全文获取类型
收费全文 | 24119篇 |
免费 | 1932篇 |
国内免费 | 1087篇 |
专业分类
化学 | 12128篇 |
晶体学 | 446篇 |
力学 | 1390篇 |
综合类 | 91篇 |
数学 | 2281篇 |
物理学 | 10802篇 |
出版年
2024年 | 26篇 |
2023年 | 244篇 |
2022年 | 449篇 |
2021年 | 481篇 |
2020年 | 502篇 |
2019年 | 561篇 |
2018年 | 560篇 |
2017年 | 492篇 |
2016年 | 765篇 |
2015年 | 668篇 |
2014年 | 891篇 |
2013年 | 1367篇 |
2012年 | 1709篇 |
2011年 | 1939篇 |
2010年 | 1407篇 |
2009年 | 1296篇 |
2008年 | 1474篇 |
2007年 | 1437篇 |
2006年 | 1349篇 |
2005年 | 1068篇 |
2004年 | 889篇 |
2003年 | 732篇 |
2002年 | 746篇 |
2001年 | 1143篇 |
2000年 | 747篇 |
1999年 | 672篇 |
1998年 | 449篇 |
1997年 | 423篇 |
1996年 | 335篇 |
1995年 | 268篇 |
1994年 | 265篇 |
1993年 | 218篇 |
1992年 | 226篇 |
1991年 | 202篇 |
1990年 | 184篇 |
1989年 | 154篇 |
1988年 | 118篇 |
1987年 | 104篇 |
1986年 | 83篇 |
1985年 | 85篇 |
1984年 | 63篇 |
1983年 | 45篇 |
1982年 | 31篇 |
1981年 | 30篇 |
1980年 | 19篇 |
1977年 | 18篇 |
1976年 | 27篇 |
1975年 | 27篇 |
1974年 | 21篇 |
1973年 | 19篇 |
排序方式: 共有10000条查询结果,搜索用时 25 毫秒
991.
Two new coordination polymers, [Pb(IDPT)2(NO3)2] (I) and [Mn(IDPT)(SO4)(H2O)2] (II) (IDPT = imidazo[4,5-f][1,10]phenanthroline), were synthesized by hydrothermal method and characterized by elemental analysis and single-crystal X-ray diffraction technique. The results reveal that the complex I belongs to monoclinic crystal system, space group C2/c and complex II belongs to monoclinic crystal system, P21/c space group. The cell parameters are: a = 19.1970(13), b = 7.3875(5), c = 17.3825(12) Å, β = 100.47(10)°, V = 2424.0(3) Å3, Z = 4, F(000) = 1488 for I; a = 10.9135(6), b = 7.0230(4), c = 19.7034(10) Å, β = 99.32(10)°, V = 1490.25(14) Å3, Z = 4, F(000) = 828 for II. In the structure of complex I, the metal center Pb(II) is six-coordinated, displays an octahedral geometry. Each molecule is further connected with neighboring one via π-π interactions into 1D chain. In complex II, Mn(II) is six-coordinated to form a distorted octahedral geometry. Compound II displays 1D supramolecular chain formed through hydrogen bonds. Additionally, the fluorescent properties for the complexes were investigated. Complexes I and II exhibit strong photoluminescence with emission maximum at 583 and 529 nm at room temperature. 相似文献
992.
W. Chen X. L. Xu P. Zhou Y. M. Cui Y. G. Li 《Russian Journal of Coordination Chemistry》2013,39(3):301-304
Two silver(I) compounds, [Ag(R,R-hxn)](C7H4BrO2) · 2H2O (I) (Chxn = 1,2-diaminocyclohexane) and [Ag(C5H6N2)2]2(C8H4O4) · 10H2O (II), were synthesized and complex I was structurally characterized by X-ray crystallography. Compound I contains a catena-(trans-1,2-diaminocyclohexane) silver polycation ([Ag(Chxn)]∞) in a roughly linear fashion, while II possesses a linear-type silver monocation. Compounds I and II were evaluated for their inhibitory activities against Helicobacter pylori urease in vitro. Both were found to have strong inhibitory activities against H. pylori urease comparable to that of acetohydroxamic acid. 相似文献
993.
H. Xia X. Jiang L. Lin C. Jiang G. Liao 《Russian Journal of Coordination Chemistry》2013,39(12):896-901
Reaction of a macrocyclic copper(II) complex [Cu(L)](ClO4)2 · 3H2O (I) (L = 1,3,10,12,16,19-hexaazatetracyclotetracosane) with a hexapod carboxylate ligand H6TTHA (H6TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetic acid) and a tripod carboxylate ligand H3TATB (H3TATB = 4,4′,4″-S-triazine-2,4,6-triyl-tribenzoic acid) yielded two mononuclear copper(II) complexes [Cu(L)][H4TTHA] · 4H2O (II) and [Cu(L)][HTATB] · 4H2O (III). The complexes I–III have been structurally characterized. The crystal structures of complexes II and III show the copper(II) ion has a distorted pentacoordinate square-pyramidal geometry with two secondary and two tertiary amines from the macrocyclic complex [Cu(L)]2+ and one oxygen atom from the carboxylate ligand group at the axial position. The UV-Vis spectra are utilized to discuss the hydrolysis of the complex II. 相似文献
994.
Binbin Wei Qing Li Ronghua Fan Dan Su Xiuli Ou Kelin Chen Xiaohui Chen Ying Jia Kaishun Bi 《Journal of mass spectrometry : JMS》2013,48(4):448-458
Schisandra chinensis (Turcz.) Baill., a traditional Chinese medicine, has been clinically used for the treatment of insomnia for centuries. The insomnia mechanism and the possible active ingredients of S. chinensis remain largely unknown. The objective of this study was to develop a method to detect its components which could pass through the blood brain barrier (BBB) by determining the brain microdialysate and brain tissue homogenate samples and then obtain the pharmacokinetic profile in brain for comprehensive understanding of its hypnotic clinical efficacy. Therefore, an efficient, sensitive and selective ultra fast liquid chromatography/tandem mass spectrometry method for the simultaneous determination of six sedative and hypnotic lignans (schisandrin, schisandrol B, schisantherin A, deoxyshisandrin, γ‐schisandrin and gomisin N) of Schisandra chinensis (Turcz.) Baill. in rat brain tissue homogenate and brain microdialysates has been developed and validated. The analysis was performed on a Shim‐pack XR‐ODS column (75 mm × 3.0 mm, 2.2 µm) using gradient elution with the mobile phase consisting of acetonitrile and 0.1% formic acid water. The method was validated in brain homogenate and microdialysate samples, which all showed good linearity over a wide concentration range (r2 > 0.99), and the obtained lower limit of quantification was 0.1 ng · ml?1 for the analytes in brain microdialysate samples. The intra‐ and inter‐day assay variability was less than 15% for all analytes. The study proved the six lignans, as sedative and hypnotic ingredients, could pass through the BBB with brain targeting, distributed mainly in the hypothalamus and possessed complete pharmacokinetics process in brain. The results also indicated that significant difference in pharmacokinetic parameters of the analytes was observed between two groups, while absorptions of these analytes in insomniac group were significantly better than those in normal group. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
995.
Yi-Bo Li Jin-Zhou Zhao Wan-Fen Pu Hu Jia Huan Peng Dong Zhong Sheng-Kui Wang 《Journal of Thermal Analysis and Calorimetry》2013,113(2):579-587
This research aimed at the investigation of the effect of different metallic additive on the combustion and kinetic behavior of crude oil. For this purpose, the thermal behavior of the oil-only and oil–metallic salts mixtures were studies by the thermogravimetry (TG)/derivative thermogravimetry and differential scanning calorimetry (DSC) on heating rate at 10 °C min?1. The result shows that Dagang crude oil exhibited apparent low temperature oxidation (LTO), fuel deposition, and high temperature oxidation processes. With the addition of metallic salts, the LTO process has been shortened and samples added CuSO4, CrCl3·6H2O, and AlCl3·6H2O achieved a much lower peak temperature than that of oil. Based on the Arrhenius model, metallic additives were proven to have obvious influence on the combustion activation energy. And, by comprehensive analysis of TG/DSC profile and activation energy, ZnSO4 exhibited a positive influence on light crude oil combustion during the high pressure air injection process. 相似文献
996.
Jia‐Xing Zhao Dr. Yan‐Zhen Zheng Xin‐Hong Lu Prof. Jian‐Feng Chen Prof. Xia Tao Prof. Weilie Zhou 《Chemphyschem》2013,14(9):1977-1984
We report two novel types of hierarchically structured iodine‐doped ZnO (I? ZnO)‐based dye‐sensitized solar cells (DSCs) using indoline D205 and the ruthenium complex N719 as sensitizers. It was found that iodine doping boosts the efficiencies of D205 I? ZnO and N719 I? ZnO DSCs with an enhancement of 20.3 and 17.9 %, respectively, compared to the undoped versions. Transient absorption spectra demonstrated that iodine doping impels an increase in the decay time of I? ZnO, favoring enhanced exciton life. Mott–Schottky analysis results indicated a negative shift of the flat‐band potential (Vfb) of ZnO, caused by iodine doping, and this shift correlated with the enhancement of the open circuit voltage (Voc). To reveal the effect of iodine doping on the effective separation of e?‐h+ pairs which is responsible for cell efficiency, direct visualization of light‐induced changes in the surface potential between I? ZnO particles and dye molecules were traced by Kelvin probe force microscopy. We found that potential changes of iodine‐doped ZnO films by irradiation were above one hundred millivolts and thus significantly greater. In order to correlate enhanced cell performance with iodine doping, electrochemical impedance spectroscopy, incident‐photon‐current efficiency, and cyclic voltammetry investigations on I? ZnO cells were carried out. The results revealed several favorable features of I? ZnO cells, that is, longer electron lifetime, lower charge‐transfer resistance, stronger peak current, and extended visible light harvest, all of which serve to promote cell performance. 相似文献
997.
A facile synthetic route of linezolid 1 has been developed.Using commercially available(R)epichlorohydrin as the starting material,1 was obtained through a sequence of cyclization,substitution, a Goldberg coupling,aminolysis and acetylation reactions.The synthetic route is easy to perform and can be scaled up. 相似文献
998.
Hui Tang Can-Hui Zheng Xiao-Hui Ren Jia Liu Na Liu Jia-Guo Lv Ju Zhu You-Jun Zhou 《中国化学快报》2013,24(3):219-222
A series of 1-(benzylamino)-2-(2,4-difluorophenyl)-3-(1H-1,2,4-triazol-l-yl)propan-2-ols compounds were synthesized and evaluated for their antifungal activities in vitro.The results showed that compounds 6A and 6B exhibited good antifungal activity.Compound 6A8 showed the strongest antifungal activity,which was significantly higher than that of the lead compounds and positive-control drugs Fluconazole and Itraconazole.In particular,the antifungal activity of compound 6A8 against Candida albicans and Candida krusei(MIC80 both at 0.00097μg/mL) was 515 and 64 times that of Fluconazole,respectively.The structure-activity relationships of the synthesized compounds were discussed,and the docking model of the target compounds with fungal lanosterol 14α-demethylase (CYP51) was analyzed. 相似文献
999.
In this paper,we developed and validated a simple,sensitive,and selective high-performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS) method to identify and measure the following prohibited substances that may be found in cosmetic products:minoxidil,hydrocortisone, spironolactone,estrone,canrenone,triamcinolone acetonide and progesterone.Chromatographic separation was performed on a Waters Symmetry C18(100 mm×2.1 mm,3.5μm particle size) with a gradient elution system composed of 0.2%(v/v) formic acid aqueous solution and methanol containing 0.2%(v/v) formic acid at a flow rate of 0.3 mL/min.The substances were detected using a triple quadrupole mass spectrometer in the multiple reaction monitoring mode with an electrospray ionization source.All of the calibration curves showed good linearity(r > 0.999) within the tested concentration ranges.The limit of detection was <25 pg.The relative standard deviations for intraday precision for each of the prohibited substances were <3.5%at two concentration levels(2μg/g,10μg/g). The relative recovery rate for each of the prohibited substances ranged from 91.8%to 111%at three concentration levels(0.1μg/g,2μg/g,10μg/g),including the limit of quantification.In conclusion,we have developed and validated a method that can identify seven prohibited substances in cosmetic products. 相似文献
1000.