全文获取类型
收费全文 | 101605篇 |
免费 | 8197篇 |
国内免费 | 8889篇 |
专业分类
化学 | 43536篇 |
晶体学 | 2074篇 |
力学 | 4399篇 |
综合类 | 550篇 |
数学 | 20426篇 |
物理学 | 47706篇 |
出版年
2023年 | 352篇 |
2022年 | 451篇 |
2021年 | 1055篇 |
2020年 | 1246篇 |
2019年 | 1516篇 |
2018年 | 1384篇 |
2017年 | 1231篇 |
2016年 | 1108篇 |
2015年 | 1047篇 |
2014年 | 1913篇 |
2013年 | 3532篇 |
2012年 | 2509篇 |
2011年 | 3153篇 |
2010年 | 3468篇 |
2009年 | 8415篇 |
2008年 | 9485篇 |
2007年 | 7909篇 |
2006年 | 7304篇 |
2005年 | 5274篇 |
2004年 | 4983篇 |
2003年 | 5059篇 |
2002年 | 6174篇 |
2001年 | 4272篇 |
2000年 | 4107篇 |
1999年 | 3823篇 |
1998年 | 3206篇 |
1997年 | 2317篇 |
1996年 | 2064篇 |
1995年 | 2568篇 |
1994年 | 2452篇 |
1993年 | 1878篇 |
1992年 | 1393篇 |
1991年 | 1031篇 |
1990年 | 805篇 |
1989年 | 748篇 |
1988年 | 687篇 |
1987年 | 475篇 |
1985年 | 994篇 |
1984年 | 686篇 |
1983年 | 512篇 |
1982年 | 675篇 |
1981年 | 831篇 |
1980年 | 743篇 |
1979年 | 584篇 |
1978年 | 595篇 |
1977年 | 549篇 |
1976年 | 545篇 |
1975年 | 322篇 |
1974年 | 354篇 |
1973年 | 468篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
51.
52.
通过等温吸附实验,探究了三氯甲烷(CHCl3)与二氯一溴甲烷(CHBrCl2)、二氯乙酸(Cl2CHCOOH)在活性炭上的竞争吸附关系,同时探究了在低浓度条件下CHBrCl2和Cl2CHCOOH浓度变化对活性炭吸附CHCl3的影响。实验结果表明,活性炭吸附CHCl3和CHBrCl2符合Freundlich模型,对Cl2CHCOOH的吸附符合Langmuir模型;活性炭对3种消毒副产物均为优先吸附,吸附能力由大到小依次为CHBrCl2、CHCl3、Cl2CHCOOH;低浓度条件下,活性炭对消毒副产物的吸附效果随体系中物质种类的增加而降低;低浓度条件下,Cl2CHCOOH的浓度变化对CHCl3的吸附效果影响不大,但吸附效果随水体中CHBrCl2浓度的升高而降低。 相似文献
53.
New dicarboxylate-functionalized pillared materials with a general formula of λ-ZrPO4(OH)1-x(OOC(CH2)nCOO)x/2(dmso) (n=6, 8 and 10) have been prepared by post-synthesis modification of the inorganic layers of λ-zirconium phosphate (λ-ZrP), where the superficial Chloride monovalent anionic ligands of λ-layer are partially exchanged with the divalent anionic ligands of a series of long-chain aliphatic dicarboxylic acids, namely octanedioic acid, decanedioic acid and dodecanedioic acid. The synthesized materials are characterized by X-ray diffractometry, FT-IR spectrophotometry, elemental and thermogravimetric analyses. The X-ray diffraction patterns show that the obtained solid phases are pure. Furthermore, the interlayer distance of λ-ZrP systematically increases from 1.02 to 1.59 nm as a result of the incorporation of the mentioned acids inside the interlayer gallery. 相似文献
54.
Development and validation of a reversed‐phase HPLC method for CYP1A2 phenotyping by use of a caffeine metabolite ratio in saliva 下载免费PDF全文
Elias Begas Evangelos Kouvaras Andreas K. Tsakalof Maria Bounitsi Eftihia Konstadinos Asprodini 《Biomedical chromatography : BMC》2015,29(11):1657-1663
CYP1A2 is important for metabolizing various clinically used drugs. Phenotyping of CYP1A2 may prove helpful for drug individualization therapy. Several HPLC methods have been developed for quantification of caffeine metabolites in plasma and urine. Aim of the present study was to develop a valid and simple HPLC method for evaluating CYP1A2 activity during exposure in xenobiotics by the use of human saliva. Caffeine and paraxanthine were isolated from saliva by liquid‐liquid extraction (chlorophorm/isopropanol 85/15v/v). Extracts were analyzed by reversed‐phase HPLC on a C18 column with mobile phase 0.1% acetic acid/methanol/acetonitrile (80/20/2 v/v) and detected at 273nm. Caffeine and paraxanthine elution times were <13min with no interferences from impurities or caffeine metabolites. Detector response was linear (0.10–8.00µg/ml, R2>0.99), recovery was >93% and bias <4.47%. Intra‐ and inter‐day precision was <5.14% (n=6). The limit of quantitation was 0.10µg/ml and the limit of detection was 0.018±0.002µg/mL for paraxanthine and 0.032±0.002µg/ml for caffeine. Paraxanthine/caffeine ratio of 34 healthy volunteers was significantly higher in smokers (p<0.001). Saliva paraxanthine/caffeine ratios and urine metabolite ratios were highly correlated (r=0.85, p<0.001). The method can be used for the monitoring of CYP1A2 activity in clinical practice and in studies relevant to exposure to environmental and pharmacological xenobiotics. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
55.
A series of chalcone ligands and their corresponding vanadyl complexes of composition [VO (LI–IV)2(H2O)2]SO4 (where LI = 1,3‐Diphenylprop‐2‐en‐1‐one, LII = 3‐(2‐Hydroxy‐phenyl)‐1‐phenyl‐propenone, LIII = 3‐(3‐Nitro‐phenyl)‐1‐phenyl‐propenone, LIV = 3‐(4‐Methoxy‐phenyl)‐1‐phenyl‐propenone) have been synthesized and characterized using various spectroscopic (Fourier‐transform infrared, electrospray ionization mass, nuclear magnetic resonance, electron paramagnetic resonance, thermogravimetric analysis, vibrating sample magnetometer) and physico‐analytic techniques. Antidiabetic activities of synthesized complexes along with chalcones were evaluated by performing in vitro and in silico α‐amylase and α‐glucosidase inhibition studies. The obtained results displayed moderate to significant inhibition activity against both the enzymes by vanadyl chalcone complexes. The most potent complexes were further investigated for the enzyme kinetic studies and displayed the mixed inhibition for both the enzymes. Further, antioxidant activity of vanadyl chalcone complexes was evaluated for their efficiency to release oxidative stress using 2,2‐diphenyl‐1‐picryl‐hydrazyl‐hydrate assay, and two complexes (Complexes 2 and 4 ) have demonstrated remarkable antioxidant activity. All the complexes were found to possess promising antidiabetic and antioxidant potential. 相似文献
56.
Palladium‐catalyzed decarboxylative coupling of α,β‐unsaturated carboxylic acids with aryl tosylates
We report a general method for selective cross‐coupling of α,β‐unsaturated carboxylic acids with aryl tosylates enabled by versatile Pd(II) complexes. This method features the general cross‐coupling of ubiquitous α,β‐unsaturated carboxylic acids by decarboxylation. The transformation is characterized by its operational simplicity, the use of inexpensive, air‐stable Pd(II) catalysts, scalability and wide substrate scope. The reaction proceeds with high trans selectivity to furnish valuable (E)‐1,2‐diarylethenes. 相似文献
57.
We consider concentrated vorticities for the Euler equation on a smooth domain in the form of supported on well-separated vortical domains , , of small diameters . A conformal mapping framework is set up to study this free boundary problem with being part of unknowns. For any given vorticities and small , through a perturbation approach, we obtain such piecewise constant steady vortex patches as well as piecewise smooth Lipschitz steady vorticities, both concentrated near non-degenerate critical configurations of the Kirchhoff–Routh Hamiltonian function. When vortex patch evolution is considered as the boundary dynamics of , through an invariant subspace decomposition, it is also proved that the spectral/linear stability of such steady vortex patches is largely determined by that of the 2N-dimensional linearized point vortex dynamics, while the motion is highly oscillatory in the 2N-codim directions corresponding to the vortical domain shapes. 相似文献
58.
59.
60.
Yanmin Yu 《Molecular physics》2019,117(9-12):1360-1366
ABSTRACTPotential energy surfaces and molecular dynamics of the intramolecular 1, 3-dipolar cycloaddition and ene reaction of a nitrile oxide with an alkene were performed in the gas phase and in dichloromethane with density functional theory. One hundred trajectories were propagated in the gas phase and in dichloromethane, respectively. Twenty percent of the trajectories in the gas phase involve bicyclic intermediate and the mean time gap is 472fs. A dynamically stepwise reaction is observed. In dichloromethane, more reactive trajectories were obtained and the time gap is larger than that in the gas phase. 相似文献