全文获取类型
收费全文 | 19079篇 |
免费 | 743篇 |
国内免费 | 99篇 |
专业分类
化学 | 13078篇 |
晶体学 | 120篇 |
力学 | 420篇 |
数学 | 2899篇 |
物理学 | 3404篇 |
出版年
2023年 | 122篇 |
2022年 | 172篇 |
2021年 | 268篇 |
2020年 | 377篇 |
2019年 | 397篇 |
2018年 | 234篇 |
2017年 | 236篇 |
2016年 | 600篇 |
2015年 | 556篇 |
2014年 | 645篇 |
2013年 | 1024篇 |
2012年 | 1115篇 |
2011年 | 1248篇 |
2010年 | 744篇 |
2009年 | 659篇 |
2008年 | 1035篇 |
2007年 | 1021篇 |
2006年 | 950篇 |
2005年 | 881篇 |
2004年 | 774篇 |
2003年 | 637篇 |
2002年 | 605篇 |
2001年 | 311篇 |
2000年 | 291篇 |
1999年 | 273篇 |
1998年 | 241篇 |
1997年 | 231篇 |
1996年 | 264篇 |
1995年 | 247篇 |
1994年 | 217篇 |
1993年 | 211篇 |
1992年 | 199篇 |
1991年 | 174篇 |
1990年 | 174篇 |
1989年 | 174篇 |
1988年 | 149篇 |
1987年 | 125篇 |
1986年 | 114篇 |
1985年 | 166篇 |
1984年 | 161篇 |
1983年 | 126篇 |
1982年 | 153篇 |
1981年 | 157篇 |
1980年 | 132篇 |
1979年 | 140篇 |
1978年 | 158篇 |
1977年 | 115篇 |
1976年 | 100篇 |
1975年 | 117篇 |
1974年 | 90篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
Nagel B Warsinke A Katterle M 《Langmuir : the ACS journal of surfaces and colloids》2007,23(12):6807-6811
A new thermoresponsive poly-N-isopropylacrylamide (PNIPAM)-ferrocene polymer was synthesized and characterized. PNIPAMFoxy bears additional oxirane groups which were used for attachment by a self-assembly process on a cysteamine-modified gold electrode to create a thin hydrophilic film. The new redox polymer enabled electrical communication between the cofactor pyrrolinoquinoline quinone (PQQ) of soluble glucose dehydrogenase (sGDH) and the electrode for sensitive detection of this enzyme as a prospective protein label. The temperature influence on the redox polymer/enzyme complex was investigated. An inverse temperature response behavior of surface bound PNIPAMFoxy compared to the soluble polymer was found and is discussed in detail. The highest efficiency of mediated electron transfer for the immobilized PNIPAMFoxy with sGDH was observed at 24 degrees C, which was twice as high as that of its soluble counterpart. A steady-state electrooxidation current densitiy of 4.5 microA.cm-2 was observed in the presence of 10 nM sGDH and 5 mM glucose. A detection limit of 0.5 nM of soluble PQQ-sGDH was obtained. 相似文献
942.
Hanczyc MM Toyota T Ikegami T Packard N Sugawara T 《Journal of the American Chemical Society》2007,129(30):9386-9391
Fatty acids have been investigated as boundary structures to construct artificial cells due to their dynamic properties and phase transitions. Here we have explored the possibility that fatty acid systems also demonstrate movement. An oil phase was loaded with a fatty acid anhydride precursor and introduced to an aqueous fatty acid micelle solution. The oil droplets showed autonomous, sustained movement through the aqueous media. Internal convection created a positive feedback loop, and the movement of the oil droplet was sustained as convection drove fresh precursor to the surface to become hydrolyzed. As the system progressed, more surfactant was produced and some of the oil droplets transformed into supramolecular aggregates resembling multilamellar vesicles. The oil droplets also moved directionally within chemical gradients and exhibited a type of chemotaxis. 相似文献
943.
Watari M Galbraith J Lang HP Sousa M Hegner M Gerber C Horton MA McKendry RA 《Journal of the American Chemical Society》2007,129(3):601-609
Free-standing cantilevers, which directly translate specific biochemical reactions into micromechanical motion, have recently attracted much attention as label-free biosensors and micro/nano robotic devices. To exploit this mechanochemical sensing technology, it is essential to develop a fundamental understanding of the origins of surface stress. Here we report a detailed study into the molecular basis of stress generation in aqueous environments focusing on the pH titration of model mercaptohexadecanoic acid self-assembled monolayers (SAMs), using in situ reference cantilevers coated with nonionizable hexadecanethiol SAMs. Semiautomated data analysis and a statistical model were developed to quantify cyclic deprotonation/protonation reactions on multiple arrays. In-plane force titrations were found to have the sensitivity to detect ionic hydrogen bond formation between protonated and nonprotonated carboxylic acid groups in the proximity of the surface pK1/2, which generated a mean tensile differential surface stress of +1.2 +/- 0.3 mN/m at pH 6.0, corresponding to 1 pN attractive force between two adjacent MHA molecules. Conversely, the magnitude of compressive differential surface stress was found to increase progressively with pH >/= 7.0, reaching a maximum of -14.5 +/- 0.5 mN/m at pH 9.0, attributed to enhanced electrostatic repulsion between deprotonated carboxylic acid groups. However, striking differences were observed in the micromechanical responses to different ionic strength and ion species present in the aqueous environment, highlighting the critical role of counter- and co-ions on surface stress. Our findings provide fundamental insights into the molecular mechanisms of in-plane mechanochemistry, which may be exploited for biosensing and nanoactuation applications. 相似文献
944.
The performance of microchip electrophoresis/electrochemistry system with carbon nanotube (CNT) film electrodes was studied. Electrocatalytic activities of different carbon materials (single-wall CNT (SWCNT), multiwall CNT (MWCNT), carbon powder) cast on different electrode substrates (glassy carbon (GC), gold, and platinum) were compared in a microfluidic setup and their performance as microchip electrochemical detectors was assessed. An MWCNT film on a GC electrode shows electrocatalytic effect toward oxidation of dopamine (E(1/2) shift of 0.09 V) and catechol (E(1/2) shift of 0.19 V) when compared to a bare GC electrode, while other CNT/carbon powder films on the GC electrode display negligible effects. Modification of a gold electrode by graphite powder results in a strong electrocatalytic effect toward oxidation of dopamine and catechol (E(1/2) shift of 0.14 and 0.11 V, respectively). A significant shift of the half-wave potentials to lower values also provide the MWCNT film (E(1/2) shift of 0.08 and 0.08 V for dopamine and catechol, respectively) and the SWCNT film (E(1/2) shift of 0.10 V for catechol) when compared to a bare gold electrode. A microfluidic device with a CNT film-modified detection electrode displays greatly improved separation resolution (R(s)) by a factor of two compared to a bare electrode, reflecting the electrocatalytic activity of CNT. 相似文献
945.
Puig E Garcia-Viloca M Gonzalez-Lafont A Lluch JM Field MJ 《The journal of physical chemistry. B》2007,111(9):2385-2397
The mechanism of the reactions catalyzed by the pyridoxal-phosphate-independent amino acid racemases and epimerases faces the difficult task of deprotonating a relatively low acidicity proton, the amino acid's alpha-hydrogen, with a relatively poor base, a cysteine. In this work, we propose a mechanism for one of these enzymes, glutamate racemase (MurI), about which many controversies exist, and the roles that its active site residues may play. The titration curves and the pK1/2 values of all of the ionizable residues for different structures leading from reactants to products have been analyzed. From these results a concerted mechanism has been proposed in which the Cys70 residue would deprotonate the alpha-hydrogen of the substrate while, at the same time, being deprotonated by the Asp7 residue. To study the consistency of this mechanism classical molecular dynamics (MD) simulations have been carried out along with pK1/2 calculations on the MD-generated structures. 相似文献
946.
Wolff H Bredow T Lerch M Schilling H Irran E Stork A Dronskowski R 《The journal of physical chemistry. A》2007,111(14):2745-2749
The geometric and electronic structure of the recently found new polymorph of tantalum oxynitride, gamma-TaON, and its structural stability were studied quantum-chemically at the density functional level. Results obtained by complementary quantum-chemical techniques with wavefunctions either expanded in atom-centered functions or in plane waves were compared, having employed pure density-functional functionals within the generalized gradient approximation as well as density-functional/Hartree-Fock hybrid methods. In particular, several plausible anion distributions were investigated and, in accordance with Pauling's second rule, it was found that the configuration in which nitrogen occupies crystallographic sites with highest coordination numbers is the most stable one. Theoretically generated local structural parameters were used to improve the accuracy of the experimentally derived information. The bonding situation in the most stable configuration was investigated by an analysis of the density of states. 相似文献
947.
948.
Müller C Wasserberg D Weemers JJ Pidko EA Hoffmann S Lutz M Spek AL Meskers SC Janssen RA van Santen RA Vogt D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(16):4548-4559
A series of donor-functionalized pyrylium salts have been prepared by classical condensation reactions which were further converted into the corresponding thienyl- and pyridyl-substituted polydentate lambda(3)-phosphinines by reaction with P(SiMe(3))(3). Further chemical modification of these phosphorus heterocycles with Hg(OAc)(2) in the presence of methanol resulted in the formation of lambda(5)-phosphinines. The photophysical properties of a selected series of thienyl- and pyridyl-functionalized pyrylium salts, lambda(3)- and lambda(5)-phosphinines, were investigated and the results compared and supported by theoretical calculations on the DFT level. Significant fluorescence was observed for the pyrylium salts and lambda(5)-phosphinines. In contrast, the heteroaromatic substituted lambda(3)-phosphinines show very little emission which is consistent with the low oscillator strength predicted by DFT calculations for this pi-->pi* transition. Furthermore, all three classes of compounds show readily observable phosphorescence in solution, which was determined by time-gated detection at low temperature. 相似文献
949.
950.
Pumera M Smíd B Peng X Golberg D Tang J Ichinose I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(27):7644-7649
A novel protocol for precisely coating individual multiwall carbon nanotubes (MWCNTs) with an ultrathin layer of polypyrrole was developed. The nanocoated MWCNTs were successfully prepared by in situ chemical deposition of polypyrrole in an aqueous suspension of MWCNTs. The coating layer was very uniform and the thickness of the layer was determined by controlling the monomer concentration used, which gave nanometer precision. The products were characterized by transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, electron energy loss spectroscopy, and conductivity and current-voltage measurements. The ultrathin polypyrrole layer could electrically insulate individual MWCNTs. 相似文献