全文获取类型
收费全文 | 735篇 |
免费 | 18篇 |
国内免费 | 2篇 |
专业分类
化学 | 450篇 |
晶体学 | 10篇 |
力学 | 14篇 |
数学 | 75篇 |
物理学 | 206篇 |
出版年
2022年 | 8篇 |
2021年 | 6篇 |
2020年 | 12篇 |
2019年 | 12篇 |
2018年 | 19篇 |
2017年 | 13篇 |
2016年 | 18篇 |
2015年 | 16篇 |
2014年 | 22篇 |
2013年 | 43篇 |
2012年 | 27篇 |
2011年 | 36篇 |
2010年 | 22篇 |
2009年 | 26篇 |
2008年 | 25篇 |
2007年 | 32篇 |
2006年 | 34篇 |
2005年 | 21篇 |
2004年 | 23篇 |
2003年 | 13篇 |
2002年 | 17篇 |
2001年 | 7篇 |
2000年 | 8篇 |
1999年 | 12篇 |
1998年 | 9篇 |
1997年 | 14篇 |
1996年 | 13篇 |
1995年 | 8篇 |
1994年 | 16篇 |
1993年 | 12篇 |
1992年 | 11篇 |
1990年 | 7篇 |
1989年 | 8篇 |
1988年 | 12篇 |
1987年 | 12篇 |
1986年 | 6篇 |
1985年 | 10篇 |
1984年 | 13篇 |
1983年 | 11篇 |
1982年 | 8篇 |
1981年 | 9篇 |
1980年 | 5篇 |
1979年 | 6篇 |
1977年 | 9篇 |
1974年 | 5篇 |
1973年 | 7篇 |
1969年 | 7篇 |
1965年 | 4篇 |
1964年 | 6篇 |
1961年 | 5篇 |
排序方式: 共有755条查询结果,搜索用时 15 毫秒
31.
Time-resolved (TR) EPR was used to study the photophysics and photochemistry of 1-(3-(methoxycarbonyl)propyl)-1-phenyl[6.6]C61 (M1). The CW TREPR spectra of M1 in the photoexcited triplet state, frozen in a rigid matrix and in liquid solution at room temperature, were compared with those of 3C60. The introduction of the substituent on C60 has a striking effect on the spectra of the triplets, which is attributed to the lifting of the orbital degeneracy by the reduction in symmetry. Fourier transform (FT) EPR was used in an investigation of electron-transfer reactions in liquid solutions mediated by 3M1. Of particular interest was the system of M1/chloranil (CA)/perylene (Pe). Photoexcitation of M1 is found to lead to the formation of the chloranil anion radical and the perylene cation radical. From the chemically induced dynamic electron polarization (CIDEP) patterns in the FTEPR spectra and the dependence of the reaction kinetics on reactant concentrations, it was deduced that CA- is formed by two competing pathways following photoexcitation of M1: (1) direct electron transfer from 3M1 to CA followed by electron transfer from Pe to M1+ and (2) energy transfer from 3M1 to Pe followed by oxidative quenching of 3Pe by CA. In both pathways, M1 acts as a light-energy harvester and mediator of electron-transfer reactions from Pe to CA without itself being consumed in the process, that is, as a photocatalyst. It is found that the functionalization of C60 makes its triplet state a worse electron donor and acceptor, but it has no significant effect on the triplet energy transfer reaction. 相似文献
32.
Srinivasachari Rajappa Kuppuswamy Nagarajan Kailasam Venkatesan Nirupa Kamath Vipanjeri Madabhusi Padmanabhan Wolfgang von Philipsborn Ban Chin Chen Raffaelo Müller 《Helvetica chimica acta》1984,67(7):1669-1680
The 1H-NMR spectra of 2-(nitromethylidene)pyrrolidine ( 7 ), 1-methyl-2-(nitromethylidene)imidazolidind ( 10 ) and 3-(nitromethylidene)tetrahydrothiazine ( 11 ) in CDCl3 and (CD3)2SO indicate that these compounds have the intramolecularly H-bonded structures (Z)- 7 , (E)- 10 and (Z)- 11 while the N-methyl derivative 8 of 7 is (E)-configurated in both solvents. 1-Benzylamino-1-(methyltio)-2-nitroehtylene ( 13 ), an acylic model, has the H-bonded configuration (E)- 13 in CDCl3 and in (CD3)2SO. 2-(Nitromethylidene)thiazolidine ( 3 ) has the (E)-configuration in CDCl3 but exists in (CD3)2SO as a mixture of (Z)- and (E)-isomers with the former predominating. Both species are detected to varying proportions in a mixture of the two solvents. 15N-NMR spectroscopy of 3 ruled out unambiguously the nitronic acid structure 6 and the nitromethyleimine structure 5 . The N-methyl derivative 4 of 3 is (Z)-configurated in (CD3)2SO. Comparison of the olefinic proton shifts of (Z)- 3 and (Z)- 4 with those of analogues and also of 1,1-bis(methylti)-2-nitroethylene ( 12 ) shows decreased conjugation of the lone pair of electrons of the ring N-atom in (Z)- 3 and (Z)- 4 . This is also supported by 13C-NMR studies. Plausible explanations for the phenomenon are offered by postulating that the ring N-atoms are pyramidal in (Z)- 3 and (Z)- 4 and planar in other cases or, alternatively, that the conjugated nitroenamine system gets twisted due to steric interaction between the NO2-group and the ring S-atom. Single-crystal X-ray studies of 3 and 8 show that the former exists in the (Z)-configuration and the latter in (E)-configuration; the ring N-atom in the former has slightly more pyramidal character than in the latter. 相似文献
33.
K. Nagarajan 《Journal of Chemical Sciences》1984,93(6):1079-1097
Recent synthetic routes to the tetrahydro, hexahydro and octahydro derivatives of indoles are reviewed. An interesting one
is the formation of 3-amino-4-oxo-4,5,6,7-tetrahydroindoles in the reaction of 2-phenacyl cyclohexane-l,3-diones with 1,1-disubstituted
hydrazines. Antifertility, cns depressant and antiinflammatory activities have been encountered for perhydroindoles besides
other biological activities. Hexahydrocinnolines are obtained from the reaction of 2-phenacyl (acetonyl) cyclohexanones and
cyclohexane-1,3-diones with hydrazines, while octahydrocinnolines are formed from cyclohexanone-2-acetic acids and hydrazines
in two steps. 5-oxo-5,6,7,8-hexahydrocinnolines and their oximes undergo anomalous and interesting aromatisation reactions.
Some hexahydrocinnolines are cns depressants while octahydrocinnolines are analgesics. More importantly, they are precursors
for interesting azamorphinans.
Contribution No. 736 from Research centre 相似文献
34.
Zusammenfassung Mit Hilfe der gruppentheoretischen Methode vonWilson wurden die Konstanten der potentiellen Energie für die Tetramethylverbindungen und-ionen der Elemente der 4. und 5. Gruppe, besonders des C, Si, Ge, Sn, Pb, N, As und Sb, sowie auch der Aluminat- und Zinkat-Ionen unter Verwendung eines Valenzkraftfeldes mit 5 Konstanten berechnet. Auf der Grundlage der vonCyvin postulierten Symmetriekoordinaten wurden die Größen der mittleren Amplitudenquadrate und die mittleren Schwingungsamplituden für gebundene und nicht-gebundene Atompaare bei den Temperaturen 298° K und 500° K berechnet. Der geringfügige Einfluß der Schwingungen der Methyl- und Hydroxylgruppen auf die Gerüstschwingungen wurde vernachlässigt, jedoch die nicht-diagonalen Elemente bei der Lösung der Säkulargleichungen in Betracht gezogen.
Diese Arbeit wurde vom US-Army Research Office, Durham, unter der Nummer AROD-31-124-6864 unterstützt. 相似文献
Potential energy constants and mean amplitudes of vibration in some XY4-molecules and-ions with tetrahedral symmetry
Potential energy constants have been evaluated by theWilson's group theoretical method for the tetramethyl compounds and ions of the elements of the fourth and fifth groups, namely, C, Si, Ge, Sn, Pb, N, As, and Sb as well as the aluminate and zincate ions employing a five-constant valence force field. On the basis of the symmetry coordinates postulated byCyvin, the mean-square amplitude quantities and mean amplitudes of vibration for the bonded and nonbonded atom pairs have also been computed at the temperatures 298° K and 500° K. The effect of the vibrations of methyl and hydroxyl groups on the skeletal modes, being small, has been neglected and the off-diagonal element has been taken into account in solving the secular equations.
Diese Arbeit wurde vom US-Army Research Office, Durham, unter der Nummer AROD-31-124-6864 unterstützt. 相似文献
35.
B.P.C. Rao† S. Ramaswamy† C. Gopalakrishnan N. Satya Vijayakumar K.R. Ganesh 《哲学杂志》2013,93(25):3463-3473
Two-dimensional carbon nanosheets have been fabricated using inductively coupled radio frequency plasma-enhanced chemical vapour deposition. The structural properties of the nanosheets have been characterised using atomic force microscopy, scanning electron microscopy and X-ray diffractometer. The magnetisation of the samples was studied using vibrating sample magnetometer. The magnetisation of the nanosheets was found to be diamagnetic for fast synthesis processes (30 and 60 min). On the other hand, the nanosheets exhibited a weak ferromagnetic response for the slow (120 min) synthesis process. Energy dispersive spectrometry and atomic absorption spectroscopy confirmed that the magnetisation exhibited by the carbon nanosheets was an intrinsic property and that it was not due to contamination from the substrate. Raman spectroscopy studies revealed that the ferromagnetic carbon nanosheets have a higher ratio (1.20) of graphite peak (I G) to disordered peak (I D) than normally expected (0.75–0.90). Available data indicated that the magnetisation was due to the presence of structural disorders. 相似文献
36.
37.
Large-scale evacuations are a recurring theme on news channels, whether in response to major natural or manmade disasters. The role of warning dissemination is a key part in the success of such large-scale evacuations and its inadequacy in certain cases has been a ‘primary contribution to deaths and injuries’ (Hayden et al., 2007). Along with technology-driven ‘official warning channels’ (e.g. sirens, mass media), the role of unofficial channel (e.g. neighbours, personal contacts, volunteer wardens) has proven to be significant in warning the public of the need to evacuate. Although post-evacuation studies identify the behaviours of evacuees as disseminators of the warning message, there has not been a detailed study that quantifies the effects of such behaviour on the warning message dissemination. This paper develops an Agent-Based Simulation (ABS) model of multiple agents (evacuee households) in a hypothetical community to investigate the impact of behaviour as an unofficial channel on the overall warning dissemination. Parameters studied include the percentage of people who warn their neighbours, the efficiency of different official warning channels, and delay time to warn neighbours. Even with a low proportion of people willing to warn their neighbour, the results showed considerable impact on the overall warning dissemination. 相似文献
38.
39.
M. Ingarsal P. Amutha M. Gopalakrishnan S. Nagarajan 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4):515-522
Abstract The 4,6-diaryl-6,7-dihydro-[1,2,3]selenadiazolo[5,4-c]pyridine-5(4H)-carbalde hydes were synthesized from 2,6-diarylpiperidin-4-ones and characterized using infrared, 1H, 13C Nuclear Magnetic Resonance (NMR), and mass spectroscopic techniques. On the NMR time scale, the compounds exist in syn and anti isomeric forms. Separate signals were obtained for isomers in the NMR spectra. The compounds’ stereodynamic nature was studied based on the intensity and position of NMR signals. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. 相似文献
40.
Suizhou Yang Ke Yang Aloke Jain Ramaswamy Nagarajan Jayant Kumar 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(11):938-941
A novel method for maskless micro-patterning of polymeric substrates is presented. First, an azobenzene functionalized polymer film is spin-coated on a Poly (ethylene terephthalate) (PET) sheet. Then surface relief structures are optically inscribed on the polymer film by interference of laser beams. The patterned azobenzene functionalized film is then etched in the plasma chamber such that the gratings are transferred to the PET substrate. Finally, any remaining azobenzene functionalized polymer is dissolved away using an appropriate solvent. This method of patterning can be broadly applied to a variety of flexible/polymeric substrates and the resolution is not limited by the substrate thermo-mechanical properties. 相似文献