全文获取类型
收费全文 | 843篇 |
免费 | 70篇 |
国内免费 | 1篇 |
专业分类
化学 | 573篇 |
晶体学 | 4篇 |
力学 | 21篇 |
数学 | 79篇 |
物理学 | 169篇 |
无线电 | 68篇 |
出版年
2023年 | 9篇 |
2022年 | 16篇 |
2021年 | 24篇 |
2020年 | 30篇 |
2019年 | 28篇 |
2018年 | 18篇 |
2017年 | 13篇 |
2016年 | 45篇 |
2015年 | 26篇 |
2014年 | 25篇 |
2013年 | 40篇 |
2012年 | 55篇 |
2011年 | 74篇 |
2010年 | 33篇 |
2009年 | 28篇 |
2008年 | 46篇 |
2007年 | 46篇 |
2006年 | 36篇 |
2005年 | 37篇 |
2004年 | 34篇 |
2003年 | 28篇 |
2002年 | 17篇 |
2001年 | 6篇 |
2000年 | 7篇 |
1999年 | 6篇 |
1998年 | 5篇 |
1997年 | 16篇 |
1996年 | 9篇 |
1995年 | 7篇 |
1994年 | 17篇 |
1993年 | 8篇 |
1992年 | 7篇 |
1991年 | 12篇 |
1990年 | 7篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 6篇 |
1986年 | 8篇 |
1985年 | 4篇 |
1983年 | 8篇 |
1982年 | 3篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1973年 | 4篇 |
1968年 | 4篇 |
1967年 | 5篇 |
1966年 | 3篇 |
1960年 | 4篇 |
1958年 | 4篇 |
排序方式: 共有914条查询结果,搜索用时 203 毫秒
831.
832.
O'Brien L Duati M Rau S Guckian AL Keyes TE O'Boyle NM Serr A Görls H Vos JG 《Dalton transactions (Cambridge, England : 2003)》2004,(4):514-522
A series of [Ru(bipy)2L]+ and [Ru(phen)2L]+ complexes where L is 2-[5-(3,4-dimethoxyphenyl)-4H-1,2,4-triazol-3-yl]pyridine (HL1) and 4-(5-pyridin-2-yl-4H-1,2,4-triazol-3-yl)benzene-1,2-diol (HL2) are reported. The compounds obtained have been characterised using X-ray crystallography, NMR, UV/Vis and emission spectroscopies. Partial deuteriation is used to determine the nature of the emitting state and to simplify the NMR spectra. The acid-base properties of the compounds are also investigated. The electronic structures of [Ru(bipy)2L1]+ and Ru(bipy)2HL1]2+ are examined using ZINDO. Electro and spectroelectrochemical studies on [Ru(bipy)2(L2)]+ suggest that proton transfer between the catechol and triazole moieties on L2 takes place upon oxidation of the L2 ligand. 相似文献
833.
Accurate force fields are essential for reproducing the conformational and dynamic behavior of condensed-phase systems. The popular AMBER force field has parameters for monophosphates, but they do not extend well to polyphorylated molecules such as ADP and ATP. This work presents parameters for the partial charges, atom types, bond angles, and torsions in simple polyphosphorylated compounds. The parameters are based on molecular orbital calculations of methyldiphosphate and methyltriphosphate at the RHF/6-31+G* level. The new parameters were fit to the entire potential energy surface (not just minima) with an RMSD of 0.62 kcal/mol. This is exceptional agreement and a significant improvement over the current parameters that produce a potential surface with an RMSD of 7.8 kcal/mol to that of the ab initio calculations. Testing has shown that the parameters are transferable and capable of reproducing the gas-phase conformations of inorganic diphosphate and triphosphate. Also, the parameters are an improvement over existing parameters in the condensed phase as shown by minimizations of ATP bound in several proteins. These parameters are intended for use with the existing AMBER 94/99 force field, and they will permit users to apply AMBER to a wider variety of important enzymatic systems. 相似文献
834.
We present a high aspect ratio microfluidic device for culturing cells inside an array of microchambers with continuous perfusion of medium. The device was designed to provide a potential tool for cost-effective and automated cell culture. The single unit of the array consists of a circular microfluidic chamber 40 microm in height surrounded by multiple narrow perfusion channels 2 microm in height. The high aspect ratio (approximately 20) between the microchamber and the perfusion channels offers advantages such as localization of the cells inside the microchamber as well as creating a uniform microenvironment for cell growth. Finite element methods were used to simulate flow profile and mass transfer of the device. Human carcinoma (HeLa) cells were cultured inside the device with continuous perfusion of medium at 37 degrees C and was grown to confluency. The microfluidic cell culture array could potentially offer an affordable platform for a wide range of applications in high throughput cell-based screening, bioinformatics, synthetic biology, quantitative cell biology, and systems biology. 相似文献
835.
Kirwan LJ Fawell PD van Bronswijk W 《Langmuir : the ACS journal of surfaces and colloids》2004,20(10):4093-4100
FTIR-ATR was used to examine in situ the interaction of polyacrylate and hematite at pH 13. Static light scattering and mobility measurements were used to assess solution polyacrylate dimensions and hematite surface charge, respectively. Polyacrylate adsorption occurred only with the addition of electrolyte (e.g., NaCl), and it was found that excess cations, up to approximately 1 M, facilitated adsorption, above which the effect was found to plateau. At pH 13 and at low ionic strength, adsorption of polyacrylate onto hematite is facilitated by cations in solution shielding both the negative acrylate functionality of the polymer and the negative hematite surface. The shielding of the hematite surface continues to increase with increasing salt concentration up to a measured 3 M. Similarly, the shielding of the polymer increased with electrolyte concentration up to approximately 1 M salt, beyond which no further increase in shielding was observed. At this concentration the polymer assumes a finite minimum size in solution that ultimately limits the amount adsorbed. The dimension of the polymer in solution was found to be independent of monovalent cation type. Thus, at high pH and high ionic strength adsorption is determined by the degree of hematite surface charge reduction. The cation-hematite surface interaction was found to be specific, with lithium leading to greater polyacrylate adsorption than sodium, which was followed by cesium. The stronger affinity of lithium for the hematite surface over sodium and cesium is indicative of the inverse lyotropic adsorption series and has been rationalized in the past by the "structure-making-structure-breaking" model. These results provide a useful insight into the likely adsorption mechanism for polyacrylate flocculants at high pH and ionic strength onto residues in the Bayer processing of bauxite. 相似文献
836.
Luke M. Geever 《European Polymer Journal》2006,42(10):2540-2548
In this contribution we have developed thermosensitive polymer matrices based on N-isopropylacrylamide (NIPAAm). Preparation of the hydrogels involved photopolymerisation of a combination of NIPAAm, 1-vinyl-2-pyrrolidinone (NVP) and distilled water, in appropriate amounts and contained a UV-light sensitive initiator called 1-hydroxycyclohexylphenylketone. As NIPAAm monomer could be readily dissolved in mixtures of liquid NVP and distilled water, the use of organic solvents was not required in the polymerisation process. Furthermore, chemical crosslinking agents are not needed in the synthesis. By alternating the feed ratio, hydrogels were synthesised to have lower critical solution temperatures (LCST) in the vicinity of 37 °C. This ability to shift the phase transition temperature of the gels provides excellent flexibility in tailoring transitions for specific uses. The transition temperature of the pseudo gels was established using cloud point measurement and modulated differential scanning calorimetry (MDSC). The chemical structure of the xerogels was characterised by means of Fourier transform infrared spectroscopy (Ftir), while swelling experiments in distilled water indicate that the swelling and dissolution behaviour of the gels is strongly temperature dependent. 相似文献
837.
Physically crosslinked complexes of polyvinyl pyrrolidinone-poly (N-isopropylacrylamide) (PVP-PNIPAAm) were prepared by photopolymerisation from a mixture of the monomers 1-vinyl-2-pyrrolidinone and N-isopropylacrylamide. IR spectroscopy and calorimetry were used to characterise the resulting xerogels. By alternating the monomer feed ratio, copolymers were synthesised to have their own distinctive lower critical solution temperature (LCST). The transition temperature of the gels was established using cloud point measurement and modulated differential scanning calorimeter (MDSC). This ability to shift the phase transition temperature of the copolymers provides excellent flexibility in tailoring transitions for specific uses. Swelling experiments were performed on the copolymer disks in distilled water at varying temperatures to establish the behaviour of the gels above and below phase transition temperature. The results obtained show that below transition temperature, the gels are water soluble but above this temperature they are slightly less water soluble; significantly less water soluble; or water insoluble; depending on the composition and LCST of the gel. 相似文献
838.
Tepavcevic S Wroble AT Bissen M Wallace DJ Choi Y Hanley L 《The journal of physical chemistry. B》2005,109(15):7134-7140
Conducting polymer films are grown by mass-selected, hyperthermal thiophene ions coincident on a surface with a thermal beam of organic monomers of either alpha-terthiophene (3T) or p-terphenyl (3P) neutrals. Mass spectrometry and X-ray photoelectron spectroscopy previously verified polymerization of both 3T and 3P by 200 eV C(4)H(4)S(+) during surface polymerization by ion-assisted deposition (SPIAD). The electronic structure of these films are probed here by ultraviolet photoelectron spectroscopy (UPS) and polarized near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and compared with similar spectra of evaporated films. The conducting polymer films formed by SPIAD display new valence band features resulting from a reduction in both their band gap and barrier to hole injection, which are calculated from the occupied and unoccupied valence band states measured by UPS and NEXAFS. These changes in film electronic structure result from an increase in the electron conjugation length and other changes in film structure induced by SPIAD. 相似文献
839.
840.