全文获取类型
收费全文 | 21733篇 |
免费 | 1375篇 |
国内免费 | 1867篇 |
专业分类
化学 | 20092篇 |
晶体学 | 400篇 |
力学 | 1226篇 |
综合类 | 84篇 |
数学 | 341篇 |
物理学 | 2832篇 |
出版年
2024年 | 7篇 |
2023年 | 203篇 |
2022年 | 330篇 |
2021年 | 360篇 |
2020年 | 635篇 |
2019年 | 665篇 |
2018年 | 716篇 |
2017年 | 955篇 |
2016年 | 1090篇 |
2015年 | 841篇 |
2014年 | 855篇 |
2013年 | 2199篇 |
2012年 | 1398篇 |
2011年 | 1177篇 |
2010年 | 1074篇 |
2009年 | 1320篇 |
2008年 | 1144篇 |
2007年 | 1213篇 |
2006年 | 1058篇 |
2005年 | 915篇 |
2004年 | 810篇 |
2003年 | 689篇 |
2002年 | 591篇 |
2001年 | 520篇 |
2000年 | 478篇 |
1999年 | 413篇 |
1998年 | 383篇 |
1997年 | 339篇 |
1996年 | 302篇 |
1995年 | 360篇 |
1994年 | 290篇 |
1993年 | 235篇 |
1992年 | 188篇 |
1991年 | 161篇 |
1990年 | 156篇 |
1989年 | 134篇 |
1988年 | 159篇 |
1987年 | 168篇 |
1986年 | 102篇 |
1985年 | 80篇 |
1984年 | 94篇 |
1983年 | 21篇 |
1982年 | 58篇 |
1981年 | 25篇 |
1980年 | 19篇 |
1979年 | 17篇 |
1978年 | 8篇 |
1977年 | 4篇 |
1973年 | 6篇 |
1959年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
Ferroelectric Coordination Polymers Self‐Assembled from Mesogenic Zinc(II) Porphyrin and Dipolar Bridging Ligands 下载免费PDF全文
Dr. Joseph K.‐H. Hui Hiroyuki Kishida Keita Ishiba Kenta Takemasu Dr. Masa‐aki Morikawa Prof. Dr. Nobuo Kimizuka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14213-14218
A new class of ferroelectric coordination‐based polymers has been developed by the self‐assembly of lipophilic zinc porphyrin ( ZnP ) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination‐based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization–electric field (P–E) loops and inversion current peaks in current–voltage (I–V) loops. The observed ferroelectric properties are explainable by flip–flop rotation of the dipolar axle ligands induced by the applied electric field, as demonstrated by the positive‐up–negative‐down (PUND) measurements. The present system provides a new operating principle in supramolecular ferroelectrics. 相似文献
92.
Chiral separation of phenylalanine and tryptophan by capillary electrophoresis using a mixture of β‐CD and chiral ionic liquid ([TBA] [l‐ASP]) as selectors 下载免费PDF全文
Wu Yujiao Wang Guoyan Zhao Wenyan Zhang Hongfen Jing Huanwang Chen Anjia 《Biomedical chromatography : BMC》2014,28(5):610-614
In this paper, a simple, effective and green capillary electrophoresis separation and detection method was developed for the quantification of underivatized amino acids (dl ‐phenylalanine; dl ‐tryptophan) using β‐Cyclodextrin and chiral ionic liquid ([TBA] [l ‐ASP]) as selectors. Separation parameters such as buffer concentrations, pH, β‐CD and chiral ionic liquid concentrations and separation voltage were investigated for the enantioseparation in order to achieve the maximum possible resolution. A good separation was achieved in a background electrolyte composed of 15 mm sodium tetraborate, 5 mm β‐CD and 4 mm chiral ionic liquid at pH 9.5, and an applied voltage of 10 kV. Under optimum conditions, linearity was achieved within concentration ranges from 0.08 to 10 µg/mL for the analytes with correlation coefficients from 0.9956 to 0.9998, and the analytes were separated in less than 6 min with efficiencies up to 970,000 plates/m. The proposed method was successfully applied to the determination of amino acid enantiomers in compound amino acids injections, such as 18AA‐I, 18AA‐II and 3AA. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
93.
Roksana Kordala-Markiewicz Hubert Rodak Bartosz Markiewicz Filip Walkiewicz Agata Sznajdrowska Katarzyna Materna Katarzyna Marcinkowska Tadeusz Praczyk Juliusz Pernak 《Tetrahedron》2014
Ammonium ionic liquids with the 4-chloro-2-methylphenoxyacetate anion were synthesized and characterized. Physicochemical properties, such as thermal stability, phase transition temperatures, viscosity, density, refractive index, as well as surface activity and herbicidal activity were determined. Improved physicochemical properties suggest a reduced environmental impact of newly formed group of herbicidal ionic liquids (HILs). HILs with a longer substituent can be characterized with better herbicidal activity in comparison with commercial products. 相似文献
94.
Hisanao Yamamoto Akira Fujita Miyuki Harada Mitsukazu Ochi 《Molecular Crystals and Liquid Crystals》2014,588(1):41-50
A liquid crystalline epoxy resin (LCE) having α-methylstilbene as a mesogenic unit and an ethylene-oxy unit as a spacer (DGE(C2-MS-C2)) was synthesized and characterized. DGE (C2-MS-C2) has a lower melting point (MP) compared to the diglycidylether of 4,4′-dihydroxy-α-methylstilbene (DGEDHMS). The curing of DGE (C2-MS-C2) with diaminodiphenylethane (DDEt) in a mesophase generated a liquid crystalline (LC) network, which have a more highly layered structure than DGEDHMS. The LC network showed extensively large fracture energy on a tensile test. Introducing spacers outside the mesogen unit promotes the mesogen unit to form a highly ordered structure, which enhances the versatility of LC epoxy resins. 相似文献
95.
Pressurized liquid extraction (PLE) has been successfully applied for the first time to the extraction of five iodinated X-ray contrast media from sludge. Once optimized all PLE parameters, the extract has been analyzed by liquid chromatography–tandem mass spectrometry, being the method developed sensible enough to reach limit of quantifications (LOQs) of 25 μg kg−1 (d.w.). The developed method has been applied to the analysis of sludge from urban sewage treatment plants and although some compounds such as iopromide, diatrizoic acid and iopamidol have been identified, their concentrations have been lower than their LOQs. 相似文献
96.
Luis G. MacDowell Jorge Benet Nebil A. Katcho Jose M.G. Palanco 《Advances in colloid and interface science》2014
In this paper we review simulation and experimental studies of thermal capillary wave fluctuations as an ideal means for probing the underlying disjoining pressure and surface tensions, and more generally, fine details of the Interfacial Hamiltonian Model. We discuss recent simulation results that reveal a film-height-dependent surface tension not accounted for in the classical Interfacial Hamiltonian Model. We show how this observation may be explained bottom-up from sound principles of statistical thermodynamics and discuss some of its implications. 相似文献
97.
Chiral separability of boron cluster species studied by screening approaches utilizing polysaccharide‐based chiral stationary phases 下载免费PDF全文
In this study, the screening steps of chiral separation strategies with polysaccharide‐based chiral stationary phases were applied on boron cluster compounds in normal‐phase liquid chromatography (NPLC) and polar organic solvents chromatography (POSC). Since the screening steps were initially developed to analyze organic compounds, their applicability for boron clusters was investigated. Overall, the screening steps in NPLC were applicable for the separation of zwitterions, while for anions mostly no elution was observed. A hypothesis for the latter behavior is precipitation of anions in the nonpolar mobile phases. Ten out of 11 compounds could be partially or baseline separated on the NPLC screening systems. In POSC, all zwitterions were separated on at least one of the screening systems, with an overall lower retention as in NPLC. Anions were detected but not separated in the majority of the experiments. Also their retention on the chiral stationary phases was very limited. This study showed that the chiral discrimination potential of chemically modified polysaccharides is meaningful for chiral separations of structurally chiral boron cluster species, but needs further systematic research, in which recognition mechanisms should be further explored. In addition, some unusual peaks also indicated that conditions with a high separation efficiency must first be searched for some of the tested systems. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
98.
Transport of oil and gas-condensate mixtures of various compositions is found to be accompanied by a slight increase in viscosity in the coldest period when ground temperatures at depth of a condensate pipeline reach 0 – minus 4°С. Fall in temperature of oil fluids under study to minus 10 – minus 30°С is accompanied by a sharp increase in all structural and rheological parameters of the mixture. Even a slight amount of oil added to a gas-condensate mixture causes a significant decrease in viscosity in the negative temperature range. As a result, cloud and pour point of a mixture falls, its amount decreases, the structure of paraffin deposits changes. 相似文献
99.
Ionic liquid‐based dispersive liquid–liquid microextraction followed by RP‐HPLC determination of saquinavir in rat serum: application to pharmacokinetics 下载免费PDF全文
Nageswara Rao Ramisetti Narendra Varma Nimmu Gangu Naidu Challa 《Biomedical chromatography : BMC》2014,28(12):1874-1880
An ionic liquid‐based dispersive liquid–liquid microextraction followed by RP‐HPLC determination of the most commonly prescribed protease inhibitor, saquinavir, in rat plasma was developed and validated. The effects of different ionic liquids, dispersive solvents, extractant/disperser ratio and salt concentration on sample recovery and enrichment were studied. Among the ionic liquids investigated, 1‐butyl‐3‐methylimidazolium hexafluorophosphate was found to be most effective for extraction of saquinavir from rat serum. The recovery was found to be 95% at an extractant/disperser ratio of 0.43 using 1‐butyl‐3‐methylimidazolium hexafluorophosphate and methanol as extraction and dispersive solvents. The recovery was further enhanced to 99.5% by addition of 5.0% NaCl. A threefold enhancement in detection and quantification limits was achieved, at 0.01 and 0.03 µg/mL, compared with the conventional protein precipitation method. A linear relationship was observed in the range of 0.035–10.0 µg/mL with a correlation coefficient (r2) of 0.9996. The method was validated and applied to study pharmacokinetics of saquinavir in rat serum. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
100.
Laura Rubio María Leticia Oca Luis Sarabia Inmaculada García María Cruz Ortiz 《Journal of Chemometrics》2016,30(2):58-69
Internal standards can be added at different stages of an analytical procedure. When they are added at the beginning of a multiresidue method and their behavior is not exactly the same as that of the analytes, the intended correction for small variations within the analytical process could not be achieved. Because of this, in the present work, the use of d ‐optimal designs together with desirability functions is proposed to state the experimental response under study. The overall desirability function used relates two analytical criteria: to assess a similar chemical behavior of each analyte in relation to its internal standard and to avoid a significant reduction of the absolute peak area of the internal standards. This strategy has been applied to the analysis of the effect of four factors related to the extraction and purification steps of six tranquillizers and a β‐blocker from pig muscle analyzed by liquid chromatography–tandem mass spectrometry. The effect of those factors has been evaluated by means of an ad hoc d ‐optimal design consisting of only 11 experiments. The resulting levels of the four factors that enable to achieve the greatest overall desirability have also been compared with those obtained when either the standardized or absolute peak area has been considered as response. Differences in both the significant factors and their optimum levels have been observed. It is noticeable that the experimental effort necessary to study the effect of the factors has been reduced by more than 50% thanks to the d ‐optimal design. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献