全文获取类型
收费全文 | 2271篇 |
免费 | 103篇 |
国内免费 | 16篇 |
专业分类
化学 | 1556篇 |
晶体学 | 7篇 |
力学 | 49篇 |
数学 | 354篇 |
物理学 | 424篇 |
出版年
2024年 | 5篇 |
2023年 | 30篇 |
2022年 | 74篇 |
2021年 | 84篇 |
2020年 | 70篇 |
2019年 | 116篇 |
2018年 | 76篇 |
2017年 | 73篇 |
2016年 | 93篇 |
2015年 | 80篇 |
2014年 | 105篇 |
2013年 | 125篇 |
2012年 | 168篇 |
2011年 | 186篇 |
2010年 | 114篇 |
2009年 | 81篇 |
2008年 | 156篇 |
2007年 | 133篇 |
2006年 | 134篇 |
2005年 | 120篇 |
2004年 | 100篇 |
2003年 | 56篇 |
2002年 | 53篇 |
2001年 | 22篇 |
2000年 | 25篇 |
1999年 | 23篇 |
1998年 | 11篇 |
1997年 | 21篇 |
1996年 | 11篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 1篇 |
1990年 | 2篇 |
1988年 | 2篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1971年 | 2篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有2390条查询结果,搜索用时 15 毫秒
991.
992.
We describe a model of electron transfer reactions affected by local binding to the donor or acceptor sites of a particle in equilibrium with the solution. The statistics of fluctuations of the donor–acceptor energy gap caused by binding/unbinding events are non-Gaussian, and the resulting free energy surfaces of electron transfer are non-parabolic. The band-width of the charge-transfer optical transition is predicted to pass through a maximum as a function of the concentration of binding particles in the solution. The breakdown of the link between the Stokes shift and the reorganization energy of electron transfer is also predicted by the model. 相似文献
993.
Burkhardt M Ruppel M Tea S Drechsler M Schweins R Pergushov DV Gradzielski M Zezin AB Müller AH 《Langmuir : the ACS journal of surfaces and colloids》2008,24(5):1769-1777
We report on interpolyelectrolyte complexes (IPECs) formed by micelles of ionic amphiphilic diblock copolymers with polyisobutylene (PIB) and poly(sodium methacrylate) (PMANa) blocks interacting with quaternized poly(4-vinylpyridine) (P4VPQ). The interpolyelectrolyte complexation was followed by turbidimetry and small angle neutron scattering (SANS). The data obtained by means of a combination of SANS, dynamic light scattering (DLS), and cryogenic transmission electron microscopy (cryo-TEM) provide evidence on the core-shell-corona structure of the complex species with the shell assembled from fragments of electrostatically bound PMANa and quaternized P4VPQ fragments, original PIBx-b-PMAAy micelles apparently playing a lyophilizing part. The complex formation is followed by potentiometric titration as well. This process is initially kinetically controlled. In the second step larger aggregates rearrange in favor of smaller complexes with core-shell-corona structure, which are thermodynamically more stable. An increase in ionic strength of the solution results in dissociation of the complex species as proven by SANS and analytical ultracentrifugation (AUC). This process begins at the certain threshold ionic strength and proceeds via a salt-induced gradual release of chains of the cationic polyectrolyte from the complex species. 相似文献
994.
Wampler HP Zemlyanov DY Lee K Janes DB Ivanisevic A 《Langmuir : the ACS journal of surfaces and colloids》2008,24(7):3164-3170
Homogeneous and mixed adlayers composed of an alkanethiol (1-octadecanethiol, ODT) and a peptide (CGISYGRKKRRQRRR) on GaAs(100) were formed in two different solvent systems: phosphate-buffered saline (PBS) and N,N-dimethylformamide (DMF). The chemical composition of each adlayer was characterized by X-ray photoelectron spectroscopy (XPS). The data showed that the makeup of the adlayer and its stability largely depends on the solvent used. Angle-resolved XPS also revealed that the adlayer thickness and tilt angles were different from values obtained from ellipsometry measurements and vastly varied between the two solvents used. The coverage data extracted from the XPS measurements indicated that homogeneous adlayers of peptide in PBS buffer form a multilayered film. Homogeneous alkanethiol adlayers exhibited monolayer coverage under all solvent treatments. Coadsorbed layers containing both alkanethiol and peptide have fractional monolayer coverage in both solvents. 相似文献
995.
Shakhvorostov D Müser MH Mosey NJ Munoz-Paniagua DJ Pereira G Song Y Kasrai M Norton PR 《The Journal of chemical physics》2008,128(7):074706
A recently suggested mechanism for the stress memory of various metal phosphates is investigated experimentally. Based on first-principles simulations [N. J. Mosey et al., Science 307, 1612 (2005)], it had been argued that atoms with flexible coordination, such as zinc or heavy-metal cations, act as network-forming agents, undergoing irreversible pressure-induced changes in bonding that lead to increased connectivity between phosphate anions. In the present study, orthophosphates of zinc and calcium were exposed to high pressures on surfaces and in diamond anvil cells. An additional set of first-principles simulations was accomplished on alpha-orthophosphate of zinc, which suggested that this material was already cross-linked before compression but that it nevertheless underwent a reversible coordination change under pressure in agreement with the experimental results presented here. Raman spectra indicate an irreversible, pressure-induced loss of long-range crystallinity. The pressures required to induce these changes are around 7 GPa for the zinc phosphates, while they are close to 21 GPa for the calcium phosphates. Hydrogenation of the metal phosphate lowers the threshold pressure by approximately 2-3 GPa in both cases. Moreover, alpha-orthophosphate of zinc could be partially amorphisized under nonisotropic pressure on copper foils. 相似文献
996.
Mass transport across surfactant-covered oil-water interfaces of microemulsions plays an important role in numerous applications. In the current work, we use coarse-grained molecular dynamics simulations to investigate model systems containing flat hexadecane-water interfaces covered by monolayers of nonionic surfactants of various lengths. Several properties of the surfactant monolayers relevant to the mass transport are considered, including the monolayer microstructure, dynamics, and a free energy barrier to the solute transport. It is observed that the dominant contribution of a surfactant monolayer to the free energy barrier is a steric repulsion caused by a local density increase inside the monolayer. The local densities, and hence the free energy barriers, are larger for monolayers composed of longer surfactants. Since it is likely that the solute transport mechanism involves a sequence of jumps between short-lived pores within a monolayer, we perform a detailed analysis of structure, size, and lifetime of these pores. We demonstrate that the pore statistics is consistent with predictions of percolation theory and apply this theory to identify the characteristic length scale of the monolayer microstructure. The obtained pore structures are sensitive to minute changes of surfactant configurations occurring on the picosecond time scale. To reduce this sensitivity, the pores are averaged over short time intervals. The optimal duration of these time intervals is estimated from analysis of dynamics of pores with diameters comparable to or exceeding the characteristic percolation length scale. The developed approach allows one to filter out transient events of the pore dynamics and to focus on events leading to substantial changes of the monolayer microstructure. 相似文献
997.
Victor M. Chernyshev Dmitry A. Khoroshkin Andrey N. Sokolov Vitaly A. Taranushich Eugene S. Gladkov Svetlana V. Shishkina Oleg V. Shishkin Sergey M. Desenko 《Journal of heterocyclic chemistry》2008,45(5):1419-1427
2′‐Substituted 5′,6′,7′,8′‐tetrahydro‐4′H‐spiro[cyclohexane‐1,9′‐[1,2,4]triazolo[5,1‐b]quinazolines] 3a‐d were synthesized by condensation of 3‐substituted 5‐amino‐1,2,4‐triazoles 1a‐d with 2‐cyclohexylidene cyclohexanone 2 in DMF. The compounds 3 were hydrogenated with sodium borohydride in ethanol to give 2′‐substituted cis‐4a',5′,6′,7′,8′,8a'‐hexahydro‐4′H‐spiro[cyclohexane‐1,9′‐[1,2,4]triazolo[5,1‐b]quinazolines] 4a‐d in high yields. The reactions of alkylation, acylation and sulfonylation of the compounds 4 were studied. The structure of the synthesized compounds was determined on the basis of NMR measurements including HSQC, HMBC, NOESY techniques and confirmed by the X‐ray analysis of 6 and 11b . The described synthetic protocols provide rapid access to novel and diversely substituted hydrogenated [1,2,4]triazolo[5,1‐b]quinazolines. 相似文献
998.
999.
Woo HY Hong JW Liu B Mikhailovsky A Korystov D Bazan GC 《Journal of the American Chemical Society》2005,127(3):820-821
A series of alpha,omega-donor-substituted distyrylbenzene dimers held together by the [2.2]paracyclophane core were designed, synthesized, and characterized. Different substituents were chosen to modulate the strength of the donor nitrogen groups and to allow the molecules to be either neutral and soluble in nonpolar organic solvents or charged and water-soluble. The specific neutral structures are (in order of decreasing donor strength) 4,7,12,15-tetra[N,N-bis(6' '-chlorohexyl)-4'-aminostyryl]-[2.2]paracyclophane (1N), 4,7,12,15-tetra[(N-(6' '-chlorohexyl)carbazol-3'-yl)vinyl]-[2.2]paracyclophane (2N), and 4,7,12,15-tetra[N,N-bis(4' '-(6' '-chlorohexyl)phenyl)-4'-aminostyryl]-[2.2]paracyclophane (3N). The charged species are 4,7,12,15-tetra[N,N-bis(6' '-(N,N,N-trimethylammonium)hexyl)-4'-aminostyryl]-[2.2]paracyclophane octaiodide (1C), 4,7,12,15-tetra[(N-(6' '-(N,N,N-trimethylammonium)hexyl)carbazol-3'-yl)vinyl]-[2.2]paracyclophane octaiodide (2C), and 4,7,12,15-tetra[N,N-bis(4' '-(6' '-(N,N,N-trimethylammonium)hexyl)phenyl)-4'-aminostyryl]-[2.2]paracyclophane octaiodide (3C). Two-photon excitation spectra, measured using the two-photon induced fluorescence technique, show in toluene the following trend for the two-photon cross sections (delta): 3N > 2N > 1N. In water the delta values follow the same order, 3C approximately 2C > 1C, but are smaller (approximately one-third). Significantly, the fluorescence quantum yield (eta) in water decreases much more for 1, relative to 2 and 3. The two-photon action cross sections (deltaeta) of 2C and 3C are 294 GM and 359 GM, respectively. These values are among the highest reported thus far. These results show that, to maximize the deltaeta in this class of chromophores, one needs to fine-tune the magnitude of the charge transfer character of the excited state, to minimize fluorescence quenching in polar media. 相似文献
1000.
Both society and industry are interested in increasing the safety of pharmaceuticals. Potentially dangerous compounds could be filtered out at early stages of R&D by computer prediction of biological activity and ADMET characteristics. Accuracy of such predictions strongly depends on the quality & quantity of information contained in a training set. Suggestion that some relevant chemical information can be added to such training sets without disclosing chemical structures was generated at the recent ACS Symposium. We presented arguments that such safety exchange of relevant chemical information is impossible. Any relevant information about chemical structures can be used for search of either a particular compound itself or its close analogues. Risk of identifying such structures is enough to prevent pharma industry from relevant chemical information exchange. 相似文献