全文获取类型
收费全文 | 995篇 |
免费 | 59篇 |
国内免费 | 8篇 |
专业分类
化学 | 803篇 |
晶体学 | 14篇 |
力学 | 8篇 |
数学 | 83篇 |
物理学 | 154篇 |
出版年
2023年 | 10篇 |
2022年 | 11篇 |
2021年 | 9篇 |
2020年 | 24篇 |
2019年 | 27篇 |
2018年 | 12篇 |
2017年 | 13篇 |
2016年 | 36篇 |
2015年 | 28篇 |
2014年 | 23篇 |
2013年 | 57篇 |
2012年 | 49篇 |
2011年 | 62篇 |
2010年 | 36篇 |
2009年 | 45篇 |
2008年 | 78篇 |
2007年 | 62篇 |
2006年 | 68篇 |
2005年 | 61篇 |
2004年 | 48篇 |
2003年 | 46篇 |
2002年 | 42篇 |
2001年 | 13篇 |
2000年 | 12篇 |
1999年 | 9篇 |
1998年 | 11篇 |
1997年 | 4篇 |
1996年 | 7篇 |
1995年 | 9篇 |
1994年 | 4篇 |
1993年 | 7篇 |
1992年 | 5篇 |
1991年 | 8篇 |
1990年 | 5篇 |
1988年 | 10篇 |
1987年 | 6篇 |
1986年 | 3篇 |
1985年 | 9篇 |
1984年 | 14篇 |
1983年 | 8篇 |
1982年 | 15篇 |
1981年 | 14篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1974年 | 3篇 |
1973年 | 5篇 |
1972年 | 4篇 |
1969年 | 3篇 |
排序方式: 共有1062条查询结果,搜索用时 296 毫秒
1.
2.
Intramolecular (2+2) photocycloaddition of β-stilbazoles tethered by silyl chains took place with high efficiency. Complexation with dicarboxylic acid or catechol further enhanced both the efficiency and stereoselectivity. 相似文献
3.
Tetraoctylammonium cation forms a room-temperature molten salt (RTMS) with 2,4,6-trinitrophenolate anion. The RTMS is immiscible with water (W) and forms a stable RTMS/W interface. It has been shown that the RTMS/W interface can be electrochemically polarized. A well-defined voltammetric wave due to the transfer of thiocyanate ion across the RTMS/W interface was observed within the potential window. This is the first example of a polarized RTMS/W interface. 相似文献
4.
The double-bond conversion of UV-cured resins prepared from pentaerythritol triacrylate (PETA) was determined by pyrolysis-gas chromatography in the presence of an organic alkali, tetramethylammonium hydroxide (TMAH). The pyrogram of the uncured prepolymer compound, consisting of PETA and a photoinitiator, 2,2-dimethoxy-2-phenylacetophenone, contained specific products reflecting the original acrylate structure, such as methyl acrylate (MA) and methyl ethers of pentaerithritol. Meanwhile, in pyrograms of the UV-cured PETA, the yields of MA considerably decreased. The double-bond conversions of the cured resins, irradiated with various UV dosages, were calculated based on the relative yields of MA among specific products in the pyrograms. The conversions determined by this approach were analyzed by comparing them with those estimated by Fourier-transform infrared spectroscopy. 相似文献
5.
Tsutomu Nakanishi Hajime Okamoto Maki Kasahara Kyozaburo Takeda 《Journal of Polymer Science.Polymer Physics》2003,41(22):2829-2849
We theoretically investigated the polymorphy of the stereostructures of a periodic polymer. Using the polymer's internal conformation parameters of bond lengths, bond angles, and internal rotation angles, we extended the mathematical treatment for designing polymer backbones. We considered those periodic polymers whose unit cell consists of one (m = 1), two (m = 2), or three (m = 3) kinds of atoms. Moreover, for these three types of polymers, we supposed two catenation types for the skeleton atoms; one is a “homorotatory” sequence and the other is a “heterorotatory” one. To specify the backbone's stereostructure, we introduced several conformation parameters such as the helical pitch number n, the translation distance d, and the inclination angle of the skeleton plane Θ. By combining these parameters, we can systematically understand the variety and the possible polymorphy in the stereostructure of a periodic polymer backbone. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2829–2849, 2003 相似文献
6.
7.
Kumar D Hirao H de Visser SP Zheng J Wang D Thiel W Shaik S 《The journal of physical chemistry. B》2005,109(42):19946-19951
Density functional theory (DFT) is applied to the dark section of the catalytic cycle of the enzyme cytochrome P450, namely, the formation of the active species, Compound I (Cpd I), from the ferric-hydroperoxide species (Cpd 0) by a protonation-assisted mechanism. The chosen 96-atom model includes the key functionalities deduced from experiment: Asp(251), Thr(252), Glu(366), and the water channels that relay the protons. The DFT model calculations show that (a) Cpd I is not formed spontaneously from Cpd 0 by direct protonation, nor is the process very exothermic. The process is virtually thermoneutral and involves a significant barrier such that formation of Cpd I is not facile on this route. (b) Along the protonation pathway, there exists an intermediate, a protonated Cpd 0, which is a potent oxidant since it is a ferric complex of water oxide. Preliminary quantum mechanical/molecular mechanical calculations confirm that Cpd 0 and Cpd I are of similar energy for the chosen model and that protonated Cpd 0 may exist as an unstable intermediate. The paper also addresses the essential role of Thr(252) as a hydrogen-bond acceptor (in accord with mutation studies of the OH group to OMe). 相似文献
8.
ATPases are important molecular machines that convert the chemical energies stored in ATP to mechanical actions within the cell. ATPases are among the most abundant proteins with diverse functions involved in almost every cellular pathway. The well characterised ATPases include the various motor proteins responsible for cargo transfers, cell motilities, and muscle contractions; the protein degradation machinery - the proteasome; the ATP synthase, F-ATPase; and the chaperone systems. Other ATPases include DNA helicases and DNA replication complex; proteins responsible for protein/complex disassembly; and certain gene regulators. It is beyond the scope of this review to cover the complete range of ATPases. Instead, we will focus on a few representative ATPases, chosen based on their diverse mechanisms and properties. Furthermore, this review is by no means trying to cover comprehensively the literature for each ATPase nor the historical aspects in each field. We will focus on describing the various techniques being employed to derive the mechanisms and properties of the chosen ATPases. Among them, high and low resolution structural studies combined with biochemical assays seem to be the dominant technical advances adapted to reveal mechanisms for most of the ATPases except the bacterial sigma54 activators, whose mechanism of action is mostly derived from large amount of biochemical studies. A number of them, especially the F-ATPase and motor proteins, have been studied successfully by various single molecule and imaging techniques. We will therefore discuss them in greater details in order to describe the wide range techniques being utilised. 相似文献
9.
Solid sampling technique for direct detection of condensed tannins in bark by matrix-assisted laser desorption/ionization mass spectrometry 总被引:2,自引:0,他引:2
Ishida Y Kitagawa K Goto K Ohtani H 《Rapid communications in mass spectrometry : RCM》2005,19(5):706-710
A novel method for the direct analysis of condensed tannin components in bark was developed on the basis of matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) combined with a simple solid sampling technique. The MALDI mass spectra obtained from the wood (bark) powder sample clearly showed a series of peaks corresponding to the sodium ion adducts of condensed tannin oligomers up to around m/z 3000. The results indicate that the condensed tannins in the bark sample used in this work mostly consist of combinations of flavan-3-ol units such as profisetinidin (PF), prorobinetinidin (PR) and prodelphinidin (PD), at least up to 10-mers (m/z approximately 3000). 相似文献
10.
A cationic CpRu(II) complex in combination with quinaldic acid shows high reactivity and chemoselectivity for the catalytic deprotection of hydroxyl groups protected as allyl ethers. The catalyst operates in alcoholic solvents without the need for any additional nucleophiles, satisfying the practical requirements of operational simplicity, safety, and environmental friendliness. The wide applicability of this deprotection strategy to a variety of multifunctional molecules, including peptides and nucleosides, may provide new opportunities in protective group chemistry. [structure: see text] 相似文献