全文获取类型
收费全文 | 2373篇 |
免费 | 110篇 |
国内免费 | 3篇 |
专业分类
化学 | 1741篇 |
晶体学 | 11篇 |
力学 | 49篇 |
数学 | 189篇 |
物理学 | 496篇 |
出版年
2024年 | 9篇 |
2023年 | 23篇 |
2022年 | 76篇 |
2021年 | 99篇 |
2020年 | 79篇 |
2019年 | 112篇 |
2018年 | 109篇 |
2017年 | 83篇 |
2016年 | 111篇 |
2015年 | 98篇 |
2014年 | 101篇 |
2013年 | 124篇 |
2012年 | 189篇 |
2011年 | 197篇 |
2010年 | 127篇 |
2009年 | 73篇 |
2008年 | 129篇 |
2007年 | 138篇 |
2006年 | 142篇 |
2005年 | 125篇 |
2004年 | 95篇 |
2003年 | 58篇 |
2002年 | 58篇 |
2001年 | 21篇 |
2000年 | 11篇 |
1999年 | 11篇 |
1998年 | 13篇 |
1997年 | 9篇 |
1996年 | 16篇 |
1995年 | 2篇 |
1994年 | 11篇 |
1993年 | 8篇 |
1992年 | 7篇 |
1991年 | 1篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1985年 | 4篇 |
1983年 | 1篇 |
1981年 | 3篇 |
1977年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有2486条查询结果,搜索用时 15 毫秒
71.
Konstantin V. Pochivalov Yaroslav V. Kudryavtsev Tatyana N. Lebedeva Lyubov A. Antina Anna N. Ilyasova Mikhail Yu. Yurov Andrey V. Basko Alexander E. Zavadskii 《Journal of Thermal Analysis and Calorimetry》2018,131(3):2225-2233
Constructing phase diagrams for the mixtures of semicrystalline polymers and low molecular mass substances by DSC can meet with difficulties in the case of slow polymer crystallization. A problem of this kind is encountered for high-energy compositions poly[3,3-bis(azidomethyl)oxetane] (PBAMO)–2,4-dinitro-2,4-diazapentane (DNAP). In this study, the experimental phase diagram PBAMO–DNAP is constructed by an optical method, which makes it possible to visualize structural transformations. The kinetic studies by DSC and XRD reveal that 30–50 days of storing a homogenized PBAMO–DNAP mixture at room temperature are needed to attain stationary values of the crystallinity degree and heat of fusion. Even after that, the DSC method cannot deliver a solubility curve of DNAP in PBAMO, which is naturally generated by the optical method. This curve separates a domain of physical gels, effectively crosslinked by polymer crystallites and swollen with the plasticizer molecules, from a two-phase domain, in which the above gel reaches osmotic equilibrium with the pure plasticizer. It is also shown that the melting temperature of DNAP drops with growing the PBAMO content in the mixture, which is consistent with a decrease in the mean size of plasticizer crystals formed in polymer pores during the previous cooling. 相似文献
72.
73.
74.
75.
76.
A Planar‐Chiral Rhodium(III) Catalyst with a Sterically Demanding Cyclopentadienyl Ligand and Its Application in the Enantioselective Synthesis of Dihydroisoquinolones 下载免费PDF全文
Dr. Evgeniya A. Trifonova Nikita M. Ankudinov Dr. Andrey A. Mikhaylov Dr. Denis A. Chusov Dr. Yulia V. Nelyubina Prof. Dr. Dmitry S. Perekalin 《Angewandte Chemie (International ed. in English)》2018,57(26):7714-7718
The rapid development of enantioselective C?H activation reactions has created a demand for new types of catalysts. Herein, we report the synthesis of a novel planar‐chiral rhodium catalyst [(C5H2tBu2CH2tBu)RhI2]2 in two steps from commercially available [(cod)RhCl]2 and tert‐butylacetylene. Pure enantiomers of the catalyst were obtained through separation of its diastereomeric adducts with natural (S)‐proline. The catalyst promoted enantioselective reactions of aryl hydroxamic acids with strained alkenes to give dihydroisoquinolones in high yields (up to 97 %) and with good stereoselectivity (up to 95 % ee). 相似文献
77.
Dr. Andrey Berezin Nicolas Biot Tommaso Battisti Prof. Dr. Davide Bonifazi 《Angewandte Chemie (International ed. in English)》2018,57(29):8942-8946
The synthesis of a zig‐zag oxygen‐doped molecular rhombic ribbon has been achieved. This includes oxidative C?C and C?O bond formations that allowed the stepwise elongation and planarization of an oxa‐congener of 2,7‐periacenoacene. X‐ray diffraction analysis corroborated the flat structure and the zig‐zag topology of the O‐doped edges. Photophysical and electrochemical investigations showed that the extension of the peri‐xanthenoxanthene (PXX) into the molecular ribbon induces a noticeable shrinking of the molecular band gap devised by a rising of the HOMO energy level, a desirable property for p‐type organic semiconductors. 相似文献
78.
Lilija I. Kasyan Igor N. Tarabara Oxana A. Savel'yeva Andrey O. Kasyan 《Heteroatom Chemistry》2001,12(3):119-130
A number of stereoisomeric N‐[aryl(alkyl, cycloalkyl)carbonyl]‐exo(endo)‐5‐aminomethylbicyclo[2.2.1]hept‐2‐enes have been synthesized from bicyclo[2.2.1]hept‐2‐en‐exo(endo)‐5‐carbonitrile via reduction of the latter by lithium aluminum hydride and subsequent reactions of the resulting amines with aryl(alkyl, cycloalkyl)carbonyl chlorides and anhydrides. The direction of reaction of amides with peroxy acids does not depend on orientation of substituents in the bicyclic fragment: that is, for both exo‐ and endo‐isomers the epoxidations are completed by the formation of N‐[aryl(alkyl, cycloalkyl)carbonyl]‐exo(endo)‐5‐aminomethyl‐exo‐2,3‐epoxybicyclo[2.2.1] heptanes. The reduction of stereoisomeric epoxides by lithium aluminium hydride proceeds in different directions; that is, isomers with an exo‐oriented amido group form the substituted exo‐5‐alkylaminomethyl‐exo‐2,3‐epoxybicyclo[2.2.1]heptanes and the reactions of epoxides of endo‐amides are accompanied by intramolecular cyclization and completed by the formation of N‐[aryl(alkyl, cycloalkyl)]‐exo‐2‐hydroxy‐4‐azatricyclo[4.2.1.03,7]nonanes. The structures and stereochemical homogenity of the products have been confirmed by the analysis of 1H and 13C NMR spectra, correlation spectroscopy, and nuclear Overhauser enhancement spectroscopy experiments. We discuss the behavior of epoxides and provide an analysis of the coefficients of the atomic orbitals in the molecular orbital–linear combination of atomic orbitals equation (AM1 method). © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:119–130, 2001 相似文献
79.
An experimental study of the dependence of the OH uptake coefficient gamma OH over a relative humidity of 0-48% was carried out at 100 Torr and room temperature, using a differential bead-filled flow tube coupled to a high-pressure chemical ionization mass spectrometer. Various organic (paraffin wax, pyrene, glutaric acid, and soot) and inorganic (NaCl, KCl, MgCl2, CaCl2, Na2SO4, and sea salt) surfaces served as proxies for tropospheric aerosols. A virtual cylindrical flow tube approximation and a surface coating dilution technique were successfully employed in the study, which included measurements of high radical uptake with an initial probability of near unity. For inorganic salts, the effect of water vapor, enhancement or inhibition of gamma OH, was found to be dependent on the blocking of anions and changes in surface pH. Although OH uptake by NaCl, the major component of sea-salt aerosols, is weakly dependent on water vapor, it is enhanced by a factor of approximately 2 for MgCl2 and determines the net relative humidity dependence of the radical uptake on sea salt, which is enhanced by a factor of approximately 4. For the organic surfaces studied, the enhancement effect of a factor 4 was also observed only for a hydrophilic organic surface, namely, glutaric acid. Results of the uptake studies suggest that the effect of relative humidity is important and should be accounted for in atmospheric modeling of tropospheric aerosol chemistry. 相似文献
80.
Schalk O Boguslavskiy AE Stolow A Schuurman MS 《Journal of the American Chemical Society》2011,133(41):16451-16458
The influence of through-bond interactions on nonadiabatic excited-state dynamics is investigated by time-resolved photoelectron spectroscopy (TRPES) and ab initio computation. We compare the dynamics of cyclohexa-1,4-diene, which exhibits a through-bond interaction known as homoconjugation (the electronic correlation between nonconjugated double bonds), with the nonconjugated cyclohexene. Each molecule was initially excited to a 3s Rydberg state using a 200 nm femtosecond pump pulse. The TRPES spectra of these molecules display similar structure and time constants on a subpicosecond time scale. Our ab initio calculations show that similar sets of conical intersections (a [1,2]- and [1,3]-hydrogen shift, as well as carbon-carbon bond cleavage) are energetically accessible to both molecules and that the geometry and orbital composition at the minimum energy crossing points to the ground state are directly analogous. These experimental and computational results suggest that the excited-state dynamics of cyclohexa-1,4-diene become localized at a single double bond and that the effects of through-bond interaction, dominant in the absorption spectrum, are absent in the excited-state dynamics. The notion of excited-state dynamics being localized at specific sites within the nuclear framework is analogous to the localization of light absorption by a subsystem within the molecule, designated a chromophore. We propose the utility of the analogous concept, denoted here as a dynamophore. 相似文献