全文获取类型
收费全文 | 744篇 |
免费 | 6篇 |
国内免费 | 1篇 |
专业分类
化学 | 243篇 |
晶体学 | 3篇 |
力学 | 26篇 |
数学 | 238篇 |
物理学 | 241篇 |
出版年
2021年 | 9篇 |
2020年 | 9篇 |
2019年 | 9篇 |
2018年 | 9篇 |
2016年 | 10篇 |
2015年 | 6篇 |
2014年 | 8篇 |
2013年 | 50篇 |
2012年 | 21篇 |
2011年 | 34篇 |
2010年 | 14篇 |
2009年 | 23篇 |
2008年 | 35篇 |
2007年 | 39篇 |
2006年 | 34篇 |
2005年 | 22篇 |
2004年 | 22篇 |
2003年 | 21篇 |
2002年 | 18篇 |
2001年 | 10篇 |
2000年 | 9篇 |
1997年 | 13篇 |
1996年 | 7篇 |
1995年 | 11篇 |
1994年 | 14篇 |
1993年 | 4篇 |
1992年 | 16篇 |
1991年 | 12篇 |
1990年 | 18篇 |
1989年 | 15篇 |
1988年 | 19篇 |
1987年 | 12篇 |
1986年 | 10篇 |
1985年 | 17篇 |
1984年 | 19篇 |
1983年 | 14篇 |
1982年 | 11篇 |
1981年 | 18篇 |
1980年 | 12篇 |
1979年 | 7篇 |
1978年 | 14篇 |
1977年 | 12篇 |
1976年 | 6篇 |
1975年 | 5篇 |
1974年 | 6篇 |
1973年 | 8篇 |
1972年 | 10篇 |
1971年 | 4篇 |
1969年 | 4篇 |
1967年 | 3篇 |
排序方式: 共有751条查询结果,搜索用时 156 毫秒
11.
We say that a graphG ishomomorphic to a graphH if there is a mappingp from the vertices of G onto the vertices ofH such thatp(u) andp() are adjacent inH wheneveru and are adjacent in G. Thehomomorphism polynomial of a graphG is a polynomial in two variables that counts the number of homomorphisms ofG onto the complete graph of each order. This polynomial can be computed recursively in an analog to the chromatic polynomial. In this paper, we present some results regarding the homomorphism polynomials of the graphs of chemical compounds — in particular, alkane isomers. The coefficients of the homomorphism polynomial can be used to predict the rankings of compounds with respect to several chemical properties. Our results seem to refine those obtained by Randi et al. from path lengths. 相似文献
12.
J. C. Y. Le Blanc D. Beuchemin K. W. M. Siu R. Guevremont S. S. Berman 《Journal of mass spectrometry : JMS》1991,26(10):831-839
The effects of beat on the electrospray mass spectra of eight globular proteins in solution were studied. These ranged from hardly noticeable to a dramatic shift in the mass spectrometric profile and a concomitant increase in ion abundance. This change is believed to be the result of thermal denaturation of the protein species in solution resulting in a transition from a more compact to a less compact conformation. We accounted for this transition by means of a recently proposed model based on aqueous solution acid/base equilibria. For cytochrome c, profiles calculated by means of this model agree well with experimental data. The ΔH of the denaturation reaction of cytochrome c in aqueous solution containing 0.2% acetic acid was calculated from experimental data to be 103.8 ± 9.2 kJ mol?1, in good agreement with previous measurements. 相似文献
13.
Berman Abraham Shaked-Monderer Naomi 《Central European Journal of Operations Research》2022,30(3):1093-1099
Central European Journal of Operations Research - Completely positive matrices are matrices that can be decomposed as $$BB^T$$ , where B is an entrywise nonnegative matrix. These matrices have many... 相似文献
14.
15.
16.
A simple and rapid acid digestion method for the decomposition of estuarine sediments is described. Quantitative recovery of Cd, Pb, Cu, Ni, Co, Be and Co is demonstrated. Sensitive, precise and accurate determination of these trace metals by graphite-furnace atomic absorption spectrometry in combination with the L'vov Platform provides an interference-free technique that permits calibration with simple aqueous solutions of metal standards. The accuracy of the method has been confirmed by analysis of two marine sediment reference materials, MESS-1 and BCSS-1. 相似文献
17.
S. S. Berman K. W. M. Siu P. S. Maxwell D. Beauchemin V. P. Clancy 《Fresenius' Journal of Analytical Chemistry》1989,333(6):641-644
Summary The methylmercury concentrations in three existing marine biological certified reference materials — TORT-1, DORM-1 and DOLT-1 — are determined by gas chromatography with electron capture detection, cold vapour atomic absorption spectrometry and inductively coupled plasma mass spectrometry after selective isolation of methylmercury. Two such procedures were used. These and the three analytical techniques are evaluated and compared. The certified methylmercury concentrations are: TORT-1, 0.128 ± 0.014; DORM-1, 0.731±0.060; and DOLT-1, 0.080 ± 0.011 g Hg/g dry weight.
Meeresbioligische Referenzmaterialien für Methylquecksilber: Analytische Methoden der Zertifizierung相似文献
18.
Appelhans LN Zuccaccia D Kovacevic A Chianese AR Miecznikowski JR Macchioni A Clot E Eisenstein O Crabtree RH 《Journal of the American Chemical Society》2005,127(46):16299-16311
Changing the counteranion along the series Br, BF4, PF6, SbF6 in their ion-paired 2-pyridylmethyl imidazolium salts causes the kinetic reaction products with IrH5(PPh3)2 to switch from chelating N-heterocyclic carbenes (NHCs) having normal C2 (N path) to abnormal C5 binding (AN path). Computational work (DFT) suggests that the AN path involves C-H oxidative addition to Ir(III) to give Ir(V) with little anion dependence. The N path, in contrast, goes by heterolytic C-H activation with proton transfer to the adjacent hydride. The proton that is transferred is accompanied by the counteranion in an anion-coupled proton transfer, leading to an anion dependence of the N path, and therefore of the N/AN selectivity. The N path goes via Ir(III), not Ir(V), because the normal NHC is a much less strong donor ligand than the abnormal NHC. PGSE NMR experiments support the formation of ion-pair in both the reactants and the products. 19F,1H-HOESY NMR experiments indicate an ion-pair structure for the products that is consistent with the computational prediction (ONIOM(B3PW91/UFF)). 相似文献
19.
Vera A. Vil' Yana A. Barsegyan Leah Kuhn Maria V. Ekimova Egor A. Semenov Alexander A. Korlyukov Alexander O. Terent'ev Igor V. Alabugin 《Chemical science》2020,11(20):5313
How far can we push the limits in removing stereoelectronic protection from an unstable intermediate? We address this question by exploring the interplay between the primary and secondary stereoelectronic effects in the Baeyer–Villiger (BV) rearrangement by experimental and computational studies of γ-OR-substituted γ-peroxylactones, the previously elusive non-strained Criegee intermediates (CI). These new cyclic peroxides were synthesized by the peroxidation of γ-ketoesters followed by in situ cyclization using a BF3·Et2O/H2O2 system. Although the primary effect (alignment of the migrating C–Rm bond with the breaking O–O bond) is active in the 6-membered ring, weakening of the secondary effect (donation from the OR lone pair to the breaking C–Rm bond) provides sufficient kinetic stabilization to allow the formation and isolation of stable γ-hydroperoxy-γ-peroxylactones with a methyl-substituent in the C6-position. Furthermore, supplementary protection is also provided by reactant stabilization originating from two new stereoelectronic factors, both identified and quantified for the first time in the present work. First, an unexpected boat preference in the γ-hydroperoxy-γ-peroxylactones weakens the primary stereoelectronic effects and introduces a ∼2 kcal mol−1 Curtin–Hammett penalty for reacquiring the more reactive chair conformation. Second, activation of the secondary stereoelectronic effect in the TS comes with a ∼2–3 kcal mol−1 penalty for giving up the exo-anomeric stabilization in the 6-membered Criegee intermediate. Together, the three new stereoelectronic factors (inverse α-effect, misalignment of reacting bonds in the boat conformation, and the exo-anomeric effect) illustrate the richness of stereoelectronic patterns in peroxide chemistry and provide experimentally significant kinetic stabilization to this new class of bisperoxides. Furthermore, mild reduction of γ-hydroperoxy-γ-peroxylactone with Ph3P produced an isolable γ-hydroxy-γ-peroxylactone, the first example of a structurally unencumbered CI where neither the primary nor the secondary stereoelectronic effect are impeded. Although this compound is relatively unstable, it does not undergo the BV reaction and instead follows a new mode of reactivity for the CI – a ring-opening process.Protecting stereoelectronic effects prevent Baeyer–Villiger rearrangement and stabilize γ-OX-γ-peroxylactones (X = H, OH), the previously elusive non-strained Criegee intermediates. 相似文献
20.
A conventional ion-exchange amino acid analyser kit has been simply and economically constructed for use with existing high-performance liquid chromatography (HPLC) apparatus. Sequential elution conditions are fully programmable by virtue of a 32K BBC microcomputer interfaced with an elution buffer selection valve and a thermostatically controlled column. Post-column derivatization with o-phthaladehyde-2-mercaptoethanol reagent enables fluorimetric detection at the picomole level. The system enables sensitive amino acid analysis of complex mixtures to be carried out by clinical and research laboratories who already possess HPLC apparatus but whose sample turnover does not merit purchase of a dedicated fully automated analyser. 相似文献