全文获取类型
收费全文 | 195篇 |
免费 | 12篇 |
专业分类
化学 | 188篇 |
晶体学 | 1篇 |
力学 | 1篇 |
数学 | 7篇 |
物理学 | 10篇 |
出版年
2024年 | 1篇 |
2023年 | 3篇 |
2022年 | 6篇 |
2021年 | 6篇 |
2020年 | 6篇 |
2019年 | 7篇 |
2018年 | 8篇 |
2017年 | 5篇 |
2016年 | 10篇 |
2015年 | 9篇 |
2014年 | 6篇 |
2013年 | 16篇 |
2012年 | 10篇 |
2011年 | 13篇 |
2010年 | 13篇 |
2009年 | 6篇 |
2008年 | 8篇 |
2007年 | 8篇 |
2006年 | 8篇 |
2005年 | 7篇 |
2004年 | 9篇 |
2003年 | 7篇 |
2002年 | 5篇 |
2001年 | 1篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1998年 | 6篇 |
1997年 | 3篇 |
1995年 | 2篇 |
1994年 | 5篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1989年 | 1篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有207条查询结果,搜索用时 0 毫秒
1.
Cayuela E Jalón FA Manzano BR Espino G Weissensteiner W Mereiter K 《Journal of the American Chemical Society》2004,126(22):7049-7062
Diastereomerically pure complexes of formula CpRuCl(PP) and CpRuH(PP) with chiral ferrocenyl diphosphines were prepared and the selectivity of proton-transfer processes over the monohydride compounds with different acids was studied. With 1 equiv of HBF(4) the cis-dihydrogen and trans-dihydride complexes were formed while with 3 equiv of CF(3)CO(2)H the trans-dihydride derivative was the only product. However, the use of 1 equiv of CF(3)CO(2)H led to a dihydrogen bonded complex with an extremely short RuH...HO(2)CF(3) interaction that exhibits proton-hydride exchange. Using the labeled acid CF(3)CO(2)D, a stereoselective transference of the deuteron was demonstrated that implies the previous epimerization of the monohydride and the subsequent attack of the acid in the position previously occupied by the hydride. 相似文献
2.
Zhou C Friedt JM Angelova A Choi KH Laureyn W Frederix F Francis LA Campitelli A Engelborghs Y Borghs G 《Langmuir : the ACS journal of surfaces and colloids》2004,20(14):5870-5878
Time-resolved adsorption behavior of a human immunoglobin G (hIgG) protein on a hydrophobized gold surface is investigated using multitechniques: quartz crystal microbalance/dissipation (QCM-D) technique; combined surface plasmon resonance (SPR) and Love mode surface acoustic wave (SAW) technique; combined QCM-D and atomic force microscopy (AFM) technique. The adsorbed hIgG forms interfacial structures varying in organization from a submonolayer to a multilayer. An "end-on" IgG orientation in the monolayer film, associated with the surface coverage results, does not corroborate with the effective protein thickness determined from SPR/SAW measurements. This inconsistence is interpreted by a deformation effect induced by conformation change. This conformation change is confirmed by QCM-D measurement. Combined SPR/SAW measurements suggest that the adsorbed protein barely contains water after extended contact with the hydrophobic surface. This limited interfacial hydration also contributed to a continuous conformation change in the adsorbed protein layer. The viscoelastic variation associated with interfacial conformation changes induces about 1.5 times overestimation of the mass uptake in the QCM-D measurements. The merit of combined multitechnique measurements is demonstrated. 相似文献
3.
4.
5.
Galina A. Gazieva Yurii B. Vikharev Lada V. Anikina Tatyana B. Karpova Angelina N. Kravchenko Evgenii A. Permyakov Igor V. Svitanko 《Mendeleev Communications》2013,23(4):202-203
Target synthesis of substituted thioglycolurils possessing sedative activity predicted by preliminary 3D-QSAR simulation of bioactive structures has been carried out. 相似文献
6.
7.
D. Cayuela M. Cot M. Riva R. J. Sanchez M. G. Sánchez-Loredo I. Algaba 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):831-841
The effect of untreated and tri-n-octylphosphine oxide (TOPO) surface-treated TiO2 nanoparticles when included as filler in poly(ethylene terephthalate) on its compatibility, non-isothermal crystallization behavior, viscoelastic transitions and cold crystallization has been studied. The effectiveness of the surface treatment has been studied using infrared spectrophotometry (FTIR) and thermogravimetric analysis (TGA). The effect of the untreated and surface-treated nanofiller content in the polymer, added by an extrusion process, on the non-isothermal crystallization has been studied by differential scanning calorimetry (DSC). The influence on the viscoelastic transitions and cold crystallization of PET nanocomposites has been studied through thermomechanical analysis (TMA). The surface treatment and the concentration of nanofiller influence the non-isothermal crystallization behavior, the viscoelastic transitions and the cold crystallization of the PET nanocomposites, enables us to evaluate the compatibility and the level of dispersion/aggregation of the nanofiller in the poly(ethylene terephthalate). 相似文献
8.
Angelina Biitseva Ulrich Groth Olga Hordiyenko 《Journal of heterocyclic chemistry》2013,50(5):1140-1145
A reaction of phthalonitrile with thiosemicarbazide and α‐haloketones proceeded in one‐pot, giving rise to 3‐amino‐1H‐isoindol‐1‐one thiazol‐2‐ylhydrazones in high yields. 相似文献
9.
Angelina Osipyan Dr. Shabnam Shaabani Robert Warmerdam Dr. Svitlana V. Shishkina Harry Boltz Prof. Dr. Alexander Dömling 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(30):12523-12527
Miniaturization and acceleration of synthetic chemistry is an emerging area in pharmaceutical, agrochemical, and materials research and development. Herein, we describe the synthesis of iminopyrrolidine-2-carboxylic acid derivatives using chiral glutamine, oxo components, and isocyanide building blocks in an unprecedented Ugi-3-component reaction. We used I-DOT, a positive-pressure-based low-volume and non-contact dispensing technology to prepare more than 1000 different derivatives in a fully automated fashion. In general, the reaction is stereoselective, proceeds in good yields, and tolerates a wide variety of functional groups. We exemplify a pipeline of fast and efficient nanomole-scale scouting to millimole-scale synthesis for the discovery of a useful novel reaction with great scope. 相似文献
10.
Valentina S. Borovkova Yuriy N. Malyar Irina G. Sudakova Anna I. Chudina Andrey M. Skripnikov Olga Yu. Fetisova Alexander S. Kazachenko Angelina V. Miroshnikova Dmitriy V. Zimonin Vladislav A. Ionin Anastasia A. Seliverstova Ekaterina D. Samoylova Noureddine Issaoui 《Molecules (Basel, Switzerland)》2022,27(1)
Spruce (Picea abies) wood hemicelluloses have been obtained by the noncatalytic and catalytic oxidative delignification in the acetic acid-water-hydrogen peroxide medium in a processing time of 3–4 h and temperatures of 90–100 °C. In the catalytic process, the H2SO4, MnSO4, TiO2, and (NH4)6Mo7O24 catalysts have been used. A polysaccharide yield of up to 11.7 wt% has been found. The hemicellulose composition and structure have been studied by a complex of physicochemical methods, including gas and gel permeation chromatography, Fourier-transform infrared spectroscopy, and thermogravimetric analysis. The galactose:mannose:glucose:arabinose:xylose monomeric units in a ratio of 5:3:2:1:1 have been identified in the hemicelluloses by gas chromatography. Using gel permeation chromatography, the weight average molar mass Mw of hemicelluloses has been found to attain 47,654 g/mol in noncatalytic delignification and up to 42,793 g/mol in catalytic delignification. Based on the same technique, a method for determining the α and k parameters of the Mark–Kuhn–Houwink equation for hemicelluloses has been developed; it has been established that these parameters change between 0.33–1.01 and 1.57–472.17, respectively, depending on the catalyst concentration and process temperature and time. Moreover, the FTIR spectra of the hemicellulose samples contain all the bands characteristic of heteropolysaccharides, specifically, 1069 cm−1 (C–O–C and C–O–H), 1738 cm−1 (ester C=O), 1375 cm−1 (–C–CH3), 1243 cm−1 (–C–O–), etc. It has been determined by the thermogravimetric analysis that the hemicelluloses isolated from spruce wood are resistant to heating to temperatures of up to ~100 °C and, upon further heating, start destructing at an increasing rate. The antioxidant activity of the hemicelluloses has been examined using the compounds simulating the 2,2-diphenyl-2-picrylhydrazyl free radicals. 相似文献