全文获取类型
收费全文 | 503篇 |
免费 | 19篇 |
国内免费 | 2篇 |
专业分类
化学 | 391篇 |
晶体学 | 11篇 |
力学 | 6篇 |
数学 | 54篇 |
物理学 | 62篇 |
出版年
2023年 | 5篇 |
2022年 | 5篇 |
2021年 | 13篇 |
2020年 | 12篇 |
2019年 | 6篇 |
2018年 | 5篇 |
2017年 | 7篇 |
2016年 | 19篇 |
2015年 | 14篇 |
2014年 | 16篇 |
2013年 | 39篇 |
2012年 | 35篇 |
2011年 | 39篇 |
2010年 | 20篇 |
2009年 | 21篇 |
2008年 | 30篇 |
2007年 | 28篇 |
2006年 | 23篇 |
2005年 | 24篇 |
2004年 | 25篇 |
2003年 | 15篇 |
2002年 | 21篇 |
2001年 | 5篇 |
2000年 | 7篇 |
1999年 | 4篇 |
1998年 | 7篇 |
1997年 | 3篇 |
1996年 | 4篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 7篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1989年 | 6篇 |
1988年 | 2篇 |
1987年 | 5篇 |
1986年 | 1篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1982年 | 6篇 |
1981年 | 2篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 3篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有524条查询结果,搜索用时 31 毫秒
11.
12.
The characters, dynamics, and relaxation pathways of low-lying excited states of the complexes [W(CO)(5)L] [L = 4-cyanopyridine (pyCN) and piperidine (pip)] were investigated using theoretical and spectroscopic methods. DFT calculations revealed the delocalized character of chemically and spectroscopicaly relevant molecular orbitals and the presence of a low-lying manifold of CO pi-based unoccupied molecular orbitals. Traditional ligand-field arguments are not applicable. The lowest excited states of [W(CO)(5)(pyCN)] are W --> pyCN MLCT in character. They are closely followed in energy by W --> CO MLCT states. Excitation at 400 or 500 nm populates the (3)MLCT(pyCN) excited state, which was characterized by picosecond time-resolved IR and resonance Raman spectroscopy. Excited-state vibrations were assigned using DFT calculations. The (3)MLCT(pyCN) excited state is initially formed highly excited in low-frequency vibrations which cool with time constants between 1 and 20 ps, depending on the excitation wavelength, solvent, and particular high-frequency nu(CO) or nu(CN) mode. The lowest excited states of [W(CO)(5)(pip)] are W --> CO MLCT, as revealed by TD-DFT interpretation of a nanosecond time-resolved IR spectrum that was measured earlier in a low-temperature glass (Johnson, F. P. A.; George, M. W.; Morrison, S. L.; Turner, J. J. J. Chem. Soc., Chem. Commun. 1995, 391-393). MLCT(CO) excitation involves transfer of electron density from the W atom and, to a lesser extent, the trans CO to the pi orbitals of the four cis CO ligands. Optical excitation into MLCT(CO) transition of either complex in fluid solution triggers femtosecond dissociation of a W-N bond, producing [W(CO)(5)(solvent)]. It is initially vibrationally excited both in nu(CO) and anharmonicaly coupled low-frequency modes. Vibrational cooling occurs with time constants of 16-22 ps while the intramolecular vibrational energy redistribution from the v = 1 nu(CO) modes is much slower, 160-220 ps. No LF excited states have been found for the complexes studied in a spectroscopically relevant range up to 6-7 eV. It follows that spectroscopy, photophysics, and photochemistry of [W(CO)(5)L] and related complexes are well described by an interplay of close-lying MLCT(L) and MLCT(CO) excited states. The high-lying LF states play only an indirect photochemical role by modifying potential energy curves of MLCT(CO) states, making them dissociative. 相似文献
13.
A new method for the synthesis of fluoromethylenecyclopropane nucleosides by alkylation-elimination procedure is described. Fluorination of methylenecyclopropane carboxylate 6 gave fluoroester 7. Treatment of 7 with phenylselenenyl bromide afforded the desired ethyl (E)-2-bromomethyl-1-fluoro-2-phenylselenenylcyclopropane-1-carboxylate 11 in 85% yield. DIBALH reduction of 11 gave 13, which after acetylation to 14 was reacted with 2-amino-6-chloropurine to give the 9-alkylated product 15 in 87% yield. Se-oxidation of 15 with hydrogen peroxide afforded 16, which underwent smooth elimination in a mixture of THF-DMF at 60 °C giving rise to a Z,E mixture of protected nucleosides 17. Deacetylation gave Z-1a and E-1a which were separated on a silica gel column. Both Z-1a and E-1a were converted into the respective guanine analogues Z-1b and E-1b. 相似文献
14.
Stanoeva T Neshchadin D Gescheidt G Ludvik J Lajoie B Batchelor SN 《The journal of physical chemistry. A》2005,109(49):11103-11109
The degradation of dyes is frequently initiated by one-electron oxidation or reduction; however, relatively little is known about the initially formed radicals. Acid Green 25 (AG25), Crystal Violet (CVI), Methylene Blue (MB), and Acid Orange 7 (AO7), representing paradigms of four types of commercial organic dyes, were therefore investigated in terms of their redox behavior. Their redox potentials in MeCN and buffered aqueous solutions were determined by cyclic voltammetry. The structures of the one-electron reduced and oxidized dyes were established by EPR spectroscopy and by theoretical calculations on the density functional level of theory. 相似文献
15.
Polacco G Stastna J Biondi D Antonelli F Vlachovicova Z Zanzotto L 《Journal of colloid and interface science》2004,280(2):366-373
Asphalt is known to be a colloidal suspension in which asphaltenes are covered by a stabilizing phase of polar resins and form complex micelles that are dispersed in the oily maltenic phase. In order to enhance its mechanical properties (e.g., in road paving), asphalts are often loaded with polymeric materials, thereby obtaining blends that can have different physical or chemical structures, depending on the composition of the added polymer. Asphalts modified by the addition of reactive ethylene terpolymers were prepared and their dielectric and rheological properties were measured both before and after a cure at high temperature. Even if it is not possible to determine the exact nature of the chemical interactions between asphalt and polymer, master curves obtained from dynamic data clearly show that during the cure the material tends to the behavior of a cross-linked network. 相似文献
16.
Klara Markova Klaudia Chmelova Srgio M. Marques Philippe Carpentier David Bednar Jiri Damborsky Martin Marek 《Chemical science》2020,11(41):11162
Computational design of protein catalysts with enhanced stabilities for use in research and enzyme technologies is a challenging task. Using force-field calculations and phylogenetic analysis, we previously designed the haloalkane dehalogenase DhaA115 which contains 11 mutations that confer upon it outstanding thermostability (Tm = 73.5 °C; ΔTm > 23 °C). An understanding of the structural basis of this hyperstabilization is required in order to develop computer algorithms and predictive tools. Here, we report X-ray structures of DhaA115 at 1.55 Å and 1.6 Å resolutions and their molecular dynamics trajectories, which unravel the intricate network of interactions that reinforce the αβα-sandwich architecture. Unexpectedly, mutations toward bulky aromatic amino acids at the protein surface triggered long-distance (∼27 Å) backbone changes due to cooperative effects. These cooperative interactions produced an unprecedented double-lock system that: (i) induced backbone changes, (ii) closed the molecular gates to the active site, (iii) reduced the volumes of the main and slot access tunnels, and (iv) occluded the active site. Despite these spatial restrictions, experimental tracing of the access tunnels using krypton derivative crystals demonstrates that transport of ligands is still effective. Our findings highlight key thermostabilization effects and provide a structural basis for designing new thermostable protein catalysts.Illustration of cooperative thermostabilization effects of the double-lock system that: (i) induced backbone changes, (ii) closed the molecular gates, (iii) reduced the volumes of the main and slot access tunnels, and (iv) occluded the active site. 相似文献
17.
Jarmila Duskova Jiri Labsky Ivana Cisarova Tereza Skalova Jan Dohnalek Jindrich Hasek 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(9):o563-o566
The asymmetric unit of the title compound, C11H5D16N2O2·0.33H2O, is formed by three crystallographically independent piperidin‐1‐yloxyl molecules and a molecule of water. The molecules are crosslinked by nine hydrogen bonds into layers parallel with the ac plane. The water molecule contributes to the stability of the low‐symmetry arrangement by four hydrogen bonds. 相似文献
18.
A sample pretreatment technique for silicon nitride involving digestion and matrix/traces separation was developed by means of radiotracers and applied to analysis of this material by inductively coupled plasma atomic emission spectrometry, inductively coupled plasma mass spectrometry and graphite furnace atomic absorption spectrometry. The results obtained for a high purity silicon nitride material by these methods are compared each with the other and with those obtained by neutron activation analysis. The limits of detection and the capabilities of the methods are compared and discussed. 相似文献
19.
Zhang X Hines W Adamec J Asara JM Naylor S Regnier FE 《Journal of the American Society for Mass Spectrometry》2005,16(7):1181-1191
An algorithm is presented for the generation of a reliable peptide component peak table from liquid chromatography-mass spectrometry (LC-MS) and subsequent quantitative analysis of stable isotope coded peptide samples. The method uses chemical noise filtering, charge state fitting, and deisotoping toward improved analysis of complex peptide samples. Overlapping peptide signals in mass spectra were deconvoluted by correlation with modeled peptide isotopic peak profiles. Isotopic peak profiles for peptides were generated in silico from a protein database producing reference model distributions. Doublets of heavy and light labeled peak clusters were identified and compared to provide differential quantification of pairs of stable isotope coded peptides. Algorithms were evaluated using peptides from digests of a single protein and a seven-protein mixture that had been differentially coded with stable isotope labeling agents and mixed in known ratios. The experimental results correlated well with known mixing ratios. 相似文献
20.
In this paper we investigate a class of Lie group actions on
, the so-calledpolar actions, that naturally generalize the standard
actions. For a domain invariant under such an action (i.e., a generalized Reinhardt domain) we characterize the invariant
plurisubharmonic functions and determine the envelope of holomorphy in geometric terms. For a generalized Reinhardt domain
containing the origin of
we also compute its automorphism group.
Supported in part by NSF Grant 8602020 相似文献