全文获取类型
收费全文 | 648篇 |
免费 | 26篇 |
国内免费 | 3篇 |
专业分类
化学 | 386篇 |
晶体学 | 1篇 |
力学 | 31篇 |
数学 | 171篇 |
物理学 | 88篇 |
出版年
2024年 | 1篇 |
2023年 | 5篇 |
2022年 | 13篇 |
2021年 | 28篇 |
2020年 | 7篇 |
2019年 | 13篇 |
2018年 | 8篇 |
2017年 | 15篇 |
2016年 | 24篇 |
2015年 | 23篇 |
2014年 | 27篇 |
2013年 | 28篇 |
2012年 | 51篇 |
2011年 | 49篇 |
2010年 | 51篇 |
2009年 | 37篇 |
2008年 | 35篇 |
2007年 | 48篇 |
2006年 | 34篇 |
2005年 | 20篇 |
2004年 | 30篇 |
2003年 | 15篇 |
2002年 | 10篇 |
2001年 | 7篇 |
2000年 | 4篇 |
1999年 | 11篇 |
1998年 | 4篇 |
1997年 | 6篇 |
1996年 | 8篇 |
1995年 | 6篇 |
1994年 | 4篇 |
1993年 | 4篇 |
1992年 | 5篇 |
1991年 | 2篇 |
1990年 | 7篇 |
1989年 | 6篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1983年 | 5篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1979年 | 5篇 |
1978年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有677条查询结果,搜索用时 15 毫秒
111.
This work reports the fabrication of disposable three-electrode cells with integrated sputtered metal-film electrodes. The working electrode was a bismuth-film electrode (BiFE) while the reference and counter electrodes were made of Ag and Pt, respectively. The deposition of the metal layers was carried out by sputtering of the respective metals on a silicon substrate while the exact geometry of the electrodes was defined via a metal mask placed on the substrate during the deposition process. Initially, the electrodes were characterised by cyclic voltammetry. The utility of these devices was tested for the trace determination of Ni(II) by square wave adsorptive stripping voltammetry (SWAdSV) after complexation with dimethylglyoxime (DMG). The experimental variables (the presence of oxygen, the DMG concentration, the preconcentration potential, the accumulation time and the SW parameters), as well as potential interferences, were investigated. Using the selected conditions, the 3sigma limit of detection was 100 ng L(-1) for Ni(II) (for 90 s of preconcentration) and the relative standard deviation for Ni(II) was 2.3% at the 10 microg L(-1) level (n=8). Finally, the method was applied to the determination of Ni(II) in a certified river water sample. 相似文献
112.
Stamatatos TC Christou AG Mukherjee S Poole KM Lampropoulos C Abboud KA O'Brien TA Christou G 《Inorganic chemistry》2008,47(19):9021-9034
Convenient, high-yield routes have been developed to [Fe 10(OMe) 20(O 2CR) 10] ( 1) "ferric wheels" involving the alcoholysis of [Fe 3O(O 2CR) 6(H 2O) 3] (+) salts in MeOH in the presence of NEt 3. Reactivity studies have established [Fe 10(OMe) 20(O 2CMe) 10] ( 1a) to undergo clean carboxylate substitution with a variety of other RCO 2H groups to the corresponding [Fe 10(OMe) 20(O 2CR) 10] product. In contrast, the reaction with phenol causes a nuclearity change to give a smaller [Fe 8(OH) 4(OPh) 8(O 2CR) 12] ( 2) wheel. Similarly, reactions of [Fe 10(OMe) 20(O 2CR) 10] with the bidentate chelate ethylenediamine (en) cause a structural change to give either [Fe 8O 5(O 2CMe) 8(en) 8](ClO 4) 6 ( 3) or [Fe 2O(O 2CBu (t))(en) 4](NO 3) 3 ( 4), depending on conditions. Complex 3 possesses a "Christmas-star" Fe 8 topology comprising a central planar [Fe 4(mu 4-O)] (10+) square subunit edge-fused to four oxide-centered [Fe 3(mu 3-O)] (7+) triangular units. Variable-temperature, solid-state dc and ac magnetization studies on complexes 1a- 4 in the 5.0-300 K range established that all the complexes possess an S = 0 ground state. The magnetic susceptibility data for 4 were fit to the theoretical chi M versus T expression derived by the use of an isotropic Heisenberg spin Hamiltonian and the Van Vleck equation, and this revealed an antiferromagnetic exchange parameter with a value of J = -107.7(5) cm (-1). This value is consistent with that predicted by a previously published magnetostructural relationship. Theoretically computed values of the exchange constants in 3 were obtained with the ZILSH method, and the pattern of spin frustration within its core and the origin of its S = 0 ground state have been analyzed in detail. 相似文献
113.
114.
Silvia Valera Dr. Katrin Ackermann Dr. Christos Pliotas Dr. Hexian Huang Prof. James H. Naismith Dr. Bela E. Bode 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4700-4703
Pulse electron paramagnetic resonance (EPR) is gaining increasing importance in structural biology. The PELDOR (pulsed electron–electron double resonance) method allows extracting distance information on the nanometer scale. Here, we demonstrate the efficient extraction of distances from multimeric systems such as membrane‐embedded ion channels where data analysis is commonly hindered by multi‐spin effects. 相似文献
115.
Marta Falcone Dr. Christos E. Kefalidis Rosario Scopelliti Prof. Laurent Maron Prof. Marinella Mazzanti 《Angewandte Chemie (International ed. in English)》2016,55(40):12290-12294
Uranium nitrides are important materials with potential for application as fuels for nuclear power generation, and as highly active catalysts. Molecular nitride compounds could provide important insight into the nature of the uranium–nitride bond, but currently little is known about their reactivity. In this study, we found that a complex containing a nitride bridging two uranium centers and a cesium cation readily cleaved the C≡O bond (one of the strongest bonds in nature) under ambient conditions. The product formed has a [CsU2(μ‐CN)(μ‐O)] core, thus indicating that the three cations cooperate to cleave CO. Moreover, the addition of MeOTf to the nitride complex led to an exceptional valence disproportionation of the CsUIV–N–UIV core to yield CsUIII(OTf) and [MeN=UV] fragments. The important role of multimetallic cooperativity in both reactions is illustrated by the computed reaction mechanisms. 相似文献
116.
Epoxy terpenes cyclize readily, by confinement within zeolite NaY, to form exomethylenic cyclohexanols as the major products. The selective monocyclization of 10,11-epoxyfarnesyl acetate within NaY provides a short and efficient biomimetic route to (+/-)-elengasidiol and (+/-)-farnesiferols B-D. [reaction: see text]. 相似文献
117.
Moushi EE Lampropoulos C Wernsdorfer W Nastopoulos V Christou G Tasiopoulos AJ 《Inorganic chemistry》2007,46(10):3795-3797
A large [Mn10Na]4 loop-of-loops aggregate was prepared from the use of 1,3-propanediol (pdH2) in manganese carboxylate chemistry. It is constructed from four [Mn10(mu3-O)2(O2CMe)13(pd)6(py)2]- loops linked through Na+ ions and exhibits a saddlelike topology. Magnetic characterization showed that the Mn10 loop has an S approximately 4 ground-state spin and displays frequency-dependent in-phase and out-of-phase alternating current signals and also hysteresis loops that, however, are not typical of single-molecule magnets because of the existence of intermolecular interactions between the Mn10 units. 相似文献
118.
The compounds alpha-TlBiP2Se6 (I), beta-TlBiP2Se6 (II), TlBiP2S6 (III), Tl3Bi3(PS4)4 (IV), TlBiP2S7 (V), and Tl3Bi(PS4)2 (VI) were synthesized, and the structures of I-V were determined by single-crystal X-ray diffraction analysis. The structure of I features infinite chains. Those of compounds II, III, and V are layered. The structure of IV features a three-dimensional framework. Tl4Bi2(PS4)2(P2S6) (VII) was also prepared for comparison to the title compounds. The band gaps of each compound are 1.23, 1.27, 1.81, 1.88, 2.06, 1.98, and 1.97 eV for I-VII, respectively. Compounds I, III, IV, and VI melt congruently at 544, 595, 495, and 563 degrees C, respectively, and compounds II, V, and VII melt incongruently at 544, 509, and 600 degrees C, respectively. Solid-state 31P NMR spectroscopy of the reported compounds demonstrates chemical shifts and chemical shift anisotropies in line with related chalcophosphate materials. Evidence for two-bond P-Tl J coupling was observed in 31P NMR spectra (J=481-1781 Hz), and to the best of our knowledge, this is the first example of two-bond P-Tl J coupling and the first example of P-Tl coupling in the solid state. It was possible to assign chemical shifts of inequivalent 31P atoms from the same [PxQy]z- anion type based on different modes of metal ion coordination to the chalcogen. These assignments provide information about the vicinal metal ion contribution to the 31P chemical shift. 相似文献
119.
Shir DJ Jeon S Liao H Highland M Cahill DG Su MF El-Kady IF Christodoulou CG Bogart GR Hamza AV Rogers JA 《The journal of physical chemistry. B》2007,111(45):12945-12958
This Feature Article reviews recent work on an optical technique for fabricating, in a single exposure step, three-dimensional (3D) nanostructures with diverse structural layouts. The approach, which we refer to as proximity field nanopatterning, uses conformable, elastomeric phase masks to pattern thick layers of transparent, photosensitive materials in a conformal contact mode geometry. Aspects of the optics, the materials, and the physical chemistry associated with this method are outlined. A range of 3D structures illustrate its capabilities, and several application examples demonstrate possible areas of use in technologies ranging from microfluidics to photonic materials to density gradient structures for chemical release and high-energy density science. 相似文献
120.
Eric Dickinson Christos Ritzoulis Yukiko Yamamoto Heather Logan 《Colloids and surfaces. B, Biointerfaces》1999,12(3-6):139-146
Ostwald ripening in n-alkane oil-in-water emulsions stabilized by sodium caseinate at neutral pH has been studied by monitoring time-dependent changes in the number-average droplet diameter and the droplet-size distribution. In qualitative agreement with theory, the destabilization rate has been shown to increase with reduction of the n-alkane chain length and on addition of ethanol to the aqueous phase. Replacement of caseinate by β-lactoglobulin also leads to improved stability, but addition of calcium ions does not. The potential use of transglutaminase-induced crosslinking of adsorbed protein as a way of inhibiting the Ostwald ripening of caseinate-stabilized emulsions has been examined. It is shown that enzymic crosslinking before emulsification can lead to a modest reduction in the coarsening rate at long storage times. Crosslinking of caseinate after emulsification produces enhanced stability at short times, but there is a catastrophic loss of stability at long times due to droplet coalescence. 相似文献