首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   2752篇
  免费   929篇
  国内免费   246篇
化学   991篇
晶体学   61篇
力学   166篇
综合类   70篇
数学   163篇
物理学   2476篇
  2024年   3篇
  2023年   16篇
  2022年   60篇
  2021年   69篇
  2020年   103篇
  2019年   61篇
  2018年   69篇
  2017年   127篇
  2016年   133篇
  2015年   112篇
  2014年   177篇
  2013年   223篇
  2012年   241篇
  2011年   237篇
  2010年   219篇
  2009年   211篇
  2008年   209篇
  2007年   194篇
  2006年   191篇
  2005年   177篇
  2004年   162篇
  2003年   123篇
  2002年   97篇
  2001年   121篇
  2000年   108篇
  1999年   50篇
  1998年   70篇
  1997年   47篇
  1996年   44篇
  1995年   47篇
  1994年   24篇
  1993年   35篇
  1992年   25篇
  1991年   23篇
  1990年   17篇
  1989年   10篇
  1988年   24篇
  1987年   9篇
  1986年   10篇
  1985年   7篇
  1984年   5篇
  1983年   3篇
  1982年   3篇
  1980年   4篇
  1979年   5篇
  1978年   3篇
  1977年   5篇
  1976年   3篇
  1974年   5篇
  1973年   2篇
排序方式: 共有3927条查询结果,搜索用时 852 毫秒
101.
We investigate the injection of a pure spin current into a non-magnetic Cu wire in a lateral spin valve. We detect the spin accumulation occurring at the interfaces between the magnetic nanopillars and the non-magnetic wire in the non-local geometry. We confirm that the accumulated spins diffuse equally in the Cu wire irrespective of the presence of a charge current. The inversion of the injector and detector magnetic nanopillars does not affect the spin signal, in agreement with analytical predictions for this system.  相似文献   
102.
A new model of nonlinear electrodynamics with two parameters is investigated. We also consider a model with one dimensional parameter. It was shown that the electric field of a point-like charge is not singular at the origin and there is the finiteness of the static electric energy of point-like charged particle. We obtain the canonical and symmetrical Belinfante energy–momentum tensors and dilatation currents. It is demonstrated that the dilatation symmetry and dual symmetry are broken in the models suggested. We have calculated the static electric energy of point-like particles.  相似文献   
103.
Abstract

Alkyl substituents appended to polymers play the determining role on self-assembly and film-forming properties, and on device performance. In this work, we highlight the effects of the linear and branched flexible chains appended to the acceptor moiety (A) in D-A type copolymers. Two thieno[3,4-c]-pyrrole-4,6-dione (TPD) based copolymers PT1 and PT2 with different alkyl chains, were designed and synthesized. By comparison their UV-vis absorptions, HOMO/LUMO energy levels, as well as the characters in polymer solar cells, the influences of alkyl chains were investigated. Both copolymers showed molecular weights of 21?kDa and similar optical properties with a medium band gap of 1.93?eV, while PT2 with the branched chain exhibited a lower HOMO than that of PT1 (?5.43 vs???5.37?eV). In bulk heterojunction (BHJ) solar cells, PT1 with a linear chain presented a short circuit current (Jsc) of 6.76?mA cm?2, open circuit voltage (Voc) of 0.89?V and power conversion efficiency (PCE) of 2.92%. To the contrary, PT2 showed a Jsc of 3.53?mA cm?2, Voc of 0.99?V, delivering a relatively lower PCE of 2.05%. The result indicates that appending a linear alkyl chain to the TPD unit could sufficient enhance the Jsc value of the related polymer.  相似文献   
104.
This study aimed to seek an efficient method to extract and purify yunaconitine and 8‐deacetylyunaconitine from Aconitum vilmorinianum Kom. by accelerated solvent extraction combined with pH‐zone‐refining counter‐current chromatography. The major extraction parameters for accelerated solvent extraction were optimized by an orthogonal test design L9 (3)4. Then a separation and purification method was established using pH‐zone‐refining counter‐current chromatography with a two‐phase solvent system composed of petroleum ether/ethyl acetate/methanol/water (5:5:2:8, v/v) with 10 mM triethylamine in the upper phase and 10 mM HCl in the lower phase. From 2 g crude extract, 224 mg of 8‐deacetylyunaconitine (I) and 841 mg of yunaconitine (II) were obtained with a purity of over 98.0%. The chemical structures were identified by ESI‐MS and 1H and 13C NMR spectroscopy.  相似文献   
105.
An efficient strategy for extracting and separating five lignans from Schisandra chinensis (Turcz.) Baill has been developed using supercritical fluid extraction (SFE) and high‐speed counter‐current chromatography (HSCCC) in the present study. First, the extraction was performed by a preparative SFE system under 15 MPa of pressure at 36°C for 4 h. Then, the SFE extract was successfully separated and purified by HSCCC with a two‐phase solvent system composed of n‐hexane/ethyl acetate/methanol/water (6:4:5:5, 6:4:6:4, 6:4:8:2, v/v) in a stepwise elution mode. The fractions were analyzed by HPLC, and the chemical structures of the products were identified by ESI‐MS and 1H NMR spectroscopy. As a result, a total of 12.5 mg of schisandrin at 98.0% purity, 7.1 mg of gomisin A at 98.1% purity, 1.8 mg of schisantherin B at 93.3% purity, 4.4 mg of deoxyschisandrin at 92.9% purity, and 6.8 mg of γ‐schisandrin at 89.1% purity were obtained from 300 mg crude extract in a one‐step purification.  相似文献   
106.
A rapid and efficient high‐performance counter‐current chromatography (HPCCC) method was developed to separate five oligostilbenes from the roots of Vitis amurensis. An n‐hexane/ethyl acetate/methanol/water system (4:8:4:10, v/v/v/v) was selected as an optimal two‐phase solvent system of which the upper phase was used as the stationary phase and the lower phase was used as the mobile one. Partition coefficient values for the target compounds under these optimized conditions were 0.28 ( 1 , ampleosin A), 7.12 ( 2 , (+)‐g‐viniferin), 2.26 ( 3 , vitisin A), 5.38 ( 4 , wilsonol C), and 11.23 ( 5 , vitisin B). Flow‐rate gradient HPCCC (4 mL/min in 0–70 min, 8 mL/min in 70–250 min) was applied to isolate the target compounds in as high purity as possible within the shortest possible run time. Under these conditions, ampelopsin A (12.1 mg), (+)‐g‐viniferin (10.4 mg), vitisin A (2.8 mg), wilsonol C (3.2 mg), and vitisin B (37 mg) were isolated with >95% purity from 150 mg of enriched oligostilbene extract. Although the KD of the last eluted compound, vitisin B (KD = 11.23), was relatively large, it was eluted in 115–145 min using the two‐phase solvent system. This study shows that HPCCC is an efficient tool for the isolation and purification of natural products.  相似文献   
107.
In this study, bioactive components from Ampelopsis heterophylla were separated by counter‐current chromatography (CCC). The antioxidant activity of the crude extract was initially evaluated by an online HPLC method. Five compounds in the crude extract exhibited good antioxidant activities, namely, hyperoside ( 1 ), isoquercitrin ( 2 ), rutin ( 3 ), kaempferol‐3‐rutinoside ( 4 ), and quercetin ( 5 ). These compounds were further separated by CCC with biphasic solvent systems and their structures were identified by MS and NMR spectroscopy. All the compounds exhibited significant 1,1‐diphenyl‐2‐picryl‐hydrazyl radical scavenging activities with IC50 values at 18.2 ± 1.3, 17.0 ± 1.4, 24.2 ± 1.2, 38.1 ± 1.7, and 9.0 ± 1.2 μM, respectively. The scavenging ratios of the compounds against hydroxyl radicals were 65 ± 5, 68 ± 4, 96 ± 2, 70 ± 4, and 98 ± 2%, respectively.  相似文献   
108.
This work concentrates on extending the utilization of multiple dual mode (MDM) counter‐current chromatography in chiral separations. Two aromatic acids, 2‐(6‐methoxy‐2‐naphthyl)propionic acid (NAP) and 2‐phenylpropionic acid (2‐PPA), were enantioseparated by MDM counter‐current chromatography using hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) as chiral selector. The two‐phase solvent systems consisting of n‐hexane/ethyl acetate 0.1 mol/L phosphate buffer pH 2.67 containing 0.1 mol/L HP‐β‐CD (7.5:2.5:10 for NAP and 7:3:10 for 2‐PPA, v/v/v) were used. Conventional MDM and modified MDM were compared according to peak resolution under current separation mechanism. The influence of elution time after the first‐phase inversion and number of cycles for MDM were investigated. Peak resolution of NAP and 2‐PPA increased from 0.62 to 1.05 and 0.72 to 0.84, respectively, using optimized MDM conditions. Being an alternative elution method for counter‐current chromatography, MDM elution greatly improved peak resolution in chiral separations.  相似文献   
109.
Two‐phase solvent system plays crucial role in successful separation of organic compounds using counter‐current chromatography (CCC). An interesting two‐phase solvent system, composed of chloroform/ethyl acetate/methanol/water, is reported here, in which both phases contain sufficient organic solvents to balance their dissolving capacities. Adjusting the solvent system to get satisfactory partition coefficients (K values) for target compounds becomes relatively simple. This solvent system succeeded in sample preparation of aconitine (8.07 mg, 93.69%), hypaconitine (7.74 mg, 93.17%), mesaconitine (1.95 mg, 94.52%) from raw aconite roots (102.24 mg, crude extract), benzoylmesaconine (34.79 mg, 98.67%) from processed aconite roots (400.01 mg, crude extract), and yunaconitine (253.59 mg, 98.65%) from a crude extract of Aconitum forrestii (326.69 mg, crude extract).  相似文献   
110.
Supercritical fluid extraction (SFE) coupled with high‐speed counter‐current chromatography (HSCCC) was successfully used for the extraction and online isolation of the unstable compounds from Rosa damascene in a single extraction and separation operation in two stages. The solvent systems of SFE/HSCCC were optimized with the help of multiexponential function model. At the first stage, the upper phase of the solvent system of n‐butanol–tert‐butyl methyl ether–acetonitrile–0.1% aqueous TFA (1.7:1.0:0.8:4.0, v/v/v/v) was used as both the SFE entrainer and the HSCCC stationary phase, and the target compounds were eluted with the corresponding lower phase to separate the hydrophobic compounds. At the second stage, the upper phase of the solvent system of n‐hexane–ethyl acetate–methanol–water (3.2:1.0:2.8:2.6, v/v/v/v) was used as both the SFE entrainer and the HSCCC stationary phase, followed by elution with the corresponding lower phase to separate the moderate hydrophobic compounds. Six compounds including formononetin, delphinidin, cyaniding, 5,6,4′‐trihydroxy‐7,8‐dimethoxy flavone, 5,3′‐dihydroxy‐7,8‐dimethoxy flavone, and 5‐hydroxy‐6,7,8,3′,4′‐pentamethoxy flavone were successfully separated in one extraction–separation operation within 300 min. The targeted compounds were identified by MS and NMR spectroscopy. This research has opened up great prospects for industrial application of SFE/HSCCC to the extraction and separation of unstable compounds.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号