. The digestates were combined, fractionated by strong cation exchange chromatography, and analyzed by nanoflow reversed-phase liquid chromatography coupled online with tandem mass spectrometry, resulting in the identification of 6003 proteins identified by at least a single, fully tryptic peptide. Almost 1650 proteins were identified and quantitated by two or more fully tryptic peptides. The methodology adopted in this work provides the means for future quantitative measurements in comparative animal models of disease and in human disease cohorts. 相似文献
992.
R. A. Alieva S. Z. Gamidov F. M. Chyragov A. A Azizov 《Journal of Analytical Chemistry》2005,60(12):1114-1117
A method is developed for cadmium and zinc preconcentration on a minicolumn packed with a new chelating polymer sorbent. The effects of the test solution pH and volume, the sample matrix composition, the eluent volume, and the sample and eluent flow rates are studied. Zinc and cadmium in the eluate are determined by flame atomic absorption spectrometry. Under optimal conditions, the determined ion recovery is more than 95%. The detection limits (3σ, n = 20) are found to be 15.0 (Cd) and 17.2 (Zn) ng/mL. The developed method is employed for cadmium and zinc determination in samples of seawater and water obtained after oil pumping. 相似文献
993.
An amperometric detector with a small thin mercury film electrode is described. The device demonstrates advantageous operational
characteristics such as small dispersion (D<2) and “memory effect” (me<0.6%), extensive maximum sample frequency (msf −200
samples/h), and high sensitivity. It has been proven useful in flow-injection analysis at a constant potential under hydrodynamic
conditions. 相似文献
994.
In the course of investigations on equestrian supplemental products for the presence of doping substances, two products were found to contain forbidden substances. As reported earlier a plant extract (Mexican cactus extract) named “Energy 5” contained the anabolic androgenic steroids (AAS) stanozolol, 17β-hydroxy-17α-methyl-5α-androstane-3β-ol (3β,5α-THMT) as well as mestanolone not declared on the label. In the present study, a product called “Super Kalm Paste” was tested. Analysis by gas chromatography - mass spectrometry (GC-MS) revealed that the preparation contained the class I anti-arrhythmics quinine (trade names KinidinTM, Durules) and cinchonine. The samples were prepared according to a sample preparation procedure established for anabolic steroids in nutritional supplements for humans. The sample treatment comprised the extraction and purification of the analytes as well as the chemical conversion with N-methyl-N-trimethylsilyl-trifluoracetamide (MSTFA) to yield the trimethylsilyl (TMS)-derivatives. To verify whether the administration of such products could lead to positive doping tests, a pilot excretion study on “Energy 5” was conducted with two geldings, and urine samples were collected. Gas chromatography - high resolution mass spectrometry (GC-HRMS) after solid phase extraction and mixed derivatisation has demonstrated the presence of the stanozolol metabolite 16β-hydroxy-stanozolol in urine samples after “Energy 5” application. 相似文献
995.
Assefa Z Omary MA McBurnett BG Mohamed AA Patterson HH Staples RJ Fackler JP 《Inorganic chemistry》2002,41(24):6274-6280
The structures and temperature-dependent photoluminescence properties of the one-dimensional compounds [(TPA)(2)Au][Au(CN)(2)], 1, and (TPA)AuCl, 2, are reported. An extended linear chain with weak Au.Au interactions along the c-axis is evident in the structure of 1, and a helical chain with a pitch of 3.271 A is seen for 2. The intrachain Au...Au separation is 3.457(1) and 3.396(2) A in 1 and 2, respectively. As a result of this weak Au...Au interaction, the physical properties of these compounds are anisotropic. Scanning electron microscopy (SEM) studies indicate that single crystals of both compounds are noninsulating. Single crystals of 1 do not luminesce visibly, but grinding the crystals finely initiates a strong green emission under UV irradiation at room temperature. Further interesting optical properties include the dependence of the emission profile of the powder on the exciting wavelength and luminescence thermochromism. When excited at wavelengths < 360 nm, the powder exhibits a blue emission at 425 nm while excitation with longer wavelengths leads to a green emission near 500 nm. While the green emission dominates at ambient temperature, cooling to cryogenic temperatures leads to the dominance of the blue emission. Fibers of 2 are luminescent at 78 K with an emission band centered at 580 nm. Compound 1 crystallizes in the orthorhombic space group Cccm (No. 66), with Z = 2, a = 6.011(1) A, b = 23.877(6) A, c = 6.914(1) A, V = 992.3(3) A(3), and R = 0.0337. Compound 2 crystallizes in the trigonal space group R3 (No. 148), with Z = 18, a = 22.587(2) A, b = 22.587(2) A, c = 9.814(2) A, V = 4336 A(3), and R = 0.0283. 相似文献
996.
Michael I. Bruce Jennifer K. Walton Michael L. Williams Brian W. Skelton Allan H. White 《Journal of organometallic chemistry》1981,212(3):C35-C38
Contrary to some previously depicted structures, the proton in HC5(CO2Me)5 is bonded to two oxygens rather than to carbon; the lithium ion in Li[C5(CO2Me)5] (H2O) is tetrahedrally coordinated by two carbonyl oxygens from one C5 anion, one from a second anion, and a water molecule. 相似文献
997.
Gottfried Lichti Brian S. Hawkett Robert G. Gilbert Donald H. Napper David F. Sangster 《Journal of polymer science. Part A, Polymer chemistry》1981,19(4):925-938
Data are presented on the time evolution of particle-size distributions (PSDs) in seeded and ab initio styrene emulsion polymerization systems. Initiation was by chemical reagent (potassium persulfate) or γ-radiation. The unswollen PSDs at various times during interval II of the polymerization were obtained by direct measurement of calibrated electron micrographs. Experimental results were fitted with the equations that describe the time evolution of an initial PSD. Analytic solutions to these equations that allow for entry, exit, and propagation of free radicals were obtained. The values of the rate coefficients for these processes used to fit the experimental data were in excellent agreement with those obtained from dilatometric kinetics experiments. 相似文献
998.
William H. Pearson Joseph E. Celebuski Yam-Foo Poon Brian R. Dixon Jeffrey H. Glans 《Tetrahedron letters》1986,27(52):6301-6304
Cyclization of heterosubstituted ω-azidodienes 11 provides fused bicyclic 3-pyrrolines 12 in one operation. These pyrrolines are potentially useful intermediates for natural products synthesis, as illustrated by further functionalization. 相似文献
999.
The new methylidene trinickel cluster complexes, [RCNi3(η5-C5H53] (R CMe3 or SiMe3) and [Me3SiCNi3(η5-C5H5)2(η5-C5H4CH2SiMe3)] have been isolated in low yield from reactions between nickelocene and the corresponding alkyllithium reagents, RCH2Li. The compounds [RCNi3(η5-C5H5)3] (R Ph, CMe3 or SiMe3) have also been obtained by treatment of the σ-alkylnickel complexes [(η5-C5H5)Ni(CH2R)(PPh3)] with n-BuLi in the presence of an excess of nickelocene, but under similar conditions [(η5-C5H5)Ni(CH2C1OH7-2)-(PPh3)] (where C1OH7-2 2-naphthyl) failed to give [2-C1OH7CNi3(η5-C5H5)3]. The attempted synthesis of [(η5-C5H5)Ni(CH2CCH)(PPh3)] from [(η5-C5H5)-NiBr(PPh3)] and CHCCH2MgBr gave only [(η5-C5H5)Ni(CCMe)(PPh3)] by an unusual rearrangement reaction. 相似文献
1000.
Dusanka Ž. Obadović Anikó Vajda Maya Garić A. Bubnov Vera Hamplová M. Kašpar Katalin Fodor-Csorba 《Journal of Thermal Analysis and Calorimetry》2005,80(2):519-523
Summary Thermal properties of a homologous series of ferroelectric liquid crystals S-(-)-[4-(2-n-alkoxy-propionyloxy)]biphenyl-4'-[n-alkoxy-(3,5-dimethyl)]benzoate have been investigated by polarizing optical microscopy and differential scanning calorimetry.
The mesophases were identified and confirmed by X-ray too. Three binary mixtures were prepared from the individual homologues.
In one of the mixtures (Mix1), the ferroelectric SmC* phase has broadened and became enantiotropic. This mesophase remained
monotropic in the other two mixtures (Mix2, Mix3). The chiral nematic N* phase did not appear in Mix1, but remained monotropic
for the other two mixtures. Two molecular parameters, the layer spacing and the average intermolecular distance have been
calculated from the X-ray results for the homologues and their mixtures. An intercalated tail-to-tail packing of molecules
was found both in the single compounds and their mixtures resulting in the layer spacing about half of the molecular length
of the single compounds. 相似文献