全文获取类型
收费全文 | 734篇 |
免费 | 38篇 |
国内免费 | 3篇 |
专业分类
化学 | 656篇 |
力学 | 2篇 |
数学 | 79篇 |
物理学 | 38篇 |
出版年
2023年 | 2篇 |
2022年 | 2篇 |
2021年 | 7篇 |
2020年 | 9篇 |
2019年 | 9篇 |
2018年 | 3篇 |
2017年 | 5篇 |
2016年 | 21篇 |
2015年 | 20篇 |
2014年 | 25篇 |
2013年 | 40篇 |
2012年 | 59篇 |
2011年 | 65篇 |
2010年 | 37篇 |
2009年 | 32篇 |
2008年 | 74篇 |
2007年 | 66篇 |
2006年 | 58篇 |
2005年 | 44篇 |
2004年 | 52篇 |
2003年 | 36篇 |
2002年 | 28篇 |
2001年 | 6篇 |
2000年 | 13篇 |
1999年 | 3篇 |
1998年 | 4篇 |
1997年 | 2篇 |
1996年 | 9篇 |
1995年 | 5篇 |
1994年 | 9篇 |
1993年 | 7篇 |
1991年 | 5篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有775条查询结果,搜索用时 15 毫秒
271.
Valcárcel A Clotet A Illas F Ricart JM 《Physical chemistry chemical physics : PCCP》2007,9(2):311-317
We have studied the adsorption properties of propyne on the Rh(111) surface by means of the generalized gradient approach of density functional theory using periodic slab models. The simulation of the vibrational spectra has permitted us to corroborate and complete the experimental band assignment and to confirm the adsorption site preference. Propyne prefers to sit on a 3-fold hollow site, with the C[triple bond]C axis parallel to a Rh-Rh bond and the molecular plane tilted away from the surface normal. The comparison between the adsorption behaviour of propyne on Rh(111) and on other (111) metal surfaces allows one to provide an explanation for the different reactivity observed experimentally. 相似文献
272.
Pedrouzo M Reverté S Borrull F Pocurull E Marcé RM 《Journal of separation science》2007,30(3):297-303
A method was developed to determine 11 pharmaceutical compounds in water samples. The method uses SPE and HPLC coupled to MS (LC/MS) using ESI in both positive and negative modes. Three different sorbents were compared for the extraction of analytes from river and sewage treatment plant (STP) waters and OASIS HLB provided the best results. For the solid-phase extraction of 500 mL of river water samples, the recoveries were between 41 and 101% with the exception of acetaminophen, salicylic acid and naproxen. The LODs were between 3 and 5 ng/L for all the compounds, except naproxen which had an LOD of 15 ng/L. Acetaminophen, caffeine, carbamazepine, bezafibrate and ibuprofen were found in three of the tested river samples at ng/L levels and among them, the highest values were for caffeine and bezafibrate with 305 and 363 ng/L, respectively. For the influent and effluent water samples of the STP, volumes of 100 and 250 mL were used, respectively, to obtain acceptable recoveries. All the compounds showed recoveries between 33 and 91% for effluent samples and 33-72% for influent samples, with the exception of acetaminophen, salicylic acid and bezafibrate, which had lower recoveries. The method developed enabled pharmaceuticals in the influent and effluent sewage waters to be determined in five campaigns carried out between February 2004 and June 2005. Several pharmaceuticals were found in the influent samples: for instance, maximum concentrations of ibuprofen and caffeine were 6 and 40 microg/L, respectively. 相似文献
273.
Martínez-Lillo J Armentano D De Munno G Cano J Lloret F Julve M Faus J 《Inorganic chemistry》2011,50(24):12405-12407
The use of the [ReCl(4)(bpym)] precursor as a ligand toward the fully solvated nickel(II) metal ion affords the first example of a 2,2'-bipyrimidine-bridged Re(IV)-Ni(II) complex, [ReCl(4)(μ-bpym)NiBr(2)(H(2)O)(2)] (1), whose intramolecular ferromagnetic coupling has been substantiated from both experimental and theoretical studies. 相似文献
274.
This study presents the development of an analytical method for determining 9 synthetic musks in water matrices. The developed method is based on stir bar sorptive extraction (SBSE), coated with polydimethylsiloxane, and coupled with a thermal desorption–gas chromatography–mass spectrometry system (TD–GC–MS). SBSE can efficiently trap and desorb the analytes providing low limits of detection (between 0.02 ng L−1 and 0.3 ng L−1). Method validation showed good linearity, repeatability and reproducibility for all compounds. Furthermore, the limited manipulation of the sample required in this method implies a significant decrease of the risk of external contamination of the samples. The performance of the method in real samples was evaluated by analysing biological wastewater treatment plant (WWTP) influent and effluent samples, reverse osmosis treatment plant effluents and river waters. The most abundant musk was galaxolide with values up to 2069 ng L−1 and 1432 ng L−1 in the influent and effluent of urban WWTP samples, respectively. Cashmeran, Pantolide and Tonalide were also detected in all the matrices with values up to 94 ng L−1, 26 ng L−1 and 88 ng L−1, respectively. Although in Europe the use of nitromusks in cosmetics is prohibited, musk xylene and musk ketone were detected both in the WWTP and in the river samples. As far as we know, this is the first time than a SBSE method coupled with TD is applied for the determination of synthetic musks in water samples. 相似文献
275.
Pepiol A Teixidor F Sillanpää R Lupu M Viñas C 《Angewandte Chemie (International ed. in English)》2011,50(52):12491-12495
Step by step: The cluster [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-) is an excellent platform for making a stepwise tunable redox potential system by dehydroiodination. With the addition of up to eight iodine substituents (purple; see picture), there is a fall in the E(1/2)(Co(III)/Co(II)) value from -1.80?V to -0.68?V (vs. Fc(+)/Fc; Fc = ferrocene). A practical application of this tunability has been observed in the growth of polypyrrole. 相似文献
276.
Eudald Vilaseca Isabel Pastor Adriana Isvoran Sergio Madurga Josep-Llu��s Garc��s Francesc Mas 《Theoretical chemistry accounts》2011,128(4-6):795-805
The diffusion of tracer particles in 3D macromolecular crowded media has been studied using two methodologies, simulation and experimental, with the aim of comparing their results. First, the diffusion of a tracer in an obstructed 3D lattice with mobile and big size obstacles has been analyzed through a Monte Carlo (MC) simulation procedure. Secondly, fluorescence recovery after photobleaching (FRAP) experiments have been carried out to study the diffusion of a model protein (alpha-chymotrypsin) in in vitro crowded solution where two type of Dextran molecules are used as crowder agents. To facilitate the comparison, the relative size between the tracer and the crowder is the same in both studies. The results indicate a qualitative agreement between the diffusional behaviors observed in the two studies. The dependence of the anomalous diffusion exponent and the limiting diffusion coefficient on the obstacle size and excluded volume shows, in both cases, a similar tendency. The introduction of a reduced mobility parameter in the simulation model accounting for the short-range tracer?Cobstacle interactions allows obtaining a quantitative agreement between the limiting diffusion coefficient values yielded by both procedures. The simulation?Cexperiment quantitative agreement for the anomalous diffusion exponent requires further improvements. As far as we know, this is the first reported work where both techniques are used in parallel to study the diffusion in macromolecular crowded media. 相似文献
277.
Florez E Gomez T Rodriguez JA Illas F 《Physical chemistry chemical physics : PCCP》2011,13(15):6865-6871
A systematic density functional study of the adsorption and dissociation of H(2) on the clean (001) surface of various transition metal carbides (TMCs; TM = Ti, Zr, V, Mo) and on Au(4) nanoclusters supported on these TMCs is presented. It is found that the H(2) dissociation on the bare clean TMCs strongly depends on the chemical nature of the support. Thus, the H(2) molecule interacts rather strongly with TiC(001) and ZrC(001) but very weakly with VC(001) and δ-MoC(001). For the supported Au(4) cluster, two different types of molecular mechanisms are found. For Au(4)/TiC(001) and Au(4)/ZrC(001), H(2) dissociation leads to a H atom directly interacting with the Au(4) cluster while the second H atom is transferred to the support. In contrast, for Au(4)/VC(001) and Au(4)/δ-MoC(001), both H atoms interact with the Au(4) cluster. Overall, the present study suggests that, among the systems studied, Au/ZrC is the best substrate for H(2) dissociation. 相似文献
278.
Vilaseca E Isvoran A Madurga S Pastor I Garcés JL Mas F 《Physical chemistry chemical physics : PCCP》2011,13(16):7396-7407
Particle diffusion in crowded media was studied through Monte Carlo simulations in 3D obstructed lattices. Three particular aspects affecting the diffusion, not extensively treated in a three-dimensional geometry, were analysed: the relative particle-obstacle size, the relative particle-obstacle mobility and the way of having the obstacles distributed in the simulation space (randomly or uniformly). The results are interpreted in terms of the parameters that characterize the time dependence of the diffusion coefficient: the anomalous diffusion exponent (α), the crossover time from anomalous to normal diffusion regimes (τ) and the long time diffusion coefficient (D*). Simulation results indicate that there are a more anomalous diffusion (smaller α) and a lower long time diffusion coefficient (D*) when obstacle concentration increases, and that, for a given total excluded volume and immobile obstacles, the anomalous diffusion effect is less important for bigger size obstacles. However, for the case of mobile obstacles, this size effect is inverted yielding values that are in qualitatively good agreement with in vitro experiments of protein diffusion in crowded media. These results underline that the pattern of the spatial partitioning of the obstacle excluded volume is a factor to be considered together with the value of the excluded volume itself. 相似文献
279.
Luckas N Gotterbarm K Streber R Lorenz MP Höfert O Viñes F Papp C Görling A Steinrück HP 《Physical chemistry chemical physics : PCCP》2011,13(36):16227-16235
We studied the adsorption and reactivity of SO(2) on clean and oxygen precovered Pd(100) with high resolution X-ray photoelectron spectroscopy and density functional calculations. Upon adsorption at 120 K two different SO(2) species were detected, which were identified as upright-standing and flat-lying molecules by comparing the calculated core level shifts. In agreement with the relative stabilities determined by the calculations the intensities of the photoelectron spectra indicate that the majority species are upright-standing SO(2). Upon heating the quantitative analysis of the data indicates desorption of SO(3) and formation of atomic sulfur. On the oxygen precovered surface small amounts of SO(3) are formed already upon SO(2) adsorption at low temperatures. Upon heating stepwise oxidation of SO(2) to SO(3) and, eventually, to SO(4) is found. Two different SO(4) species were detected, which are assigned to SO(4) bound in the proximity of or remote from oxygen adatoms, according to core level shift estimates. 相似文献
280.
Lerouge F Ferrer-Ugalde A Viñas C Teixidor F Sillanpää R Abreu A Xochitiotzi E Farfán N Santillan R Núñez R 《Dalton transactions (Cambridge, England : 2003)》2011,40(29):7541-7550
A new family of photoluminescent neutral and anionic di-carboranyl and tetra-carboranyl derivatives have been synthesized and characterized. The reaction of α,α'-bis(3,5-bis(bromomethyl)phenoxy-m-xylene with 4 equiv. of the monolithium salt of 1-Ph-1,2-C(2)B(10)H(11) or 1-Me-1,2-C(2)B(10)H(11) gives the neutral tetracarboranyl-functionalized aryl ether derivatives closo-1 and closo-2, respectively. The addition of the monolithium salt of 1-Ph-1,2-closo-C(2)B(10)H(11) to α,α,'-dibromo-m-xylene or 2,6-dibromomethyl-pyridine gives the corresponding di-carboranyl derivatives closo-3 and closo-4. These compounds, which contain four or two closo clusters, were degraded using the classical method, KOH in EtOH, affording the corresponding nido species, which were isolated as potassium or tetramethylammonium salts. All the compounds were characterized by IR, (1)H, (11)B and (13)C NMR spectroscopy, and the crystal structure of closo-3 was analysed by X-ray diffraction. The carboranyl fragments are bonded through CH(2) units to different organic moieties, and their influence on the photoluminescent properties of the final molecules has been studied. All the closo- and nido-carborane derivatives exhibit a blue emission under ultraviolet excitation at room temperature in different solvents. The fluorescence properties of these closo and nido-derivatives depend on the substituent (Ph or Me) bonded to the C(cluster), the solvent polarity, and the organic unit bearing the carborane clusters (benzene or pyridine). In the case of nido-derivatives, an important effect of the cation is also observed. 相似文献