全文获取类型
收费全文 | 1001篇 |
免费 | 49篇 |
国内免费 | 21篇 |
专业分类
化学 | 686篇 |
晶体学 | 5篇 |
力学 | 13篇 |
数学 | 208篇 |
物理学 | 159篇 |
出版年
2023年 | 9篇 |
2022年 | 7篇 |
2021年 | 10篇 |
2020年 | 15篇 |
2019年 | 22篇 |
2018年 | 21篇 |
2017年 | 17篇 |
2016年 | 45篇 |
2015年 | 39篇 |
2014年 | 37篇 |
2013年 | 68篇 |
2012年 | 71篇 |
2011年 | 82篇 |
2010年 | 43篇 |
2009年 | 44篇 |
2008年 | 71篇 |
2007年 | 75篇 |
2006年 | 79篇 |
2005年 | 53篇 |
2004年 | 56篇 |
2003年 | 39篇 |
2002年 | 36篇 |
2001年 | 9篇 |
2000年 | 4篇 |
1999年 | 14篇 |
1998年 | 5篇 |
1997年 | 12篇 |
1996年 | 16篇 |
1995年 | 7篇 |
1994年 | 4篇 |
1993年 | 7篇 |
1992年 | 7篇 |
1991年 | 8篇 |
1990年 | 5篇 |
1989年 | 6篇 |
1988年 | 2篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1889年 | 2篇 |
排序方式: 共有1071条查询结果,搜索用时 31 毫秒
11.
12.
It is known that one-dimensional lattice problems with a discrete, finite set of states per site generically have periodic ground states (GSs). We consider slightly less generic cases, in which the Hamiltonian is constrained by either spin (S) or spatial (I) inversion symmetry (or both). We show that such constraints give rise to the possibility ofdisordered GSs over a finite fraction of the coupling-parameter space—that is, without invoking any nongeneric fine tuning of coupling constants, beyond that arising from symmetry. We find that such disordered GSs can arise for many values of the number of statesk at each site and the ranger of the interaction. The Ising (k=2) case is the least prone to disorder:I symmetry allows for disordered GSs (without fine tuning) only forr5, whileS symmetry never gives rise to disordered GSs. 相似文献
13.
14.
A response equation for conductivity detection in ion chromatography has been derived. This equation is applicable to non-suppressed ion chromatography using both fully ionised and partially ionised eluents. A prime assumption of this equation is that when partially ionised eluents are used (such as benzoic acid), both the ionised and neutral components of the eluent species contribute to the detector response of anionic analytes. Experimental evidence is provided to support this assumption in that pH changes accompanying the elution of an analyte have been measured. These pH changes are proportional to the concentration of analyte injected onto the column, in accordance with predictions from the response equation. Furthermore, it is shown that protonated eluents (such as benzoic acid) give more sensitive detection than equivalent ionised eluents (such as potassium benzoate) and the signal enhancement achieved using a protonated eluent species is in accordance with theory. 相似文献
15.
Thomas F.O. Lim Jerry K. Myers Greg. T. Rogers Paul Ronald Jones 《Journal of organometallic chemistry》1977,135(2):249-259
The regioselectivity of the hydroboration of the methylchlorovinylsilanes, ClnMe3?nSiCHCH2 (n= 0 ? 3), has been investigated using BH3←THF, 9-BBN, disiamyl- and dicyclohexylborane. Methylation of the adducts with methylmagnesium bromide is complicated by formation of tetraalkylboronates. Alkaline hydrogen peroxide oxidation of the boronates gives reasonable yields of the corresponding α- and β-trimethylsilylethanols forn= 0 and 1. Forn= 2 and 3, conversion of the adducts to the corresponding α- and β- deuteroethylsilanes by treatment with excess sodium methoxide in methanol-0-d provides a more effective means of derivatization. Addition of the alkenes,n= 2 or 3, to excess BH3←THF givesca. 90% of the α-boro-organo-chlorosilanes. For all of the alkenes, the dialkylboranes giveca. 80% of the β-boron adducts. 相似文献
16.
Guldi DM Zilbermann I Anderson G Kotov NA Tagmatarchis N Prato M 《Journal of the American Chemical Society》2004,126(44):14340-14341
Novel organic (positively charged fullerene)-inorganic (negatively charged CdTe nanoparticle) nanoensembles were devised through electrostatic interactions and probed as versatile donor-acceptor hybrids. Photoirradiation of their homogeneous solutions, containing the electrostatically packed components, let to very long-lived (1.3 ms) charge separated states. 相似文献
17.
18.
De la Fuente JR Jullian C Saitz C Neira V Poblete O Sobarzo-Sánchez E 《The Journal of organic chemistry》2005,70(22):8712-8716
[reaction: see text] Photoreduction of oxoisoaporphine dyes occurs via a stepwise mechanism of electron-proton-electron transfer that leads to the N-hydrogen oxoisoaporphine anion. When triethylamine, TEA, was used as the electron donor in anaerobic conditions, 1-diethylaminobutadiene, DEAB, was one of the oxidation products of TEA, among diethylamine and acetaldehyde. DEAB was identified by (1)H NMR and GC-MS experiments by comparison with the authentic 1-diethylaminobutadiene. This is the first report of a butadienyl derivative formed in the dye-sensitized photooxidation of TEA. In addition, isotopic exchange experiments with TEA-d(15) and D(2)O show that the hydrogens at carbon-2 and carbon-4 of the butadienyl moiety are exchangeable. The observed isotopic exchange pattern could be explained by the head-to-tail coupling of an N,N-diethylvinylamine intermediate that exchanges hydrogens at the C-beta via the enammonium ion. 相似文献
19.
Michelle Hernández-Arganis Rubén A. Toscano Mónica Moya-Cabrera Verónica García-Montalvo Raymundo Cea-Olivares Dr. 《无机化学与普通化学杂志》2004,630(11):1627-1631
The alkaline 1-phenyl-1H-1, 2, 3, 4-tetrazole-5-thiolate salts, M[C6H5N4CS] (M = Li ( 1 ), Na ( 2 ), K ( 3 ), Rb ( 4 ) and Cs ( 5 )) were obtained and characterized by means of mass spectrometry (FAB+) and NMR (1H; 13C) spectroscopy. The structures of Na ( 2 ), K ( 3 ), Rb ( 4 ) and Cs ( 5 ) compounds were determined by X-ray diffraction methods. The ligand shows a rich variety of coordination patterns with the alkaline cations. The formation of a four-membered ring MSCN in the compounds with heavier alkali cations (K, Rb and Cs) is shown. In all the cations the coordination number around it increases with the ionic radius. Compounds with Cs+ and Rb+ exhibited the formation of Cs-C and Rb-C interactions with the phenyl group. 相似文献
20.
A fiber-optic-based system for remote measurement of time-resolved fluorescence emission spectra is described and characterized. A pulsed nitrogen laser is used to induce fluorescence and a time-gated, one-dimensional photodiode array is used to measure the decay of the fluorescence emission spectra. The results compare favorably with reported values for well characterized compounds having fluorescence decay times in the range 4–50 ns. The potential of using time-resolved fluorimetry (TRF) over fiber-optic cables as a means of improving the specificity of remote fluorescence determinations of spectrally similar polycyclic aromatic hydrocarbons in sea water is demonstrated. 相似文献