全文获取类型
收费全文 | 3185篇 |
免费 | 122篇 |
国内免费 | 21篇 |
专业分类
化学 | 2193篇 |
晶体学 | 26篇 |
力学 | 126篇 |
数学 | 526篇 |
物理学 | 457篇 |
出版年
2023年 | 28篇 |
2022年 | 53篇 |
2021年 | 53篇 |
2020年 | 59篇 |
2019年 | 85篇 |
2018年 | 56篇 |
2017年 | 33篇 |
2016年 | 94篇 |
2015年 | 103篇 |
2014年 | 121篇 |
2013年 | 174篇 |
2012年 | 232篇 |
2011年 | 255篇 |
2010年 | 162篇 |
2009年 | 136篇 |
2008年 | 187篇 |
2007年 | 194篇 |
2006年 | 193篇 |
2005年 | 197篇 |
2004年 | 182篇 |
2003年 | 116篇 |
2002年 | 118篇 |
2001年 | 45篇 |
2000年 | 43篇 |
1999年 | 27篇 |
1998年 | 28篇 |
1997年 | 28篇 |
1996年 | 24篇 |
1995年 | 25篇 |
1994年 | 10篇 |
1993年 | 23篇 |
1992年 | 11篇 |
1991年 | 8篇 |
1990年 | 6篇 |
1989年 | 11篇 |
1987年 | 5篇 |
1986年 | 6篇 |
1985年 | 12篇 |
1984年 | 21篇 |
1983年 | 13篇 |
1982年 | 17篇 |
1981年 | 13篇 |
1980年 | 22篇 |
1979年 | 10篇 |
1978年 | 9篇 |
1977年 | 9篇 |
1976年 | 11篇 |
1975年 | 8篇 |
1974年 | 9篇 |
1973年 | 10篇 |
排序方式: 共有3328条查询结果,搜索用时 15 毫秒
201.
Danny Schuhknecht Dr. Valeri Leich Dr. Thomas P. Spaniol Iskander Douair Prof. Dr. Laurent Maron Prof. Dr. Jun Okuda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(13):2821-2825
Potassium silanide [KSiH3]∞ contains 4.2 wt % of hydrogen and has been intensely studied as hydrogen storage material. The macrocyclic ligand Me4TACD (1,4,7,10-tetramethyl-1,4,7,10-tetraaminocyclododecane, L ) stabilizes the full range of triphenylsilyl complexes [( L )MSiPh3]n (M=Li–Cs), which react with H2 or PhSiH3 to form molecular [( L )MSiH3]n that can be isolated in soluble form and fully characterized. 相似文献
202.
Marine de Person Aude Sevestre P. Chaimbault Laurent Perrot Francis Duchiron Claire Elfakir 《Analytica chimica acta》2004,520(1-2):149-158
This paper reports the use of an on-line LC–ESI–MS/MS method for the identification and quantification of di- and tripeptides in champagne wine without laborious sample pretreatment. The identification of these compounds, in their underivatised form, is based on identical retention times and ESI–MS spectra to those of reference standards. The presence of nine dipeptides (Arg–Ile, Ile–Arg, Ile–Val, Lys–Phe, Lys–Tyr, Phe–Lys, Tyr–Gln, Tyr–Lys, Val–Ile) and the absence of two tripeptides (Phe–Arg–Arg and Lys–Met–Asn) have been evidenced in the matrix. Calibration curves for each analyte were established using Phe–Arg as internal standard. The calibration curves were linear in the concentration range 0.1–10 mg L−1 with a determination coefficient, r2, better than 0.992. The accuracy for the calibration standard was estimated at between 92 and 102%. This method allows high recovery and satisfies the necessary requirements with respect to accuracy, repeatability and sensitivity. The first application of this analytical method to the measurement of di- and tri-peptides in different vintages of champagne wine is reported. Compositional changes in the peptides occurred depending on the vintage. 相似文献
203.
Manuel Tzouros Laurent Bigler Stefan Bienz Manfred Hesse Akira Inada Hiroko Murata Yuka Inatomi Tsutomu Nakanishi Dedy Darnaedi 《Helvetica chimica acta》2004,87(6):1411-1425
The investigation of the MeOH extract of the leaves of Chisocheton weinlandii Harms (Meliaceae) revealed two new open‐chain spermidine alkaloids, chisitine 1 ( 1 ) and chisitine 2 ( 2 ). Their structures were elucidated by NMR spectroscopy, tandem‐mass spectrometry, and independant syntheses (Scheme 3). Detailed MS/MS fragmentation pathways are discussed for both compounds based on H/D exchange and 18O‐labeling experiments (Schemes 1 and 2). 相似文献
204.
Tournassat C Ferrage E Poinsignon C Charlet L 《Journal of colloid and interface science》2004,273(1):234-246
The potentiometric titration and CEC data presented in part I are modeled in this paper, part II. Two models are compared: the two pK, three complexation sites plus exchange sites nonelectrostatic model developed by Baeyens and Bradbury and a model based on the MUSIC approach developed by Hiemstra and Van Riemsdijk. Both morphological and structural information is used to develop this new model. Morphological information is taken from the literature, while structural information is taken from the literature and constrained by supporting FTIR experiments. The Baeyens and Bradbury model is found to reproduce the general tendency of the titration curve, whereas the model based on the Hiemstra and Van Riemsdijk MUSIC approach provides a better fit to the experimental data. The former uses only 3 edge reaction sites, whereas the latter uses at least 27 edge reaction sites. Five main reactive sites are sufficient to fit the MUSIC model curve, but the model allows us to derive the properties of 22 other reactive sites. Logically, the greater the number of sites, the better the fit. Nevertheless, fewer adjustable parameters are necessary for the Hiemstra and Van Riemsdijk MUSIC model than for the Baeyens and Bradbury model, thanks to structural and morphological constraints. The precision of the potentiometric titration curve is insufficient to verify that the properties of the 27 sites given by the MUSIC model are effective. Thus, we coupled some properties of clay minerals, such as dissolution, to the modeled acid-base properties of these sites to assess our model. We then questioned the ability of simplified models such as the Baeyens and Bradbury model to predict the interactions between clay minerals and solutions in natural environments. In addition, we derived the cation exchange selectivity coefficients for CaCl+ ionic pairs and H+ from our CEC data and gave an estimate for the CaOH+ selectivity coefficient. 相似文献
205.
Rapid stereoselective separations of amphetamine derivatives with highly sulfated gamma-cyclodextrin
The highly sulfated gamma-CD (HS-gamma-CD) is a chiral selector widely used in CE for the enantioseparation of pharmaceutical compounds. This paper investigated different approaches to reduce the stereoselective analysis time of amphetamine (AT) derivatives according to the chiral selector concentration in the BGE. With high HS-gamma-CD concentration, tested analytes were separated in 3.5 min as anionic complexes with short-end injection technique in reversed polarity mode. However, this procedure presented some limitations in terms of efficiency and resolution, excessive Joule heating and poor compatibility with MS detection. With low HS-gamma-CD concentration, compounds were separated as cations. Conventional approaches to reduce CE analysis time demonstrated critical resolution between some analytes. Therefore, the use of the partial-filling technique compatible with MS detection was carried out. Under optimized conditions, the analysis time for the chiral separation of seven AT like compounds was reduced to 6 min. Moreover, sensitivity of CE-MS was sufficient for the determination of ATs in plasma following a simple liquid-liquid extraction. 相似文献
206.
Raimund Schwarz Günter Gliemann Laurent Chassot Philippe Jolliet Alex von Zelewsky 《Helvetica chimica acta》1989,72(2):224-236
The polarized optical absorption and emission (spectra, decay times) of single crystals of [Pd(thpy)2] and [Pt(thpy)2] (thpy ≡ C(3′)-deprotonated form of 2-(2-thienyl)pyridine) at temperatures 1.9 K ? T ? 80 K are reported. The emission of [Pt(thpy)2] can be influenced strongly by applied magnetic fields (0 ? H ? 6 T). Depending on the central ions Pd and Pt, the lowest excited electronic states of the single complexes are ligand-centered (LC) states and metal-to-ligand charge transfer (MLCT) states, respectively. This difference leads to distinctly dissimilar properties of the emission of both compounds. The experimental data show that the emission of single crystals of [Pd(thpy)2] and [Pt(thpy)2] at T ? 30 K originates from several types of traps (defect states of symmetry 3B2?stabilized below the exciton band) with LC and MLCT character, respectively. In the Pt compound, the 3B2 is split by spin-orbit coupling into three states. The states B and A, which determine the emission properties, are separated by Δv ~ 13 cm?1. Both states can mix under the influence of an applied magnetic field yielding an increase of the emission intensity by a factor of ~ 1.5 at H = 6 T. 相似文献
207.
With the aim of the radiolabeling of cytisine, a potent agonist of nicotinic receptors, with [(11)C]phosgene, the rapid synthesis of a lactam model of our target has been studied. The key step of the delta-lactam formation is a new chemoselective lithiation-annulation method, under high dilution, of a suitable piperidinylcarbamoyl chloride. This precursor was obtained from (2-hydroxyethyl)piperidine in a linear synthetic sequence involving a Corey-Fuchs olefination of the corresponding aldehyde, followed by a selective reduction, using a diimide equivalent, of an iodoalkyne into a (Z)-iodopropene piperidine. This alkene served as main precursor to study the cyclization according to several procedures using phosgene as the required carbonylating reagent. 相似文献
208.
Mialane P Lisnard L Mallard A Marrot J Antic-Fidancev E Aschehoug P Vivien D Sécheresse F 《Inorganic chemistry》2003,42(6):2102-2108
The reactivity of the [alpha-SiW(11)O(39)](8-) monovacant polyoxometalate with lanthanide has been investigated for four different trivalent rare-earth cations (Ln = Nd(III), Eu(III), Gd(III), Yb(III)). The crystal structures of KCs(4)[Yb(alpha-SiW(11)O(39))(H(2)O)(2)] x 24H(2)O (1), K(0.5)Nd(0.5)[Nd(2)(alpha-SiW(11)O(39))(H(2)O)(11)] x 17H(2)O (2a), and Na(0.5)Cs(4.5)[Eu(alpha-SiW(11)O(39))(H(2)O)(2)] x 23H(2)O (3a) are reported. The solid-state structure of compound 1 consists of linear wires built up of [alpha-SiW(11)O(39)](8-) anions connected by Yb(3+) cations, while the linkage of the building blocks by Eu(3+) centers in 3a leads to the formation of zigzag chains. In 2a, dimeric [Nd(2)(alpha-SiW(11)O(39))(2)(H(2)O)(8)](10-) entities are linked by four Nd(3+) cations. The resulting chains are connected by lanthanide ions, leading to a bidimensional arrangement. Thus, the dimensionality, the organization of the polyoxometalate building units, and the Ln/[alpha-SiW(11)O(39)](8-) ratio in the solid state can be tuned by choosing the appropriate lanthanide. The luminescent properties of compound 3a have been studied, showing that, in solution, the polymer decomposes to give the monomeric complex [Eu(alpha-SiW(11)O(39))(H(2)O)(4)](5-). The lability of the four exogenous ligands connected to the rare earth must allow the functionalization of this lanthanide polyanion. 相似文献
209.
Martínez-Viviente E Pregosin PS Vial L Herse C Lacour J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(12):2912-2918
1H, (19)F and (31)P pulsed field gradient spin-echo (PGSE) diffusion studies on chiral organic salts that contain hexacoordinate phosphate anions, namely tris(tetrachlorobenzenediolato)phosphate(V) (TRISPHAT) and bis(tetrachlorobenzenediolato)mono([1,1']binaphthalenyl-2,2'diolato)-phosphate(V) (BINPHAT), are reported. The first example of the dependence of a diffusion value on diastereomeric structure is presented. Marked solvent and concentration effects on the diffusion constants (D) of these salts are noted and the question of ion pairing is discussed. 相似文献
210.
Ab initio Car-Parinnello molecular dynamics is used to simulate the structure and the dynamics of 1-butyl-3-methylimidazolium iodide ([bmim]I) ionic liquid at 300 K. Site-site pair correlation functions reveal that the anion has a strong interaction with any three C-H's of the imidazolium ring. The ring bends over and wraps around the anion such that the two nitrogen atoms take a distance to the anion. Electron donating butyl group contributes the electronic polarization in addition to geometrical (out-of-plane) polarization of the ring due to the liquid environment. This facilitates bending of the ring along the axis passing through nitrogen atoms. The average bending angle depends largely on the alkyl chain length and slightly on the anion type. Redistribution of electron density over the ring caused by the electron donating alkyl group provides additional independent evidence to the instability of lattice structure, hence the low melting point of the ionic liquid. Simulated viscosity and diffusion coefficients of [bmim]I are in quite agreement with the experiments. 相似文献