全文获取类型
收费全文 | 67765篇 |
免费 | 1314篇 |
国内免费 | 420篇 |
专业分类
化学 | 31158篇 |
晶体学 | 452篇 |
力学 | 2434篇 |
综合类 | 16篇 |
数学 | 15372篇 |
物理学 | 20067篇 |
出版年
2022年 | 263篇 |
2021年 | 411篇 |
2020年 | 537篇 |
2019年 | 421篇 |
2018年 | 1708篇 |
2017年 | 1938篇 |
2016年 | 1797篇 |
2015年 | 1375篇 |
2014年 | 1428篇 |
2013年 | 2627篇 |
2012年 | 4760篇 |
2011年 | 4203篇 |
2010年 | 3001篇 |
2009年 | 2539篇 |
2008年 | 2357篇 |
2007年 | 2277篇 |
2006年 | 2178篇 |
2005年 | 5752篇 |
2004年 | 5050篇 |
2003年 | 3250篇 |
2002年 | 1372篇 |
2001年 | 1102篇 |
2000年 | 778篇 |
1999年 | 653篇 |
1998年 | 538篇 |
1997年 | 485篇 |
1996年 | 569篇 |
1995年 | 503篇 |
1994年 | 532篇 |
1993年 | 528篇 |
1992年 | 706篇 |
1991年 | 530篇 |
1990年 | 521篇 |
1989年 | 456篇 |
1988年 | 419篇 |
1987年 | 400篇 |
1986年 | 354篇 |
1985年 | 545篇 |
1984年 | 510篇 |
1983年 | 428篇 |
1982年 | 440篇 |
1981年 | 447篇 |
1980年 | 432篇 |
1979年 | 434篇 |
1978年 | 420篇 |
1977年 | 409篇 |
1976年 | 439篇 |
1975年 | 396篇 |
1974年 | 386篇 |
1973年 | 336篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
2.
3.
4.
Eco‐friendly ionic liquid assisted capillary electrophoresis and α‐acid glycoprotein‐assisted liquid chromatography for simultaneous determination of anticancer drugs in human fluids 下载免费PDF全文
Deia Abd El‐Hady Hassan M. Albishri Rajesh Rengarajan 《Biomedical chromatography : BMC》2015,29(6):925-934
In the current work, two eco‐friendly analytical methods based on capillary electrophoresis (CE) and reversed phase liquid chromatography (RPLC) were developed for simultaneous determination of the most commonly used anticancer drugs for Hodgkin's disease: methotrexate (MTX), vinblastine, chlorambucil and dacarbazine. A background electrolyte (BGE) of 12.5 mmol/L phosphate buffer at pH 7.4 and 0.1 µmol/L 1‐butyl‐3‐methyl imidazolium bromide (BMImBr) ionic liquid (IL) was used for CE measurements at 250 nm detection wavelength, 20 kV applied voltage and 25 °C. The rinsing protocol was significantly improved to reduce the adsorption of IL on the interior surface of capillary. Moreover, RPLC method was developed on α‐1‐acid glycoprotein (AGP) column. Mobile phase was 10 mmol/L phosphate buffer at pH 6.0 (100% v/v) and flow rate at 0.1 mL/min. As AGP is a chiral column, it was successfully separated l ‐MTX from its enantiomer impurity d ‐MTX. Good linearity of quantitative analysis was achieved with coefficients of determinations (r2) >0.995. The stability of drugs measurements was investigated with adequate recoveries up to 24 h storage time under ambient temperature. The limits of detection were <50 and 90 ng/mL by CE and RPLC, respectively. The using of short‐chain IL as an additive in BGE achieved 600‐fold sensitivity enhancement compared with conventional Capillary Zone Electrophoresis (CZE). Therefore, for the first time, the proposed methods were successfully applied to determine simultaneously the analytes in human plasma and urine samples at clinically relevant concentrations with fast and simple pretreatments. Developed IL‐assisted CE and RPLC methods were also applied to measure MTX levels in patients’ samples over time. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
5.
Saleh Z. M. Nasser H. Özkol E. Günöven M. Abak K. Canli S. Bek A. Turan R. 《Journal of nanoparticle research》2015,17(10):1-12
Journal of Nanoparticle Research - Plasmonic interfaces consisting of silver nanoparticles of different sizes (50–100&;nbsp;nm) have been processed by the self-assembled dewetting... 相似文献
6.
Immobilized Catalysts for Iridium‐Catalyzed Allylic Amination: Rate Enhancement by Immobilization 下载免费PDF全文
Dr. Chandi C. Malakar Prof. Dr. Günter Helmchen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(19):7127-7134
The first immobilized catalyst for Ir‐catalyzed asymmetric allylic aminations is described. The catalyst is a cationic (π‐allyl)Ir complex bound by cation exchange to an anionic silica gel support. Preparation of the catalyst is facile, and the supported catalyst displayed considerably enhanced activity compared with the parent homogeneous catalyst. Up to 43 consecutive amination runs were possible in recycling experiments. 相似文献
7.
8.
Thomas Wittmann Dr. Renée Siegel Nele Reimer Dr. Wolfgang Milius Prof. Dr. Norbert Stock Prof. Dr. Jürgen Senker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):314-323
The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH2 by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N2 and H2O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m2 g?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with 1H‐27Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking. 相似文献
9.
10.
We discuss an error estimation procedure for the global error of collocation schemes applied to solve singular boundary value problems with a singularity of the first kind. This a posteriori estimate of the global error was proposed by Stetter in 1978 and is based on the idea of Defect Correction, originally due to Zadunaisky. Here, we present a new, carefully designed modification of this error estimate which not only results in less computational work but also appears to perform satisfactorily for singular problems. We give a full analytical justification for the asymptotical correctness of the error estimate when it is applied to a general nonlinear regular problem. For the singular case, we are presently only able to provide computational evidence for the full convergence order, the related analysis is still work in progress. This global estimate is the basis for a grid selection routine in which the grid is modified with the aim to equidistribute the global error. This procedure yields meshes suitable for an efficient numerical solution. Most importantly, we observe that the grid is refined in a way reflecting only the behavior of the solution and remains unaffected by the unsmooth direction field close to the singular point. 相似文献