全文获取类型
收费全文 | 990篇 |
免费 | 21篇 |
国内免费 | 5篇 |
专业分类
化学 | 678篇 |
晶体学 | 3篇 |
力学 | 31篇 |
数学 | 107篇 |
物理学 | 197篇 |
出版年
2022年 | 8篇 |
2021年 | 13篇 |
2020年 | 10篇 |
2019年 | 21篇 |
2018年 | 11篇 |
2016年 | 30篇 |
2015年 | 24篇 |
2014年 | 28篇 |
2013年 | 43篇 |
2012年 | 63篇 |
2011年 | 81篇 |
2010年 | 39篇 |
2009年 | 27篇 |
2008年 | 62篇 |
2007年 | 54篇 |
2006年 | 53篇 |
2005年 | 36篇 |
2004年 | 50篇 |
2003年 | 42篇 |
2002年 | 45篇 |
2001年 | 25篇 |
2000年 | 17篇 |
1999年 | 7篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 10篇 |
1995年 | 6篇 |
1994年 | 6篇 |
1993年 | 12篇 |
1991年 | 7篇 |
1990年 | 9篇 |
1989年 | 8篇 |
1988年 | 6篇 |
1987年 | 8篇 |
1986年 | 6篇 |
1985年 | 11篇 |
1984年 | 5篇 |
1981年 | 4篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 5篇 |
1977年 | 9篇 |
1976年 | 9篇 |
1975年 | 6篇 |
1974年 | 9篇 |
1973年 | 10篇 |
1972年 | 7篇 |
1969年 | 4篇 |
1967年 | 4篇 |
1965年 | 4篇 |
排序方式: 共有1016条查询结果,搜索用时 15 毫秒
951.
Thorsten Holm 《代数通讯》2013,41(6):1957-1969
Let k be a field of characteristic P >0 and let G be a finite abelian group. We determine the structure of the Hochschild cohomology ring of the group algebra k G. Moreover, we prove that for any finite group G the Krull dimension of H H *(k G) equals the p-rank of G. 相似文献
952.
Tina A. Schuetz Stefan Becker Andreas Mang Alina Toma 《Mathematical and Computer Modelling of Dynamical Systems: Methods, Tools and Applications in Engineering and Related Sciences》2013,19(5):417-433
In this work, a mathematical model of malignant brain tumour growth is presented. In particular, the growth of glioblastoma is investigated on the intracellular and intercellular scale. The Go or Grow principle of tumour cells states that tumour cells either migrate or proliferate. For glioblastoma, microRNA-451 has been shown to be an energy dependent key regulator of the LKB1 (liver kinase B1) and AMPK (AMP-activated protein kinase) pathway that influences the signalling for migration or cell division. We introduce a mathematical model that reproduces these biological processes. The intracellular molecular interaction network is represented by a system of nine ordinary differential equations. This is put into a multiscale context by applying an agent-based approach: each cell is equipped with this interaction network and additional rules to determine its new phenotype as either migrating, proliferating or quiescent. The evaluation of the proposed model by comparison of the results with in vitro experiments indicates its validity. 相似文献
953.
954.
Hong SH Wenzel AG Salguero TT Day MW Grubbs RH 《Journal of the American Chemical Society》2007,129(25):7961-7968
The decomposition of a series of ruthenium metathesis catalysts has been examined using methylidene species as model complexes. All of the phosphine-containing methylidene complexes decomposed to generate methylphosphonium salts, and their decomposition routes followed first-order kinetics. The formation of these salts in high conversion, coupled with the observed kinetic behavior for this reaction, suggests that the major decomposition pathway involves nucleophilic attack of a dissociated phosphine on the methylidene carbon. This mechanism also is consistent with decomposition observed in the presence of ethylene as a model olefin substrate. The decomposition of phosphine-free catalyst (H2IMes)(Cl)2Ru=CH(2-C6H4-O-i-Pr) (H2IMes = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) with ethylene was found to generate unidentified ruthenium hydride species. The novel ruthenium complex (H2IMes)(pyridine)3(Cl)2Ru, which was generated during the synthetic attempts to prepare the highly unstable pyridine-based methylidene complex (H2IMes)(pyridine)2(Cl)2Ru=CH2, is also reported. 相似文献
955.
Substitution reactions at the nickel site of the cubane-type cluster [(Ph3P)NiFe3S4(LS3)]2- (2) have been investigated in the course of a synthetic approach to the C-clusters of CODH. Reaction of 2 with RS- or toluene-3,4-dithiolate affords [(RS)NiFe3S4(LS3)]3- (R = Et (5), H (6)) or [(tdt)NiFe3S4(LS3)]3- (7), demonstrating that anionic sulfur ligands can be bound at the NiII site. Clusters 5 and 6 contain tetrahedral Ni(micro3-S)3(SR) sites. Cluster 7 is of particular interest because it includes a cubanoid NiFe3(micro2-S)(micro3-S)3 core and an approximately planar Ni(tdt)(micro3-S)2 unit. The cubanoid structure is found in all C-clusters, and an NiS4-type unit has been reported in C. hydrogenoformans CODH. Clusters 5/6 are formulated to contain the core [NiFe3S4]1+ identical with Ni2+ (S = 1) + [Fe3S4]1- (S = 5/2) and 7 the core [NiFe3S4]2+ identical with Ni2+ (S = 0) + [Fe3S4]0 (S = 2) on the basis of structure, 57Fe isomer shifts, and 1H NMR isotropic shifts. Also reported are [(EtS)CuFe3S4(LS3)]3- (9) and [Fe4S4(LS3)(tdt)]3- (11). The structures of 5-7, 9, and 11 are presented. Cluster 11, with a five-coordinate Fe(tdt)(micro3-S)3 site, provides a clear structural contrast with 7, which is currently the closest approach to a C-cluster but lacks the exo iron atom found in the NiFe4S4,5 cores of the native clusters. (CODH = carbon monoxide dehydrogenase, LS3 = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzene(3-), tdt = toluene-3,4-dithiolate). 相似文献
956.
Wilson SR Malerød H Holm A Molander P Lundanes E Greibrokk T 《Journal of chromatographic science》2007,45(3):146-152
An instrumental set up including on-line solid-phase extraction, nano-liquid chromatography, and nanospray mass spectrometry is constructed to improve the sensitivity for quantitation of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in surface water. Sample volumes of 1000 microL are loaded onto a microbore 1.0-mm i.d. x 5 mm, 5 microm Kromasil C(18) enrichment column by a carrier solution consisting of 10mM ammonium acetate in acetonitrile-water (10:90, v/v) at a flow rate of 250 microL/min, providing on-line analyte enrichment and sample clean-up. Backflushed elution onto a 0.1-mm i.d. x 150 mm, 3.5 microm Kromasil C(18) analytical column is conducted using an acetonitrile-10mM ammonium acetate solvent gradient from 30% to 70% acetonitrile. Water samples are added with internal standard (perfluoroheptanoic acid) and filtrated prior to injection. The mass limits of detection of PFOA and PFOS are 0.5 and 1 pg, respectively, corresponding to concentration limits of detection of 500 pg/L and 1 ng/L, respectively. The total time spent on sample preparation, chromatography, and detection is approximately 12 min per sample. The method was employed for the determination of PFOS and PFOA in urban river water. 相似文献
957.
Hunter TM McNae IW Simpson DP Smith AM Moggach S White F Walkinshaw MD Parsons S Sadler PJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(1):40-50
Nickel(II)-xylylbicyclam is a potent anti-HIV agent and binds strongly to the CXCR4 co-receptor. We have investigated configurational equilibria of Ni(II)-cyclam derivatives, since these are important for receptor recognition. Crystallographic studies show that both trans and cis configurations are readily formed: [Ni(cyclam)(OAc)(2)] x H(2)O adopts the trans-III configuration with axial monodentate acetates, as does [Ni(benzylcyclam)(NO(3))(2)] with axial nitrate ligands, whereas [Ni(benzylcyclam)(OAc)](OAc)2 x H(2)O has an unusual folded cis-V configuration with Ni(II) coordination to bidentate acetate. UV/Vis and NMR studies show that the octahedral trans-III configuration slowly converts to square-planar trans-I in aqueous solution. For Ni(II)-xylylbicyclam, a mixture of cis-V and trans-I configurations was detected in solution. X-ray diffraction studies showed that crystals of lysozyme soaked in Ni(II)-cyclam or Ni(II) (2)-xylylbicyclam contain two major binding sites, one involving Ni(II) coordination to Asp101 and hydrophobic interactions between the cyclam ring and Trp62 and Trp63, and the second hydrophobic interactions with Trp123. For Ni(II)-cyclam bound to Asp101, the cis-V configuration predominates. 相似文献
958.
2-Siloxy-2-alkenyl-1,1-dichlorocyclopropanes with aryl-terminated side chains undergo silver-assisted electrocyclic opening/Nazarov cyclization. The resulting 2-siloxycyclopentenyl cations are intercepted by the pendant arenes to furnish tricyclic adducts in moderate to good yields. In cases where the arene trap was tethered through the cyclopropane unit, a new mode of trapping occurred to generate unique bridged carbon frameworks. 相似文献
959.
Vermoortele F Maes M Moghadam PZ Lennox MJ Ragon F Boulhout M Biswas S Laurier KG Beurroies I Denoyel R Roeffaers M Stock N Düren T Serre C De Vos DE 《Journal of the American Chemical Society》2011,133(46):18526-18529
Para-disubstituted alkylaromatics such as p-xylene are preferentially adsorbed from an isomer mixture on three isostructural metal-organic frameworks: MIL-125(Ti) ([Ti(8)O(8)(OH)(4)(BDC)(6)]), MIL-125(Ti)-NH(2) ([Ti(8)O(8)(OH)(4)(BDC-NH(2))(6)]), and CAU-1(Al)-NH(2) ([Al(8)(OH)(4)(OCH(3))(8)(BDC-NH(2))(6)]) (BDC = 1,4-benzenedicarboxylate). Their unique structure contains octahedral cages, which can separate molecules on the basis of differences in packing and interaction with the pore walls, as well as smaller tetrahedral cages, which are capable of separating molecules by molecular sieving. These experimental data are in line with predictions by molecular simulations. Additional adsorption and microcalorimetric experiments provide insight in the complementary role of the two cage types in providing the para selectivity. 相似文献
960.
Chapman KW Sava DF Halder GJ Chupas PJ Nenoff TM 《Journal of the American Chemical Society》2011,133(46):18583-18585
The release of guest species from within a nanoporous metal-organic framework (MOF) has been inhibited by amorphization of the guest-loaded framework structure under applied pressure. Thermogravimetric analyses have shown that by amorphizing ZIF-8 following sorption of molecular I(2), a hazardous radiological byproduct of nuclear energy production, the pore apertures in the framework are sufficiently distorted to kinetically trap I(2) and improve I(2) retention. Pair distribution function (PDF) analysis indicates that the local structure of the captive I(2) remains essentially unchanged upon amorphization of the framework, with the amorphization occurring under the same conditions for the vacant and guest-loaded framework. The low, accessible pressure range needed to effect this change in desorption is much lower than in tradition sorbents such as zeolites, opening the possibility for new molecular capture, interim storage, or controlled release applications. 相似文献