全文获取类型
收费全文 | 315篇 |
免费 | 14篇 |
专业分类
化学 | 291篇 |
晶体学 | 3篇 |
力学 | 3篇 |
数学 | 12篇 |
物理学 | 20篇 |
出版年
2023年 | 4篇 |
2022年 | 9篇 |
2021年 | 8篇 |
2020年 | 9篇 |
2019年 | 9篇 |
2018年 | 3篇 |
2017年 | 1篇 |
2016年 | 11篇 |
2015年 | 6篇 |
2014年 | 7篇 |
2013年 | 13篇 |
2012年 | 20篇 |
2011年 | 25篇 |
2010年 | 11篇 |
2009年 | 10篇 |
2008年 | 23篇 |
2007年 | 18篇 |
2006年 | 22篇 |
2005年 | 17篇 |
2004年 | 22篇 |
2003年 | 9篇 |
2002年 | 16篇 |
2001年 | 3篇 |
2000年 | 1篇 |
1999年 | 3篇 |
1998年 | 6篇 |
1997年 | 5篇 |
1996年 | 6篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1978年 | 3篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1973年 | 1篇 |
排序方式: 共有329条查询结果,搜索用时 0 毫秒
11.
Fernando P. Carvalho Jean-Pierre Villeneuve Chantal Cattini 《Trends in analytical chemistry : TRAC》1999,18(11):1005-664
A seaweed sample (Fucus sp.) was prepared, homogenised and distributed to laboratories worldwide as the IAEA-140 intercomparison material for the analysis of organochlorine compounds and petroleum hydrocarbons. A total of 80 laboratories from 51 countries reported results for this sample. The data sets reported by laboratories were evaluated statistically and the mean concentration values could be computed with 95% confidence limits for a large number of analytes. The accuracy of the analytical performance of each laboratory has been introduced by using Z-scores. The spread of results reported generally indicates that the accurate determination of many persistent organic pollutants, such as hexachlorobenzene, lindane, Aroclors or fluoranthene, is still difficult for many laboratories. The final results of this intercomparison exercise enable individual participants to assess their performance and, where necessary, to introduce appropriate modifications in their analytical procedures. Furthermore, as a series of statistical criteria was fulfilled for a number of compounds, the sample IAEA-140 can now be used as a reference material for quality control in the determination of chlorinated compounds and petroleum hydrocarbons in environmental samples. 相似文献
12.
A rearrangement in basic medium of the natural endoperoxide G3-factor extracted from Eucalyptus grandis is described. Evidence to support a 1,2-dioxetane intermediate that decomposes with weak luminescence emission (quantum yield) is presented. 相似文献
13.
The trans-cis isomerization of the styrylpyridine carbon-carbon double bond induced by visible light irradiation in fac-[Re(CO)(3)(bpy)(stpy)](+) (bpy = 2,2'-bipyridine; stpy = t-4-styrylpyridine) has been investigated by means of quantum-chemical methods. The structures of the various cis and trans conformers of [Re(CO)(3)(bpy)(stpy)](+) have been optimized at the density functional theory (DFT) level. Three rotational conformers for the most stable trans isomer lie within 2.3 kJ mol(-1) each other. The energy difference between the cis and trans isomers is 27.0 kJ mol(-1). The electronic spectroscopy of the most stable conformers has been investigated by time-dependent DFT (TD-DFT) and complete active space self-consistent field/CAS second order perturbation theory (CASSCF/CASPT2) calculations. The lowest absorption bands are dominated by metal-to-ligand charge-transfer (MLCT, d(Re)-->pi*(bpy)) transitions calculated at about 25,000 cm(-1) and by a strong intraligand (1)IL (pi(stpy)-->pi*(stpy)) transition in the near UV region. On the basis of CASSCF potential energy curves (PECs) calculated as a function of the torsion angle of the C=C bond of the styrylpyridine ligand, it is shown that the role of the low-lying MLCT states is important in the photoisomerization mechanism. In contrast to the free organic ligand, in which the singlet mechanism is operational via the (1)IL (S(1)) and electronic ground (S(0)) states, coordination to the rhenium steers the isomerization to the triplet PEC corresponding to the (3)IL state. From the (3)IL(t) (t = trans) the system evolves to the perpendicular intermediate (3)IL(p) (p = perpendicular) following a 90 degrees rotation around the styrylpyridine C=C bond. The metal center acts as a photosensitizer because of the presence of photoactive MLCT states under visible irradiation. The position of the crossing between the (3)IL and electronic ground state PEC determines the quantum yield of the isomerization process. 相似文献
14.
Dr. Subrata Kundu Prof. Dr. S. Chantal E. Stieber Dr. Maryline G. Ferrier Dr. Stosh A. Kozimor Dr. Jeffery A. Bertke Prof. Dr. Timothy H. Warren 《Angewandte Chemie (International ed. in English)》2016,55(35):10321-10325
Nitrosobenzene (PhNO) serves as a stable analogue of nitroxyl (HNO), a biologically relevant, redox‐active nitric oxide derivative. Capture of nitrosobenzene at the electron‐deficient β‐diketiminato nickel(I) complex [iPr2NNF6]Ni results in reduction of the PhNO ligand to a (PhNO)./? species coordinated to a square planar NiII center in [iPr2NNF6]Ni(η2‐ONPh). Ligand centered reduction leads to the (PhNO)2? moiety bound to NiII supported by XAS studies. Systematic investigation of structure–reactivity patterns of (PhNO)./? and (PhNO)2? ligands reveals parallels with superoxo (O2)./? and peroxo (O2)2? ligands, respectively, and forecasts reactivity patterns of the more transient HNO ligand. 相似文献
15.
Radka Baková Majed Chergui Chantal Daniel Antonín Vlček Stanislav Záliš 《Coordination chemistry reviews》2011,255(7-8):975-989
Spin–orbit coupling (SOC) is an essential factor in photophysics of heavy transition metal complexes. By enabling efficient population of the lowest triplet state and its strong emission, it gives rise to a very interesting photophysical behavior and underlies photonic applications such as organic light emitting diodes (OLED) or luminescent imaging agents. SOC affects excited-state characters, relaxation dynamics, radiative and nonradiative decay pathways, as well as lifetimes and reactivity. We present a new photophysical model based on mixed-spin states, illustrated by relativistic spin–orbit TDDFT and MS-CASPT2 calculations of [Re(imidazole)(CO)3(1,10-phenanthroline)]+. An excited-state scheme is constructed from spin–orbit (SO) states characterized by their energies, double-group symmetries, parentages in terms of contributing spin-free singlets and triplets, and oscillator strengths of corresponding transitions from the ground state. Some of the predictions of the relativistic SO model on the number and nature of the optically populated and intermediate excited states are qualitatively different from the spin-free model. The relativistic excited-state model accounts well for electronic absorption and emission spectra of ReI carbonyl diimines, as well as their complex photophysical behavior. Then, we discuss the SO aspects of photophysics of heavy metal complexes from a broader perspective. Qualitative SO models as well as previous relativistic excited-state calculations are briefly reviewed together with experimental manifestations of SOC in polypyridine and cyclometallated complexes of second- and third row d6 metals. It is shown that the relativistic SO model can provide a comprehensive and unifying photophysical picture. 相似文献
16.
Robin J. Marles James B. Hudson Elizabeth A. Graham Chantal Soucy-Breau Peter Morand R. Lilia Compadre Cesar M. Compadre G. H. Neil Towers J. Thor Arnason 《Photochemistry and photobiology》1992,56(4):479-487
The photoactivated antiviral and cytotoxic activities of the naturally occurring thiophene, alpha-terthienyl (1), and 15 synthetic analogues were evaluated against murine cytomegalovirus and Sindbis virus, and murine mastocytoma cells. After irradiation with near UV light, alpha-terthienyl and most of its analogues had significant toxicity, with minimum inhibitory concentrations in the range of 0.02-40 microM. In the absence of near UV irradiation, only one analogue had antiviral activity and five were cytotoxic. The most active analogues were those containing carboxylic acid, hydroxyl, or cyano substituents. Quantitative structure-activity relationship analysis of thiophene phototoxicity suggested that the rate of singlet oxygen production is the primary determinant of antiviral and cytotoxic activities. For phototoxicity against murine cytomegalovirus, a significant role for hydrophobicity was also demonstrated. Tricyclic thiophenes show significant potential for photochemotherapy of viral infections and cancer, and further evaluation in animal models is recommended. 相似文献
17.
Three-dimensional microfabrication by two-photon-initiated polymerization with a low-cost microlaser 总被引:3,自引:0,他引:3
Fabrication of submicrometer structures by two-photon-initiated polymerization is performed with an inexpensive and low-power microlaser. This is made possible by the design of photoinitiators with strong two-photon absorption cross sections. We analyze the influence of both material properties and irradiation conditions on the two-photon polymerization rate and show that resins based on our highly sensitive two-photon photoinitiator can be solidified with microlaser excitation, whereas commercial UV photoresins require ultrashort and intense laser pulses. 相似文献
18.
19.
20.
Ayad T Faugeroux V Génisson Y André C Baltas M Gorrichon L 《The Journal of organic chemistry》2004,69(25):8775-8779
We developed a stereocontrolled route allowing potential access to the eight isomers of 4-benzylaminohex-5-ene-1,2,3-triol in two or four steps and ca. 50% yield from readily available chiral nonracemic cis- or trans-alpha,beta-epoxyimine precursors. A new (NH(4))(2)CO(3)-based carboxylation/intramolecular cyclization sequence allowed regio- and stereocontrolled C-3 epoxide opening while neat C-2 hydrolysis was ensured by simple aqueous acidic treatment. 相似文献