全文获取类型
收费全文 | 2518篇 |
免费 | 130篇 |
国内免费 | 13篇 |
专业分类
化学 | 1952篇 |
晶体学 | 23篇 |
力学 | 56篇 |
数学 | 299篇 |
物理学 | 331篇 |
出版年
2024年 | 3篇 |
2023年 | 23篇 |
2022年 | 76篇 |
2021年 | 65篇 |
2020年 | 52篇 |
2019年 | 65篇 |
2018年 | 55篇 |
2017年 | 27篇 |
2016年 | 99篇 |
2015年 | 79篇 |
2014年 | 83篇 |
2013年 | 168篇 |
2012年 | 201篇 |
2011年 | 186篇 |
2010年 | 94篇 |
2009年 | 90篇 |
2008年 | 152篇 |
2007年 | 168篇 |
2006年 | 117篇 |
2005年 | 134篇 |
2004年 | 123篇 |
2003年 | 81篇 |
2002年 | 131篇 |
2001年 | 29篇 |
2000年 | 24篇 |
1999年 | 24篇 |
1998年 | 20篇 |
1997年 | 33篇 |
1996年 | 22篇 |
1995年 | 21篇 |
1994年 | 15篇 |
1993年 | 18篇 |
1992年 | 8篇 |
1991年 | 17篇 |
1990年 | 12篇 |
1989年 | 14篇 |
1988年 | 6篇 |
1987年 | 9篇 |
1986年 | 12篇 |
1985年 | 14篇 |
1984年 | 16篇 |
1983年 | 8篇 |
1982年 | 8篇 |
1981年 | 10篇 |
1980年 | 7篇 |
1979年 | 8篇 |
1978年 | 13篇 |
1977年 | 8篇 |
1976年 | 4篇 |
1973年 | 4篇 |
排序方式: 共有2661条查询结果,搜索用时 15 毫秒
51.
Jose Zavaleta Alejandra Ramirez Karla Martinez John E. Ladbury Frank A. Gomez 《Talanta》2007,71(1):192-201
Partial filling multiple injection affinity capillary electrophoresis (PFMIACE) is used to determine binding constants between vancomycin (Van) from Streptomyces orientalis, teicoplanin (Teic) from Actinoplanes teicomyceticus and ristocetin (Rist) from Nocardia lurida to d-Ala-d-Ala terminus peptides and carbonic anhydrase B (CAB, E.C.4.2.1.1) to arylsulfonamides. Two variations of PFMIACE are described herein. In the first technique, the capillary is partially filled with ligand at increasing concentrations, a non-interacting standard, three or four separate plugs of receptor each separated by small plugs of buffer, a plug containing a second non-interacting standard, and then electrophoresed in buffer. Upon continued electrophoresis, equilibrium is established between the ligand and receptors causing a shift in the migration time of the receptors with respect to the non-interacting standards. This change in migration time is utilized for estimating multiple binding constants (Kb) for the same interaction. In the second technique, separate plugs of sample containing non-interacting standards, peptide one, buffer, and peptide two, were injected into the capillary column. The capillary is partially filled with a series of buffers containing an antibiotic at increasing concentrations and electrophoresed. Peptides migrate through the column at similar electrophoretic mobilities since their charge-to-mass ratios are approximately the same but remain as distinct zones due to the buffer plug between peptides. Upon electrophoresis, the plug of antibiotic flows into the peptide plugs affecting a shift in the migration time of the peptides with respect to the non-interacting standards occurs due to formation of the of the antibiotic-peptide complex. The shift in the migration time of the peptides upon binding to the antibiotic is used for the Scatchard analysis and measurement of a Kb. The PFMIACE technique expands the functionality and potential of ACE as an analytical tool to examine receptor-ligand interactions. In PFMIACE, a smaller amount of sample is required in the assay compared to both conventional ACE and MIACE. Furthermore, a wide array of data is obtained from a single experiment, thus, expediting the assay of biological species. 相似文献
52.
Lumbierres M Palomo JM Kragol G Roehrs S Müller O Waldmann H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(24):7405-7415
A new flexible and efficient methodology for the solid-phase synthesis of lipidated peptides has been developed. The approach is based on the use of previously synthesized building blocks and overcomes the limitations of previously reported methods, since long doubly lipidated peptides can be synthesized by using this route. Furthermore, it was thus possible to prepare a large number of N- and H-Ras peptides bearing a wide range of reporter and/or linking groups--efficient tools for the investigation of biological processes. In terms of efficiency and flexibility this solid-phase method is superior to the solution-phase synthesis. It gives pure peptides in multimilligram amounts within a much shorter time and with superior overall yield. 相似文献
53.
Pinto SS Diogo HP Guedes RC Costa Cabral BJ Minas da Piedade ME Martinho Simões JA 《The journal of physical chemistry. A》2005,109(42):9700-9708
The energetics of the phenolic O-H bond in the three hydroxybenzoic acid isomers and of the intramolecular hydrogen O-H- - -O-C bond in 2-hydroxybenzoic acid, 2-OHBA, were investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of monoclinic 3- and 4-hydroxybenzoic acids, at 298.15 K, were determined as Delta(f)(3-OHBA, cr) = -593.9 +/- 2.0 kJ x mol(-1) and Delta(f)(4-OHBA, cr) = -597.2 +/- 1.4 kJ x mol(-1), by combustion calorimetry. Calvet drop-sublimation calorimetric measurements on monoclinic samples of 2-, 3-, and 4-OHBA, led to the following enthalpy of sublimation values at 298.15 K: Delta(sub)(2-OHBA) = 94.4 +/- 0.4 kJ x mol(-1), Delta(sub)(3-OHBA) = 118.3 +/- 1.1 kJ x mol(-1), and Delta(sub)(4-OHBA) = 117.0 +/- 0.5 kJ x mol(-1). From the obtained Delta(f)(cr) and Delta(sub) values and the previously reported enthalpy of formation of monoclinic 2-OHBA (-591.7 +/- 1.3 kJ x mol(-1)), it was possible to derive Delta(f)(2-OHBA, g) = -497.3 +/- 1.4 kJ x mol(-1), Delta(f)(3-OHBA, g) = -475.6 +/- 2.3 kJ x mol(-1), and Delta(f)(4-OHBA, cr) = -480.2 +/- 1.5 kJ x mol(-1). These values, together with the enthalpies of isodesmic and isogyric gas-phase reactions predicted by density functional theory (B3PW91/aug-cc-pVDZ, MPW1PW91/aug-cc-pVDZ, and MPW1PW91/aug-cc-pVTZ) and the CBS-QMPW1 methods, were used to derive the enthalpies of formation of the gaseous 2-, 3-, and 4-carboxyphenoxyl radicals as (2-HOOCC(6)H(4)O(*), g) = -322.5 +/- 3.0 kJ.mol(-1) Delta(f)(3-HOOCC(6)H(4)O(*), g) = -310.0 +/- 3.0 kJ x mol(-1), and Delta(f)(4-HOOCC(6)H(4)O(*), g) = -318.2 +/- 3.0 kJ x mol(-1). The O-H bond dissociation enthalpies in 2-OHBA, 3-OHBA, and 4-OHBA were 392.8 +/- 3.3, 383.6 +/- 3.8, and 380.0 +/- 3.4 kJ x mol(-1), respectively. Finally, by using the ortho-para method, it was found that the H- - -O intramolecular hydrogen bond in the 2-carboxyphenoxyl radical is 25.7 kJ x mol(-1), which is ca. 6-9 kJ x mol(-1) above the one estimated in its parent (2-OHBA), viz. 20.2 kJ x mol(-1) (theoretical) or 17.1 +/- 2.1 kJ x mol(-1) (experimental). 相似文献
54.
Chinchilla D Zavaleta J Martinez K Gomez FA 《Analytical and bioanalytical chemistry》2005,383(4):625-631
Multiple-injection affinity capillary electrophoresis (MIACE) is used to determine binding constants (K
b) between receptors and ligands using as model systems vancomycin and teicoplanin from Streptomyces orientalis and Actinoplanes teichomyceticus, respectively, and their binding to D-Ala-D-Ala peptides and carbonic anhydrase B (CAB. EC 4.2.1.1) and the binding of the latter to arylsulfonamides. A sample plug
containing a non-interacting standard is first injected followed by multiple plugs of sample containing the receptor and then
a final injection of sample containing a second standard. Between each injection of sample, a small plug of buffer is injected
which contains an increasing concentration of ligand to effect separation between the multiple injections of sample. Electrophoresis
is then carried out in an increasing concentration of ligand in the running buffer. Continued electrophoresis results in a
shift in the migration time of the receptor in the sample plugs upon binding to their respective ligand. Analysis of the change
in the relative migration time ratio (RMTR) or electrophoretic mobility (μ) of the resultant receptor–ligand complex relative to the non-interacting standards, as a function of the concentration of
ligand yields a value for K
b. The MIACE technique is a modification in the ACE method that allows for the estimation of binding affinities between biological
interactions on a timescale faster than that found for standard ACE. In addition sample volume requirements for the technique
are reduced compared to traditional ACE assays. These findings demonstrate the advantage of using MIACE to estimate binding
parameters between receptors and ligands. 相似文献
55.
Lopes SC Goormaghtigh E Cabral BJ Castanho MA 《Journal of the American Chemical Society》2004,126(17):5396-5402
The organization of the polyene antibiotic filipin in membranes containing cholesterol is a controversial matter of debate. Two contradictory models exist, one suggesting a parallel and the other perpendicular organization of filipin with respect to the plane of the membrane. UV-vis linear dichroism, ATR-FTIR, and fluorescence anisotropy decay techniques were combined to study the orientation of filipin in model systems of membranes composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) or 1,2-palmitoyl-sn-glycero-3-phosphocholine (DPPC) with and without cholesterol. Filipin's orientation is determined by the presence/absence of cholesterol when it is inserted in gel crystalline phase model membranes. When cholesterol (33%) is present in DPPC bilayers, filipin stands perpendicular to the membrane surface as expected in "pore-forming" models. At variance, absence of cholesterol leaves filipin in an essentially random organization in the lipidic matrix. In liquid crystalline phase bilayers (POPC) filipin's orientation is perpendicular to the membrane surface even in absence of cholesterol. Thus filipin's activity/organization depends not only on cholesterol presence but also in the lipid phase domain it is inserted in. These findings were combined with spectroscopy and microscopy data in the literature, solving controversial matters of debate. 相似文献
56.
Efficient and simple colorimetric fluoride ion sensor based on receptors having urea and thiourea binding sites 总被引:6,自引:0,他引:6
[structure: see text] Novel colorimetric receptors for selective fluoride ion sensing containing anthraquinone as chromogenic signaling subunit and urea (N,N' '-(9,10-dihydro-9,10-dioxo-1,2-anthracenediyl)bis[N'-phenyl])/thiourea (N,N' '-(9,10-dihydro-9,10-dihydro-9,10-dioxo-1,2-antrhacenediyl)bis[N-phenyl]) binding sites have been reported. These receptors have shown no affinity for other halide ions (Cl-, Br-, and I- ions). Well-defined color change in the visible region of the spectrum was observed upon addition of fluoride ion in DMSO/CH3CN solution of the receptors 1 and 2. 相似文献
57.
The development of methodologies for the formation of carbon-carbon double bonds could be considered one of the most important challenges in organic synthesis. To this end, beta-elimination reactions in 1,2-difunctionalised substrates have been one of the most important means of generating C=C bonds.This review is intended to highlight the use of SmI2 in beta-elimination procedures, such that the organization of this revision highlights conventional beta-elimination processes which are promoted by samarium diiodide. The synthetic applications of SmI2 will be covered, and 1,2-elimination reactions which are involved in sequential reactions promoted by samarium diiodide, will also be illustrated. These methodologies along with the more recent developments in the area are discussed in this tutorial review. 相似文献
58.
The water-promoted hydrolysis of a highly twisted amide is studied using density functional theory in conjunction with a continuum dielectric method to introduce bulk solvent effects. The aim of these studies is to reveal how the twisting of the C-N bond affects the neutral hydrolysis of amides. To do so, both concerted and stepwise mechanisms are studied and the results compared to the ones from the hydrolysis of an undistorted amide used as reference. In addition, an extra explicit water molecule that assists in the required proton-transfer processes is taken into account. Our results predict important rate accelerations of the neutral hydrolysis of amides when the C-N bond is highly twisted, the corresponding barrier relaxation depending on the specific reaction pathway and transition state involved. Moreover, our calculations strongly suggest a change in reaction mechanism with degree of amide bond twist, and clearly point to a concerted mechanism at neutral pH for the hydrolysis of highly twisted amides. In addition, the twisting of the amide bond also provokes a higher dependence on an auxiliary water molecule for the concerted mechanism, due to the orthogonality of the lone pair of the nitrogen and the carbonyl pi orbital. There is a direct implication of these findings for biological catalytic mechanism of peptide cleavage reactions that undergoes ground-state destabilization of the peptide. 相似文献
59.
Fontana Jose D. Franco Valeria C. De Souza Silvio J. Lyra Ivone N. De Souza Angelita M. 《Applied biochemistry and biotechnology》1991,28(1):341-351
Caffeine and related xanthines were identified as potent stimulators for the bacterial cellulose production in A. xylinum. These compounds are present in several plants whose infusions are useful as culture-medium supplements for this acetobacterium.
The proposed target for these native purine-like inhibitory substances is the novel diguanyl nucleotide phosphodiesterase(s) that participate(s) in the bacterial cellulogenic complex.
A better understanding of this feature of A. xylinum physiology may facilitate the preparation of bacterial cellulose pellicles, which are applied as a biotechnological tool in the treatment of skin burns and other dermal injuries.
相似文献60.
The influence of substituents on both the aromatic rings of the catalyst, and the benzylidene unit of the substrate are investigated in the (salen)copper(II) catalysed asymmetric benzylation of alanine derivatives. Catalysts with electron-donating, and electron-withdrawing substituents of various sizes and at various locations on the aromatic rings of the salen ligand were prepared, but all exhibited inferior enantioselectivity to the parent (salen)copper(II) complex. In contrast, the introduction of halogenated substituents onto the aromatic ring of the N-benzylidene alanine methyl ester substrate was found to enhance the enantioselectivity of the alkylation with a para-chloro substituent giving optimal results. A new procedure for the preparation of the catalysts which avoids the need for chromatography on sephadex LH20 is reported, and the optimal catalyst obtained in this way was found to be a cobalt(salen) complex. 相似文献