全文获取类型
收费全文 | 71231篇 |
免费 | 22891篇 |
国内免费 | 3675篇 |
专业分类
化学 | 75076篇 |
晶体学 | 375篇 |
力学 | 3271篇 |
综合类 | 242篇 |
数学 | 5366篇 |
物理学 | 13467篇 |
出版年
2024年 | 226篇 |
2023年 | 4576篇 |
2022年 | 2335篇 |
2021年 | 3558篇 |
2020年 | 5809篇 |
2019年 | 3419篇 |
2018年 | 3303篇 |
2017年 | 1585篇 |
2016年 | 6857篇 |
2015年 | 6799篇 |
2014年 | 6663篇 |
2013年 | 7294篇 |
2012年 | 6055篇 |
2011年 | 4103篇 |
2010年 | 5359篇 |
2009年 | 5187篇 |
2008年 | 3139篇 |
2007年 | 2596篇 |
2006年 | 1917篇 |
2005年 | 1582篇 |
2004年 | 1332篇 |
2003年 | 1018篇 |
2002年 | 906篇 |
2001年 | 762篇 |
2000年 | 704篇 |
1999年 | 842篇 |
1998年 | 704篇 |
1997年 | 680篇 |
1996年 | 751篇 |
1995年 | 709篇 |
1994年 | 616篇 |
1993年 | 656篇 |
1992年 | 513篇 |
1991年 | 421篇 |
1990年 | 359篇 |
1989年 | 280篇 |
1988年 | 290篇 |
1987年 | 258篇 |
1986年 | 184篇 |
1985年 | 203篇 |
1984年 | 192篇 |
1983年 | 180篇 |
1982年 | 152篇 |
1980年 | 152篇 |
1977年 | 181篇 |
1976年 | 208篇 |
1975年 | 216篇 |
1974年 | 217篇 |
1972年 | 171篇 |
1970年 | 211篇 |
排序方式: 共有10000条查询结果,搜索用时 421 毫秒
911.
Complete 1H and 13C NMR assignments of four new steroidal glycosides from a gorgonian coral Junceella juncea 总被引:2,自引:0,他引:2
Four new cholest-type steroidal glycosides, junceellosides A-D, isolated from the EtOH/CH(2)Cl(2) extracts of the South China Sea gorgonian coral Junceella juncea, were identified. Complete assignments of the (1)H and (13)C NMR chemical shifts for these compounds were achieved by means of one- and two-dimensional NMR techniques, including (1)H-(1)H COSY, HSQC, HMBC and NOESY spectra. 相似文献
912.
A series of 1-(2,4-dichlorophenoxyacetoxy)alkylphosphonic acid dimethyl esters 5 and its corresponding phosphonate monosalts 6 were synthesized as potential herbicide. The phosphonate monosalts can be prepared from 1-(2,4-dichlorophenoxyacetoxy)alkylphosphonic acid dimethyl esters 5, which were synthesized by the condensation of O,O-dimethyl-1-hydroxyalkylphosphonates with dichlorophenoxyacetic chloride. This method provides a simple and efficient procedure for the synthesis of phosphonate derivatives containing sensitive groups to acid, base or water such as carboxylate ester bond; and the herbicidal activity of title compounds was evaluated in a set of experiments in greenhouse. Most of the compounds exhibited notable herbicidal activity. 相似文献
913.
Zhang Z Wu W Han B Jiang T Wang B Liu Z 《The journal of physical chemistry. B》2005,109(33):16176-16179
The effect of CO2 on the phase behavior of the reaction system and equilibrium conversion for esterification of acetic acid and ethanol in ionic liquid (1-butyl-3-methylimidazolium hydrogen sulfate, [bmim][HSO4]) was studied at 60.0 degrees C up to 15 MPa. It was demonstrated that there was only one phase in the reaction system in the absence of CO2. The reaction system underwent two-phase-->three-phase-->two-phase transitions with increasing pressure. The pressure of CO2 or the phase behavior of the system affected the equilibrium conversion of the reaction markedly. As the pressure was less than 3.5 MPa, there were two phases in the system, and the equilibrium conversion increased as pressure was increased. In the pressure range of 3.5-9.5 MPa, there existed three phases, and the equilibrium conversion increased more rapidly with increasing pressure. As the pressure was higher than 9.5 MPa, the reaction system entered another two-phase region and the equilibrium conversion was nearly independent of pressure. The total equilibrium conversion was 64% without CO2 and could be as high as 80% as pressure was higher than 9.0 MPa. The apparent equilibrium constants (K(x)) in different phases were also determined, showing that the K(x) in the middle phase or top phase was much greater than that in the bottom phase. 相似文献
914.
Chabinyc ML Salleo A Wu Y Liu P Ong BS Heeney M McCulloch I 《Journal of the American Chemical Society》2004,126(43):13928-13929
A method for the fabrication of polymeric thin-film transistors (TFTs) by lamination is described. Poly(dimethylsiloxane) stamps were used to delaminate thin films of semiconducting polymers from silicon wafers coated with a self-assembled monolayer (SAM) formed from octyltrichlorosilane. These supported films were laminated onto electrode structures to form coplanar TFTs. The fabrication process was used to make TFTs with poly(3-hexylthiophene), P3HT, and poly[5,5'-bis(3-dodecyl-2-thienyl)-2,2'-bithiophene], PQT-12. TFTs, where these polymers were laminated onto gate dielectrics coated with SAMs from octyltrichlorosilane, had effective field-effect mobilities of 0.03 and 0.005 cm2/(V s), respectively. TFTs where PQT-12 was laminated onto gate dielectrics that were not coated with a SAM also had mobility of 0.03 cm2/(V s). In contrast, TFTs fabricated by spin-coating PQT-12 onto the same structure had mobilities ranging from 10-3 to 10-4 cm2/(V s). These results suggest that the lower mobilities of polymer TFTs made with hydrophilic gate dielectrics are caused by molecular ordering in the semiconducting film rather than electronic effects of dipolar groups at the interface. 相似文献
915.
A liquid-phase microextraction (LPME) method has been demonstrated for the extraction and determination of organochlorine pesticides (OCPs) in aqueous solution. The method combines a dual gauge microsyringe with a hollow fiber membrane (LPME/DGM-HF) followed by detection by gas chromatography/ion trap mass spectrometry (GC/ITMS). The advantages include speed, low solvent and sample consumption, simplicity and ease of use. The extraction time, solvent selection, salt concentration and sample stirring rate have been investigated in order to optimize extraction efficiency. The viability is evaluated by measuring the linearity and detection limit of the five OCPs in aqueous solution. Detection linearity for the OCPs has been achieved over a range of concentrations between 1 and 500 microg/L (r2 > 0.930), with a detection limit of 0.1 microg/L for each OCP. 相似文献
916.
Using the mixture of cetyltrimethylammonium bromide (CTAB) and p‐Octyl polyethylene glycol phenyl ether (OP‐10) as templates, siliceous MCM‐48 materials can be synthesized with low molar ratio of CTAB to silica (0.139:1) and low concentration of mixed surfactants (ca.5%) and within a wide range of OP‐10/CTAB ratio (0.08?0.25). The materials were characterized by X‐ray powder diffraction, N2 adsorption/desorption isotherm, TEM, TG‐DSC and 29Si MAS NMR. Measurements indicated that the use of mixed surfactants allowed better condensation and higher ordering of the cubic mesostructure; at the same time, some properties of these materials were sensitive to the OP‐10/CTAB ratio. It was also found that the reduced pH of the gel which had been crystallized for a certain time gave a highly reproducible synthesis with a high silica yield (about 95%). Furthermore, the reaction mechanism of the synthesis is discussed in detail. 相似文献
917.
Liqing Wu 《Analytica chimica acta》2003,482(2):175-181
In this report, with semi-empirical quantum method, we have studied the conformation and energy of supermolecule composed of picolinamide and its positional isomers with methacrylic acid. We tried to explore the reason why picolinamide was not likely to show imprinting effect when using methacrylic acid as functional monomer in our previous work. In order to produce imprinting effect, which was not achieved based on hydrogen bonding interaction, we have synthesized a molecular-imprinted polymer (MIP) based on copper ion coordination in prepolymerization. The complex in prepolymerization was composed of copper(II), acetate, picolinamide and 4-vinylpyridine (4-Vpy). Suprisingly, the MIP had high selectivity to picolinamide-copper acetate complex, and changes of either copper ion, picolinamide or acetate would result in decrease in the imprinting effect. This is also the first example where the high selective recognition of the MIP to its template was achieved mainly by inhibiting the binding of non-template rather than enhancing the binding of the template. And this report can be also looked upon as a first step towards the solution to the problem of imprinting of template that contains intramolecular hydrogen bond. 相似文献
918.
高效液相色谱法测定糙米粉中的维生素 总被引:7,自引:1,他引:7
高效液相色谱法测定糙米粉中的维生素吴红京,唐根源,王勇(中国科学院福建物质结构研究所福州350002)(福建药品检验所福州350001)1前言众所周知,糙米粉有很高的营养价值,含有人体必需的多种维生素。用高效液相色谱法(HPLC)和薄层色谱法(TLC... 相似文献
919.
920.
Chen Luo Chenggang Zhou Jinping Wu T. J. Dhilip Kumar Naduvalath Balakrishnan Robert C. Forrey Hansong Cheng 《International journal of quantum chemistry》2007,107(7):1632-1641
Structures and physical properties of small palladium clusters Pdn up to n = 15 and several selected larger clusters were studied using density functional theory under the generalized gradient approximation. It was found that small Pdn clusters begin to grow 3‐dimensionally at n = 4 and evolve into symmetric geometric configurations, such as icosahedral and fcc‐like, near n = 15. Several isomers with nearly degenerate average binding energies were found to coexist and the physical properties of these clusters were calculated. For several selected isomers, relatively moderate energy barriers for structural interchange for a given cluster size were found, implying that isomerization could readily occur under ambient conditions. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献