全文获取类型
收费全文 | 2502篇 |
免费 | 315篇 |
国内免费 | 290篇 |
专业分类
化学 | 1146篇 |
晶体学 | 23篇 |
力学 | 319篇 |
综合类 | 40篇 |
数学 | 700篇 |
物理学 | 879篇 |
出版年
2024年 | 6篇 |
2023年 | 28篇 |
2022年 | 56篇 |
2021年 | 73篇 |
2020年 | 90篇 |
2019年 | 82篇 |
2018年 | 75篇 |
2017年 | 117篇 |
2016年 | 98篇 |
2015年 | 97篇 |
2014年 | 134篇 |
2013年 | 224篇 |
2012年 | 158篇 |
2011年 | 177篇 |
2010年 | 134篇 |
2009年 | 166篇 |
2008年 | 167篇 |
2007年 | 162篇 |
2006年 | 142篇 |
2005年 | 128篇 |
2004年 | 126篇 |
2003年 | 91篇 |
2002年 | 80篇 |
2001年 | 59篇 |
2000年 | 67篇 |
1999年 | 55篇 |
1998年 | 55篇 |
1997年 | 34篇 |
1996年 | 33篇 |
1995年 | 32篇 |
1994年 | 26篇 |
1993年 | 27篇 |
1992年 | 17篇 |
1991年 | 10篇 |
1990年 | 11篇 |
1989年 | 7篇 |
1988年 | 6篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 7篇 |
1984年 | 7篇 |
1983年 | 6篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 5篇 |
1979年 | 6篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1973年 | 4篇 |
排序方式: 共有3107条查询结果,搜索用时 546 毫秒
41.
高分散直接甲醇燃料电池Pt/C阴极电催化剂的制备过程机理与表征 总被引:4,自引:1,他引:4
通过调变的多元醇法制备了40%Pt/C直接甲醇燃料电池阴极电催化剂,应用透射电镜(TEM)及X射线衍射(XRD)方法表征催化剂.结果表明,由该制备方法可得到高分散,金属粒子粒径分布窄的高载量贵金属催化剂.TEM统计结果表明,调变多元醇法制备的40%Pt/C催化剂的金属粒子平均粒径约为2.9nm.直接甲醇燃料电池单池性能测试表明,该方法制得的40%Pt/C的电催化氧还原能力比同型商品催化剂更好.另外,利用UV-Vis光谱研究了催化剂的制备过程.结果表明,在调变的多元醇法中,Pt4+的还原是一步完成的. 相似文献
42.
DFT Study on the (S)-Proline-catalyzed Direct Aldol Reaction between Acetone and 4-Nitrobenzaldehyde
1 INTRODUCTION Aldol reaction, one of the most important C–C bond-formation reactions, is widely utilized in orga- nic synthesis[1]. Extensive efforts have been donated to the development of catalytic stereo-selective va- riants of this reaction[2]. However, the direct aldol reaction between unmodified carbonyles would be the most attractive synthetic alternative. Proline-catalyzed intermolecular direct aldol reac- tion between acetone and 4-nitrobenzaldehyde was first reported by List… 相似文献
43.
Wei SUN Dan Dan WANG Rui Fang GAO Jian SUN Kui JIAO 《中国化学快报》2006,17(12):1589-1591
In recent years the direct electron transfer of redox protein on electrode surface has attracted great attentions1. Different kind of modified electrode and various supporting films for immobilization of proteins had been proposed. But most of them are ba… 相似文献
44.
T. Ozawa 《Journal of Thermal Analysis and Calorimetry》1993,40(3):1379-1398
To satisfy the needs for industrial standards for thermal analysis in the Japanese polymer industry, round-robin tests of
differential scanning calorimetry (DSC), thermogravimetry (TG), thermomechanical analysis (TMA) and thermodilatometry (TD)
have been carried out recently. The results are discussed in this short review.
The DSC applications tested were not only for determination of transition temperature but also for measurements of the transition
heat and heat capacity. The TG task group did not aim at longterm thermal endurance studies, but relative thermal stability
in molding and estimation of filler content, residual solvent content, etc. TMA was found to be a useful tool for measuring
softening temperature and heat distortion temperature, especially for high-temperature engineering plastics, instead of the
Vicat test which has temperature limitations. For temperature calibration of DSC and TG, ICTA-NIST certified reference materials
were used together with other potential temperature standards; some inorganic substances and alloys were not found to be preferable
to pure metals. For TMA and TD metal plates were found to be very useful for temperature calibration. Analysis of the round-robin
test results also clarified present status of practical applications of thermal analysis, such as reproducibility and causes
of errors.
Plenary lecture 相似文献
45.
A recently characterized oviposition-deterring pheromone (ODP, structure 1) of the European cherry fruit fly was used as a test case for probing the potential of tandem mass spectrometry (MS/MS) in structure elucidation as a stand-alone technique. The glycolipid-taurinate 1 was subjected to MS/MS analyses under a variety of conditions with and without preceding chemical degradation. Acidic methanolysis of 1 and subsequent in-batch derivatization (trideuterioacetylation) yielded methyl 2,3,4,6-tetrakis-O-trideuterioacetyl-glucopyranoside (2), methyl 8,15-bis-trideuterioacetoxy-palmitate (3), and taurine (4) as suitable target compounds for direct mixture analysis.Low energy collision induced dissociation (CID) on selected precursor ions (MS/MS on [M + H – CH3OH]+ and [M + H]+ produced by fast atom bombardment (FAB)) allowed direct identification of 2 and 4, respectively, by comparison with appropriate reference ions. In the case of 3, low energy CID (desorption chemical ionization (DCI) instead of FAB, MS/MS on [M + H]+) permitted deduction of gross molecular structure, but failed to provide positional detail. In sharp contrast,high energy CID of trideuterioacetylated intact 1 (FAB-MS/MS on [M – H]– ions of la) clearly revealed a linear 8,15-hydroxylated palmitic acid backbone. Less certain was assignment of 15-O-glucosylation by this approach. 相似文献
46.
0IntroductionStudies of direct electrochemistry of proteins orenzymes at electrodes can serve as a basis for build-ing electrochemical biosensors,enzymatic bioreactors,and biomedical devices[1].This approach simplifiessuch devices without using mediators and is of partic-ular significance for fabricating the third generationbiosensors[2].For example,if a protein or enzyme im-mobilized on electrode surface is capable of directelectron transfer without loss of bioactivities,it can beused in the … 相似文献
47.
48.
Elena E. Ferapontova John Castillo Dmitri Hushpulian Vladimir Tishkov Tatiana Chubar Irina Gazaryan Lo Gorton 《Electrochemistry communications》2005,7(12):1291-1297
Direct electron transfer (DET) reactions of recombinant tobacco peroxidase (rTOP), namely direct electroreduction of Compound I/Compound II and heme Fe3+/2+ conversion, were studied on gold electrodes. rTOP of wild type, non-glycosylated, was produced using an Escherichia coli expression system. At pH 5.0, the redox potential for direct electrochemical transformation of the Fe3+/2+ of the peroxidase heme was −143 mV vs. AgAgCl, and 0.26 ± 0.07 pmol of the adsorbed rTOP were in DET contact with the gold electrode. The total amount of the adsorbed rTOP estimated from QCM data was 53 ± 5 pmol/cm2 or 1.67 pmol when referred to the surface area of the electrodes used for electrochemical measurements. Of 1.67 pmol of adsorbed rTOP, only 0.76 pmol were catalytically active. DET between Au and the enzyme was also studied in the reaction of the bioelectrocatalytic reduction of H2O2 by cyclic voltammetry and amperometric detection of H2O2 at +50 mV with rTOP-modified Au electrodes placed in a wall-jet flow-through electrochemical cell. Maximal bioelectrocatalytic current response of the rTOP-modified gold electrodes to H2O2 was observed at pH 5.0 and stemmed from its bioelectrocatalytic reduction based on DET between Au and the active site of rTOP. Kinetic analysis of the DET reactions gave 52% of the adsorbed rTOP molecules active in DET reactions (0.4 pmol of adsorbed catalytically active rTOP, correspondingly), which correlated well with the non-catalytic-voltammetry data. DET was characterised by a heterogeneous ET rate constant of 13.2 s−1, if one takes into account the QCM data, and 19.6 s−1, if the amount of rTOP estimated from the data on DET transformation of Fe3+/2+ couple of rTOP is considered. The sensitivity for H2O2 obtained for the rTOP-modified Au electrodes was 0.7 ± 0.1 A M−1 cm−2. These are the first ever-reported data on DET reactions of anionic plant peroxidases on bare gold electrodes. 相似文献
49.
50.
Richard J. Wiener Philip W. Hammer Charles E. Swanson David C. Samuels Russell J. Donnelly 《Journal of statistical physics》1991,64(5-6):913-926
Taylor-Couette flow subject to a Coriolis force is studied experimentally and numerically. In the experiment, the Couette apparatus is mounted on a turntable with the axis of the cylinders orthogonal to the rotation vector of the turntable. The Coriolis force stabilizes the fluid against the onset of Taylor vortices and alters the velocity fields, both above and below the transition from the initial flow. At small dimensionless turntable frequencies, the transition yields time-independent Taylor vortices which are tilted with respect to the cylinder axis. At larger there is a direct transition to turbulence. We determine the first-order correction to the classical Couette initial flow, to account for the effects of the Coriolis force, by expanding in powers of. We present numerical results for the axial velocity (the only nonvanishing correction term to order) in the infinite-cylinder approximation. 相似文献