全文获取类型
收费全文 | 70593篇 |
免费 | 2805篇 |
国内免费 | 80篇 |
专业分类
化学 | 48002篇 |
晶体学 | 362篇 |
力学 | 1930篇 |
数学 | 10699篇 |
物理学 | 12485篇 |
出版年
2023年 | 560篇 |
2022年 | 804篇 |
2021年 | 1084篇 |
2020年 | 1095篇 |
2019年 | 1100篇 |
2018年 | 1324篇 |
2017年 | 1103篇 |
2016年 | 2235篇 |
2015年 | 2130篇 |
2014年 | 2135篇 |
2013年 | 4352篇 |
2012年 | 4898篇 |
2011年 | 5019篇 |
2010年 | 3023篇 |
2009年 | 2536篇 |
2008年 | 4359篇 |
2007年 | 4283篇 |
2006年 | 3834篇 |
2005年 | 3648篇 |
2004年 | 3117篇 |
2003年 | 2553篇 |
2002年 | 2276篇 |
2001年 | 1206篇 |
2000年 | 1041篇 |
1999年 | 743篇 |
1998年 | 584篇 |
1997年 | 533篇 |
1996年 | 680篇 |
1995年 | 454篇 |
1994年 | 484篇 |
1993年 | 505篇 |
1992年 | 503篇 |
1991年 | 446篇 |
1990年 | 409篇 |
1989年 | 408篇 |
1988年 | 351篇 |
1987年 | 338篇 |
1986年 | 328篇 |
1985年 | 514篇 |
1984年 | 487篇 |
1983年 | 311篇 |
1982年 | 440篇 |
1981年 | 425篇 |
1980年 | 381篇 |
1979年 | 360篇 |
1978年 | 353篇 |
1977年 | 285篇 |
1976年 | 336篇 |
1975年 | 289篇 |
1974年 | 290篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
A high-performance liquid chromatographic method with ultraviolet detection has been developed for the determination of bretylium in plasma. Following a single-step solid-phase extraction procedure, bretylium is selectively isolated and well recovered from plasma. The assay sensitivity is 0.156 micrograms/ml from 250-microliters plasma samples and its linearity was assessed up to 40 micrograms/ml. The method is accurate (101.0 +/- 5.4%) and precise (maximum coefficient of variation of 8%). It provides a simple and time-saving alternative to existing methods and is particularly suitable for pharmacokinetic studies. 相似文献
992.
Peak distortion in the column liquid chromatographic determination of omeprazole dissolved in borax buffer. 总被引:1,自引:0,他引:1
Injection of a sample containing omeprazole dissolved in borax buffer (pH 9.2) into a reversed-phase liquid chromatographic system consisting of a mixture of acetonitrile and phosphate buffer (pH 7.6) as the mobile phase and a C18 surface-modified silica as the solid phase resulted under special conditions in split peaks of omeprazole. The degree of peak split and the retention time of omeprazole varied with the concentration of borax in the sample solution and the ionic strength of the mobile phase buffer as well as with the column used. Borax is eluted from the column in a broad zone starting from the void volume of the column. The retention is probably due to the presence of polyborate ions. The size of the zone varies with the concentration of borax in the sample injected. In the borax zone the pH is increased compared with the pH of the mobile phase, and when omeprazole (a weak acid) is co-eluting in the borax zone its retention is affected. In the front part and in the back part of the borax zone, pH gradients are formed, and these gradients can induce the peak splitting. When the dissolving medium is changed to a phosphate buffer or an ammonium buffer at pH 9 no peak distortion of omeprazole is observed. 相似文献
993.
Gold-gold interactions in small polynuclear complexes are analysed using extended Hückel calculations. They are influenced by the nature of the ligand donor atoms, by the bridging ligands, but most by the formal oxidation state of the metal. Au---Au bonds are much stronger in complexes of Au(II) and Au(III), but a weak interaction between two d10 centres exists for Au(I) complexes, owing to mixing of the s and p orbitals with the d orbitals. Phosphines induce stronger metal-metal bonds when coordinated trans to the Au---Au bond in [Au(II)[(CH2)2PPh2]L]2 (Ph = phenyl), but have the opposite effect when bonded orthogonally to the metal-metal axis in Au(I) binuclear species. When two gold atoms are bridged by a single carbon atom, belonging either to mesityl (Mes = 2,4,6-Me3C6H2) or CR2, the former produces stronger Au(I)---Au(I) interactions, reflected in shorter distances. Formal oxidation states are proposed for the gold atoms in two mixed-valence clusters, [Au4(C6F5)2((PPh3)2CH})2(PPh3)2](ClO4)2 and [{(2,4,6-C6F3H2)Au(CH2PPh2CH2)2Au{in2-Au(CH2PPh2CH2)2Au](ClO4)2. The results suggest a higher oxidation state for the outer gold atoms, in both the T-shaped tetranuclear cluster and the Au6 linear chain. 相似文献
994.
E. M. Araújo Renata Barbosa Amanda D. Oliveira Crislene R. S. Morais T. J. A. deMélo A. G. Souza 《Journal of Thermal Analysis and Calorimetry》2007,87(3):811-814
Polyethylene/montmorillonite clay nanocomposites were obtained via direct
melt intercalation. The clay was organically modified with four different
types of quaternary ammonium salts. The objective of this work is to study
the use of montmorillonite clay in the production of nanocomposites by means
on rheological, mechanical and crystallization properties of nanocomposites
and to compare to the properties of the matrix and PE/unmodified clay nanocomposites.
In general, the tensile test showed that the yield strength and modulus of
the nanocomposites are close to the pure PE. Apparently, the mixture with
Dodigen salt seems to be more stable than the pure PE and PE/unmodified clay. 相似文献
995.
Reddy BM Lakshmanan P Khan A Loridant S López-Cartes C Rojas TC Fernandez A 《The journal of physical chemistry. B》2005,109(28):13545-13552
Ce(x)Zr(1)(-)(x)O(2) solid solutions deposited over silica surface were investigated by X-ray diffraction (XRD), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HREM) techniques in order to understand the role of silica support and the temperature stability of these composite oxides. For the purpose of comparison, an unsupported Ce(x)Zr(1)(-)(x)O(2) was also synthesized and subjected to characterization by various techniques. The Ce(x)Zr(1)(-)(x)O(2)/SiO(2) (CZ/S) (1:1:2 mole ratio based on oxides) was synthesized by depositing Ce(x)Zr(1)(-)(x)O(2) solid solution over a colloidal SiO(2) support by a deposition precipitation method and unsupported Ce(x)Zr(1)(-)(x)O(2) (CZ) (1:1 mole ratio based on oxides) was prepared by a coprecipitation procedure, and the obtained catalysts were subjected to thermal treatments from 773 to 1073 K. The XRD measurements disclose the presence of cubic phases with the composition Ce(0.75)Zr(0.25)O(2) and Ce(0.6)Zr(0.4)O(2) in CZ samples, while CZ/S samples possess Ce(0.75)Zr(0.25)O(2), Ce(0.6)Zr(0.4)O(2), and Ce(0.5)Zr(0.5)O(2) in different proportions. The crystallinity of these phases increased with increasing calcination temperature. The cell a parameter estimations indicate contraction of ceria lattice due to the incorporation of zirconium cations into the CeO(2) unit cell. Raman measurements indicate the presence of oxygen vacancies, lattice defects, and displacement of oxygen ions from their normal lattice positions in both the series of samples. The HREM results reveal, in the case of CZ/S samples, a well-dispersed nanosized Ce-Zr-oxides over the surface of amorphous SiO(2). The structural features of these crystals as determined by digital diffraction analysis of experimental images reveal that the Ce-Zr-oxides are mainly in the cubic geometry and exhibit high thermal stability. Oxygen storage capacity measurements by a thermogravimetric method reveal a substantial enhancement in the oxygen vacancy concentration of CZ/S sample over the unsupported CZ sample. 相似文献
996.
Cianetti S Négrerie M Vos MH Martin JL Kruglik SG 《Journal of the American Chemical Society》2004,126(43):13932-13933
Cytochrome c (cyt c) is an electron-transfer heme protein that also binds nitric oxide (NO). In resting cyt c, two endogenous ligands of the heme iron are histidine-18 (His) and methionine-80 (Met) side chains, and NO binding requires the cleavage of one of the axial bonds. Previous femtosecond transient absorption studies suggested the photolysis of either Fe-His or Fe-Met bonds. We aimed at unequivocally identifying the internal side chain that is photodissociated in ferrous cyt c and at monitoring heme structural dynamics, by means of time-resolved resonance Raman (TR3) spectroscopy with approximately 0.6 ps time resolution. The Fe-His stretching mode at 216 cm-1 has been observed in photoproduct TR3 spectra for the first time for a c-type heme. The same transient mode was observed for a model ferrous cyt c N-fragment (residues 1-56) ligated with two His in the resting state. Our TR3 data reveal that upon ferrous cyt c photoexcitation, (i) distal Met side chain is instantly released, producing a five-coordinated domed heme structure, (ii) proximal His side chain, coupled to the heme, exhibits distortion due to strain exerted by the protein, and (iii) alteration in heme-cysteine coupling takes place along with the relaxation of the protein-induced deformations of the heme macrocycle. 相似文献
997.
Detailed comparative studies of proton relay in native and chemically modified gramicidin channels provide a unique opportunity to uncover the structural basis of biological proton transport. The function of ion channels hinges on their ability to provide surrogate solvation in narrow pore filters so as to overcome the dielectric barrier presented by biological membranes. In the potassium channel KcsA and in the cation channel gramicidin, permeant selectivity and mobility are determined by the proteinaceous matrix via hydrogen bonding, charge-dipole, and dipole-dipole interactions. In particular, main-chain carbonyl groups in these pore interiors play an essential role in the solvation of alkali ions and of protons. In this study, molecular dynamics simulations reveal how the translocation of H(+) is controlled by nanosecond conformational transitions exchanging distorted states of the peptidic backbone in the single-file region of a dioxolane-linked analogue of the gramicidin dimer. These results underline the functional role of channel dynamics and provide a mechanism for the modulation of proton currents by fluctuating dipoles. 相似文献
998.
Antonio Da Settimo Giampaolo Primofiore Bertacchi Maria Cristina Federico Da Settimo Anna Maria Marini 《Journal of heterocyclic chemistry》1995,32(3):941-945
The Ullmann reaction of 8-aminotheophylline or 8-aminocaffeine with 2-chlorobenzoic acid and of 8-bromotheophylline with ethyl-2-aminobenzoate afforded derivatives of three new heterocyclic systems: purino[7,8-α]quinazoline-5,9,11(6H,8H,10H)-trione, purino[8,9-b]quinazoline-2,4,11(1H,3H,5H)-trione and purino[8,7-b]quinazoline-2,4,6(1H,3H,11H)-trione, respectively. 相似文献
999.
Hourdin M Gouhier G Gautier A Condamine E Piettre SR 《Journal of combinatorial chemistry》2005,7(2):285-297
Ten cross-linked polystyrene-supported, protected chiral amines featuring both a spacer, comprising from 5 to 15 atoms, and a fluorinated linker have been successfully prepared. The development of the monitoring technique by gel-phase 19F NMR spectrometry on cross-linked polystyrene derivatives proved to be of high value in four steps of the process, as shown by the comparison of data gathered from both a classic NMR spectrometer and elemental analysis. Gel-phase 19F NMR spectrometry, thus, constitutes a useful technique that complements IR and 13C NMR spectrometries for the qualitative monitoring of reactions. In addition, quantitative determination of the conversion in a given transformation is possible, provided that 19F chemical shifts of the substrate and the product be different enough (Deltadelta>base width), as illustrated by the Mitsunobu coupling process (16-->17). The technique is nondestructive, and the samples used to monitor the reactions may be returned to the reaction medium. Deprotection of the above amines was achieved and furnished eight of the final resins in good to acceptable purity for future applications. 相似文献
1000.
The equilibrium distribution of species formed between Cu(II) and N-acetylneuraminic (sialic) acid (I, LH) at 298 K has been determined using a two-dimensional (2D) simulation analysis of electron paramagnetic resonance (EPR) spectra. In acidic solutions (pH values < 4), the major species present are Cu(2+), [CuL]+ [logbeta = 1.64(4)], and [CuL2] [logbeta = 2.77(5)]. At intermediate pH values (4.0 < pH < 7.5), [CuL2H-1]- [logbeta = -2.72(7)] and two isomers of [CuLH-1] [logbeta (overall) = -3.37(2)] are present. At alkaline pH values (7.5 < pH < 11), the major species present is [CuL2H-2]2-, modeled as three isomers with unique giso and Aiso values [logbeta (overall) = -8.68(3)]. Two further species ([CuLH-3]2- and [CuL2H-3]3-) appear at pH values > 11. It is proposed that [CuL]+ most likely features I coordinated via the deprotonated carboxylic acid group (O1) and the endocyclic oxygen atom (OR) forming a five-membered chelate ring. Select Cu(II)-I species of the form [CuLH-1] may feature I acting as a dianionic tridentate chelate, via oxygen atoms derived from O1, OR, and one deprotonated hydroxy group (O7 or O8) from the glycerol tail. Alternatively, I may coordinate Cu(II) in a bidentate fashion as the tert-2-hydroxycarboxylato (O1,O2) dianion. Spectra predicted for Cu(II)-I complexes in which I is coordinated in either a O1,OR {I1-} or O1,O2 {I2-} bidentate fashion {e.g., [CuL]+ (O1,O R), [CuL2] (bis-O1,O R), [CuLH-1] (isomer: O1, O2), [CuL2H-1]- (O1, O R; O1, O2), and [CuL2H-2]2- (isomer: bis-O1, O2)} have "irregular" EPR spectra that are ascribed to the existence of Cu(II)-I(monomer) <==> Cu(II)-I(polymer) equilibria. The formation of polymeric Cu(II)-I species will be favored in these complexes because the glycerol-derived hydroxyl groups at the complex periphery (O, 7O, 8O9) are available for further Cu(II) binding. The presence of polymeric Cu(II)-I species is supported by EPR spectral data from solutions of Cu(II) and the homopolymer of I, colominic acid (Ipoly). Conversely, spectra predicted for Cu(II)-I complexes where I is coordinated in a {I2-} tridentate {e.g., [CuLH-1] (isomer: O1, O R, O7, or O8) and [CuL2H-2]2- (isomer: bis-O1,O R,O7, or O8)} or tetradentate fashion {I3-} {e.g., [CuLH-3]2- (O1, O R, O, 8O9)} are typical for mononuclear tetragonally elongated Cu(II) octahedra. In this latter series of complexes, the tendency toward the formation of polymeric Cu(II)-I analogues is small because the polydentate I effectively wraps up the mononuclear Cu(II) center. This work shows that Cu(II) could potentially mediate the chemistry of sialoglycoconjugate-containing proteins in human biology, such as the sialylated amyloid precursor protein of relevance to Alzheimer's disease. 相似文献