全文获取类型
收费全文 | 434篇 |
免费 | 17篇 |
国内免费 | 1篇 |
专业分类
化学 | 228篇 |
晶体学 | 9篇 |
力学 | 29篇 |
数学 | 99篇 |
物理学 | 87篇 |
出版年
2023年 | 5篇 |
2022年 | 6篇 |
2021年 | 9篇 |
2020年 | 8篇 |
2019年 | 15篇 |
2018年 | 10篇 |
2017年 | 10篇 |
2016年 | 16篇 |
2015年 | 13篇 |
2014年 | 9篇 |
2013年 | 28篇 |
2012年 | 25篇 |
2011年 | 28篇 |
2010年 | 21篇 |
2009年 | 16篇 |
2008年 | 19篇 |
2007年 | 20篇 |
2006年 | 15篇 |
2005年 | 22篇 |
2004年 | 15篇 |
2003年 | 17篇 |
2002年 | 15篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 5篇 |
1996年 | 4篇 |
1995年 | 2篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 12篇 |
1991年 | 2篇 |
1990年 | 8篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 5篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1972年 | 1篇 |
1922年 | 1篇 |
排序方式: 共有452条查询结果,搜索用时 15 毫秒
81.
Sandra Salido-Fortuna Chiara Dal Bosco Alessandra Gentili María Castro-Puyana María Luisa Marina Giovanni D'Orazio Salvatore Fanali 《Electrophoresis》2023,44(15-16):1177-1186
The nano-LC technique is increasingly used for both fast studies on enantiomeric analysis and test beds of novel stationary phases due to the small volumes involved and the short conditioning and analysis times. In this study, the enantioseparation of 10 drugs from different families was carried out by nano-LC, utilizing silica with immobilized amylose tris(3-chloro-5-methylphenylcarbamate) column. The effect on chiral separation caused by the addition of different salts to the mobile phase was evaluated. To simultaneously separate as many enantiomers as possible, the effect of buffer concentration in the mobile phase was studied, and, to increase the sensitivity, a liquid–liquid microextraction based on the use of isoamyl acetate as sustainable extraction solvent was applied to pre-concentrate four chiral drugs from tap and environmental waters, achieving satisfactory recoveries (>70%). 相似文献
82.
M. V. Afonin S. A. Simanova N. M. Burmistrova N. S. Panina Yu. A. Karpov O. A. Dal’nova 《Russian Journal of Applied Chemistry》2008,81(11):1933-1938
The recovery of platinum(II) and platinum(IV) chloro complexes from hydrochloric acid and chloride solutions with a new heterochain S,N-containing sorbent, MITKhAT, was studied. The suggested mechanism of formation of platinum(II) mercapto-thio ether complexes in the course of sorption was confirmed by DFT calculations. The results of group and selective recovery of platinum metals with MITKhAT sorbent from simulated and real industrial solutions are reported. 相似文献
83.
Theoretical investigation of the structures and spectroscopic properties of (H2O4)n (n = 1–4) clusters
下载免费PDF全文
![点击此处可从《International journal of quantum chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Hong‐Dal Kim Hyun‐Il Seo Hui‐Seong Song Seung‐Joon Kim 《International journal of quantum chemistry》2016,116(19):1427-1436
Density functional theory and ab initio calculations were performed to elucidate the hydrogen interactions in (H2O4)n (n = 1–4) clusters. The optimized geometries, binding energies, and harmonic vibrational frequencies were predicted at various levels of theory. The trans conformer of the H2O4 monomer was predicted to be the most stable structure at the CCSD(T)/aug‐cc‐pVTZ level of theory. The binding energies per H2O4 monomer increased in absolute value by 9.0, 10.1, and 11.8 kcal/mol from n = 2 to n = 4 at the MP2/cc‐pVTZ level of theory (after the zero‐point vibrational energy and basis set superposition error corrections). This result implies that the intermolecular hydrogen bonds were stronger in the long‐chain clusters, that is, the formation of the longer chain in the (H2O4)n clusters was more energetically favorable. 相似文献
84.
85.
Dal Piaz F De Leo M Braca A De Simone F De Tommasi N 《Rapid communications in mass spectrometry : RCM》2007,21(3):286-296
Glycoconjugates are a class of complex molecules that are widely distributed in the plant kingdom and in some marine organisms. This class of compounds has a wide range of biological activities such as anti-inflammatory, antimicrobial, antifungal, anticancer, antiulcer, and immunoenhancing actions.1-3 Some of them also show various toxic activities such as cytotoxic, hemolytic, cardiotoxic, and teratogenic. Among these compounds, steroidal and triterpenoid saponins have long been known as components of widely used herbal drugs and pharmaceutical preparations; ginseng, Tribulus terrestris, Quillaja saponaria, and Digitalis ssp. are just a few examples. Thus, identification of saponins in herbal drugs used worldwide is of significance in phytochemical and toxicological quality control studies, and for the production of safe health products. Therefore, there is continuing demand for methods to rapidly identify and characterize these natural products. 相似文献
86.
Chiara Dal Bosco Flavia Bonoli Alessandra Gentili Chiara Fanali Giovanni DOrazio 《Molecules (Basel, Switzerland)》2021,26(23)
A novel chromatographic application in chiral separation by using the nano-LC technique is here reported. The chiral recognition of 12 antifungal drugs was obtained through a 75 µm I.D. fused-silica capillary, which was packed with a CSP-cellulose 3,5-dichlorophenylcarbamate (CDCPC), by means of a lab-made slurry packing procedure. The mobile phase composition and the experimental conditions were optimized in order to find the optimum chiral separation for some selected racemic mixtures of imidazole and triazole derivatives. Some important parameters, such as retention faction, enantioresolution, peak efficiency, and peak shape, were investigated as a function of the mobile phase (pH, water content, type and concentration of both the buffer and the organic modifier, and solvent dilution composition). Within one run lasting 25 min, at a flow rate of approximately 400 nL min−1, eight couples of enantiomers were baseline-resolved and four of them were separated in less than 25 min. The method was then applied to milk samples, which were pretreated using a classical dispersive liquid–liquid microextraction technique preceded by protein precipitation. Finally, the DLLME-nano-LC–UV method was validated in a matrix following the main FDA guidelines for bioanalytical methods. 相似文献
87.
Upon stretching a natural rubber sample, polymer chains orient themselves in the direction of the applied load and form crystalline regions. When the sample is retracted, the original amorphous state of the network is restored. Due to crystallization, properties of rubber change considerably. The reinforcing effect of the crystallites stiffens the rubber and increases the crack growth resistance. It is of great importance to understand the mechanism leading to strain-induced crystallization. However, limited theoretical work has been done on the investigation of the associated kinetics. A key characteristic observed in the stress–strain diagram of crystallizing rubber is the hysteresis, which is entirely attributed to strain-induced crystallization. In this work, we propose a micromechanically motivated material model for strain-induced crystallization in rubbers. Our point of departure is constructing a micromechanical model for a single crystallizing polymer chain. Subsequently, a thermodynamically consistent evolution law describing the kinetics of crystallization on the chain level is proposed. This chain model is then incorporated into the affine microsphere model. Finally, the model is numerically implemented and its performance is compared to experimental data. 相似文献
88.
Manjula Spah Dal Chand Spah Sooyoung Jun Seungmoon Lee Ho-Jun Song Koh Won-Gun Jin-Won Park 《Fluid Phase Equilibria》2009
The EMF data of different metal chlorides (2:1 electrolytes) were obtained by using a cell [MX Hg|MCl2 (m)|AgCl–Ag] at two temperatures. Stock solutions of metal chlorides (CoCl2, CuCl2 and ZnCl2) were prepared by weight in 1,4-dioxane–aqueous mixtures. There was a significant change in the EMF values with change of metal chloride, its concentration and solvents composition. The standard electrode potential (E°) values of the above cell were calculated from the measured EMF of these mixtures. The standard thermodynamic functions (ΔG°, ΔH° and ΔS°) and respective transfer parameters of MCl2 from water to 20, 45 and 70% dioxane–water mixtures were also evaluated. Equilibrium dissociation constants (K1 and K2) as well as the degrees of dissociation (α1 and α2) were obtained by iterative procedures. The data were analyzed in terms of solute–solvent interactions depending on standard and transfer thermodynamic parameters and mean activity coefficients (γ±) of electrolytes. 相似文献
89.
90.
Jang HS Ryu KE Ahn WS Chun HJ Dal Park H Park KD Kim YH 《Colloids and surfaces. B, Biointerfaces》2006,50(2):141-146
Previously, novel poly(ethylene glycol) (PEG) and sulfonated PEG acrylate (PEG-SO3A/OA) copolymers were prepared as coating and/or blending materials for biomedical applications. Surfaces modified with copolymers exhibited increased anti-coagulation properties and decreased plasma adsorption level due to increased hydrophilic properties and reorientation characteristics of PEG/PEG-SO3A chains in water phase. As continuation study, anti-complement effects of PEG-SO3/OA copolymers were investigated in vitro, and compared with those of low-density polyethylene (LDPE) and PEG/OA. C3 activation by PEG-SO3/OA samples was lower than that by PEG/OA samples, which was attributed to decreased surface nucleophile level of samples. PEG-SO3/OA samples increased inhibition of Bb production, resulting in decreased C5 activation. Owing to reduced activations of C3 and C5, PEG-SO3/OA samples markedly decreased SC5b-9 levels in plasma. 相似文献