全文获取类型
收费全文 | 315篇 |
免费 | 7篇 |
专业分类
化学 | 159篇 |
力学 | 5篇 |
数学 | 53篇 |
物理学 | 105篇 |
出版年
2023年 | 1篇 |
2022年 | 5篇 |
2021年 | 8篇 |
2020年 | 9篇 |
2019年 | 5篇 |
2018年 | 6篇 |
2017年 | 3篇 |
2016年 | 6篇 |
2015年 | 7篇 |
2014年 | 7篇 |
2013年 | 17篇 |
2012年 | 19篇 |
2011年 | 28篇 |
2010年 | 12篇 |
2009年 | 9篇 |
2008年 | 18篇 |
2007年 | 17篇 |
2006年 | 19篇 |
2005年 | 15篇 |
2004年 | 12篇 |
2003年 | 12篇 |
2002年 | 11篇 |
2001年 | 5篇 |
2000年 | 6篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1995年 | 7篇 |
1994年 | 4篇 |
1993年 | 4篇 |
1992年 | 5篇 |
1991年 | 2篇 |
1990年 | 5篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1985年 | 2篇 |
1984年 | 7篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1970年 | 2篇 |
1967年 | 2篇 |
1966年 | 1篇 |
1963年 | 1篇 |
1961年 | 1篇 |
1960年 | 1篇 |
排序方式: 共有322条查询结果,搜索用时 15 毫秒
1.
Gary H. Posner Timothy P. Kogan Stephen R. Haines Leah L. Frye 《Tetrahedron letters》1984,25(25):2627-2630
A short, reliable, and practical synthesis of ()-(+)-2-(-tolylsulfinyl)-2-buten-4-olide has been developed, and the utility of this Michael acceptor for highly enantiocontrolled synthesis of 3-substituted 4-butanolides has been demonstrated. 相似文献
2.
Harding WW Tidgewell K Schmidt M Shah K Dersch CM Snyder J Parrish D Deschamps JR Rothman RB Prisinzano TE 《Organic letters》2005,7(14):3017-3020
[reaction: see text] Two new neoclerodane diterpenes, salvinicins A (4) and B (5), were isolated from the dried leaves of Salvia divinorum. The structures of these compounds were elucidated by spectroscopic techniques, including (1)H and (13)C NMR, NOESY, HMQC, and HMBC. The absolute stereochemistry of these compounds was assigned on the basis of single-crystal X-ray crystallographic analysis of salvinicin A (4) and a 3,4-dichlorobenzoate derivative of salvinorin B. 相似文献
3.
Jay Rothman 《Journal of Fourier Analysis and Applications》1995,2(3):217-225
The Adler-Konheim theorem [Proc. Amer. Math. Soc. 13 (1962), 425-428] states that the collection of nth-order autocorrelation
functions
is a complete set of translation invariants for real-valued L1 functions on a locally compact abelian group. It is shown here that there are proper subsets of
that also form a complete set of translation invariants, and these subsets are characterized. Specifically, a subset is
complete if and only if it contains infinitely many even-order autocorrelation functions. In addition, any infinite subset
of
is complete up to a sign. While stated here for functions on
the proofs presented hold for functions on any locally compact abelian group that is not compact, in particular, on
and the integer lattice
相似文献
4.
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
5.
Khaja Basheeruddin Vicki Rothman Simeon Margolis 《Applied biochemistry and biotechnology》1985,11(2):133-140
We have immobilized E.coli alkaline phosphatase (EC 3.1.3.1) by linking it covalently to sepharose 4B. This preparation has several advantages over
the soluble enzyme. The immobilized enzyme is easily separable from other constituents in incubation mixtures. The immobilized
enzyme can be reused repeatedly and is more stable than the soluble enzyme to heat treatment in the presence of 10 mM Mg2+. The insoluble and soluble phosphatases removed 75 and77%, respectively, of the inorganic phosphorus from casein. The immobilized enzyme inactivated two enzymes believed to be active
in the phosphorylated state, acyl-CoA : cholesterol acyltransferase (ACAT) by 39% and NADPH-cytochrome P-450 reductase by
89%. The utility of immobilized alkaline phosphatase for studying the phosphorylation and dephosphorylation of soluble or
membrane-bound enzymes and proteins is discussed. 相似文献
6.
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
7.
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
8.
The glycoprotein (G) of vesicular stomatitis virus (VSV) is synthesized on membrane-bound polyribosomes. Approximately 30 min after its synthesis, it reaches the surface plasma membrane where it is incorporated into budding virus. The first part of this paper focuses on the 2 intracellular, membrane-bound, glycosylated forms of the glycoprotein which are intermediates in its biogenesis. All glycosylation and processing is completed in the smooth microsome fraction before the protein reaches the surface. Next, we turn to the mechanism by which G is synthesized on membrane-bound polyribosomes. All of the G mRNA is bound to membranes, and studies with puromycin suggest that this attachment of G mRNA is mediated by the nascent glycoprotein chain. After its synthesis G is a transmembrane protein with about 30 amino acids at the carboxyl terminus remaining on the cytoplasmic side of the endoplasmic reticulum. Since 95% of the glycoprotein, containing the carbohydrate residues, is resistant to attack by external proteases, it appears to be within the lumen of the endoplasmic reticulum or embedded within the lipid bilayer. Finally, we show that synthesis, glycosylation, and proper asymmetric insertion of G into the ER can be achieved in cell-free extracts. Both glycosylation of G and proper insertion into the ER membrane in this cell-free system require concomitant protein synthesis. 相似文献
9.
10.