全文获取类型
收费全文 | 2261篇 |
免费 | 285篇 |
国内免费 | 331篇 |
专业分类
化学 | 2797篇 |
晶体学 | 2篇 |
力学 | 3篇 |
综合类 | 9篇 |
物理学 | 66篇 |
出版年
2023年 | 38篇 |
2022年 | 202篇 |
2021年 | 249篇 |
2020年 | 173篇 |
2019年 | 135篇 |
2018年 | 111篇 |
2017年 | 98篇 |
2016年 | 117篇 |
2015年 | 125篇 |
2014年 | 114篇 |
2013年 | 185篇 |
2012年 | 103篇 |
2011年 | 111篇 |
2010年 | 84篇 |
2009年 | 109篇 |
2008年 | 77篇 |
2007年 | 88篇 |
2006年 | 84篇 |
2005年 | 72篇 |
2004年 | 69篇 |
2003年 | 81篇 |
2002年 | 66篇 |
2001年 | 41篇 |
2000年 | 47篇 |
1999年 | 36篇 |
1998年 | 29篇 |
1997年 | 37篇 |
1996年 | 24篇 |
1995年 | 49篇 |
1994年 | 27篇 |
1993年 | 24篇 |
1992年 | 13篇 |
1991年 | 10篇 |
1990年 | 9篇 |
1989年 | 6篇 |
1988年 | 7篇 |
1987年 | 1篇 |
1986年 | 7篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有2877条查询结果,搜索用时 375 毫秒
141.
H. Ahmad K. Kumar M. A. Rahman M. M. Rahman M. A. J. Miah H. Minami M. A. Nuri 《先进技术聚合物》2013,24(8):740-746
Considering the application potentials of organic materials possessing both conducting and ferromagnetic functions in various electronic devices, an attempt was made to prepare conducting polyaniline (PANI) layered magnetic nano composite polymer particles. Two routes were used to modify magnetic Fe3O4 core particles. In one route, seeded emulsion polymerization of methyl methacrylate (MMA) was carried out in presence of nano‐sized Fe3O4 core particles. In another route, cross‐linker ethyleneglycol dimethacrylate (EGDM) was used in addition to MMA. The modified composite particles were named as Fe3O4/PMMA and Fe3O4/P(MMA‐EGDM), respectively. Finally, seeded chemical oxidative polymerization of aniline was carried out in the presence of Fe3O4/PMMA and Fe3O4/P(MMA‐EGDM) composite seed particles to obtain Fe3O4/PMMA/PANI and Fe3O4/P(MMA‐EGDM)/PANI composite polymer particles. The modification of Fe3O4 core particles was confirmed by electron micrographs, FTIR, UV–visible spectra, X‐ray photoelectron spectra, X‐ray diffraction pattern and thermogravimetric analyses. A comparative study showed that crosslinking of intermediate shell improved the magnetic susceptibility and electrical conductivity of PANI layered magnetic nano composite particles. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
142.
R. Vasanthakumari 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(4):463-468
Differential scanning calorimetry has been used to study the thermal crystallization of poly(L-lactic acid) (PLLA) and pentaerythrityl tetrabromide mixtures at different compositions. The melting temperature-composition phase diagram of the system reveals that PLLA forms a simple eutectic with pentaerythrityl tetrabromide, with a eutectic composition of 46% (w/w) of PLLA and a eutectic temperature of 422 K. Investigation of the microstructures obtained after removal of the diluent from the eutectic using scanning electron microscopy shows that the simultaneous crystallization of PLLA and the diluent proceeded in such a way that the diluent rods are the leading phases. 相似文献
143.
The flammability and the thermal oxidative degradation kinetics of expandable graphite (EG) with magnesium hydroxide (MH) in flame‐retardant polypropylene (PP) composites were studied by limiting oxygen index (LOI), UL‐94 test, and thermogravimetric analysis (TGA). The results show that EG is a good synergist for improving the flame retardancy of PP/MH composite and the effect is enhanced with decreasing EG particle size. The Kissinger method and Flynn‐Wall‐Ozawa method were used to determine the apparent activation energy (E) for degradation of PP and flame retarded PP composites. The data obtained from the TGA curve indicate that EG markedly increases the thermal degradation temperature of PP/MH composites and improves the thermal stability of the composites. The kinetic results show that the values of E for degradation of flame retarded PP composites is much higher than that of neat PP, especially PP/MH composites with suitable amount of EG, which indicates that the flame retardants used in this work have a great effect on the mechanisms of pyrolysis and combustion of PP. 相似文献
144.
Bharathi Avula Babu L. Tekwani Narayan D. Chaurasiya NP Dhammika Nanayakkara Yan‐Hong Wang Shabana I. Khan Vijender R. Adelli Rajnish Sahu Mahmoud A. Elsohly James D. McChesney Ikhlas A. Khan Larry A. Walker 《Journal of mass spectrometry : JMS》2013,48(2):276-285
Therapeutic efficiency and hemolytic toxicity of primaquine (PQ), the only drug available for radical cure of relapsing vivax malaria are believed to be mediated by its metabolites. However, identification of these metabolites has remained a major challenge apparently due to low quantities and their reactive nature. Drug candidates labeled with stable isotopes afford convenient tools for tracking drug‐derived metabolites in complex matrices by liquid chromatography‐tandem mass spectrometry (LC‐MS‐MS) and filtering for masses with twin peaks attributable to the label. This study was undertaken to identify metabolites of PQ from an in vitro incubation of a 1:1 w/w mixture of 13C6‐PQ/PQ with primary human hepatocytes. Acquity ultra‐performance LC (UHPLC) was integrated with QTOF‐MS to combine the efficiency of separation with high sensitivity, selectivity of detection and accurate mass determination. UHPLC retention time, twin mass peaks with difference of 6 (originating from 13C6‐PQ/PQ), and MS‐MS fragmentation pattern were used for phenotyping. Besides carboxy‐PQ (cPQ), formed by oxidative deamination of PQ to an aldehyde and subsequent oxidation, several other metabolites were identified: including PQ alcohol, predictably generated by oxidative deamination of PQ to an aldehyde and subsequent reduction, its acetate and the alcohol's glucuronide conjugate. Trace amounts of quinone‐imine metabolites of PQ and cPQ were also detected which may be generated by hydroxylation of the PQ/cPQ quinoline ring at the 5‐position and subsequent oxidation. These findings shed additional light on the human hepatic metabolism of PQ, and the method can be applied for identification of reactive PQ metabolites generated in vivo in preclinical and clinical studies. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
145.
Eui-Soon Park Juhyeok Kim Tae-uk Ha Jong-Soon Choi Kwan Soo Hong Jaerang Rho 《Experimental & molecular medicine》2013,45(8):e35
Apoptosis has an important role in maintaining tissue homeostasis in cellular stress responses such as inflammation, endoplasmic reticulum stress, and oxidative stress. T-cell death-associated gene 51 (TDAG51) is a member of the pleckstrin homology-like domain family and was first identified as a pro-apoptotic gene in T-cell receptor-mediated cell death. However, its pro-apoptotic function remains controversial. In this study, we investigated the role of TDAG51 in oxidative stress-induced apoptotic cell death in mouse embryonic fibroblasts (MEFs). TDAG51 expression was highly increased by oxidative stress responses. In response to oxidative stress, the production of intracellular reactive oxygen species was significantly enhanced in TDAG51-deficient MEFs, resulting in the activation of caspase-3. Thus, TDAG51 deficiency promotes apoptotic cell death in MEFs, and these results indicate that TDAG51 has a protective role in oxidative stress-induced cell death in MEFs. 相似文献
146.
147.
Marek Grzybowski Kamil Skonieczny Prof. Dr. Holger Butenschön Prof. Dr. Daniel T. Gryko 《Angewandte Chemie (International ed. in English)》2013,52(38):9900-9930
Does the dehydrogenative coupling of aromatic compounds mediated by AlCl3 at high temperatures and also by FeCl3, MoCl5, PIFA, or K3[Fe(CN)6] at room temperature proceed by the same mechanism in all cases? With the growing importance of the synthesis of aromatic compounds by double C? H activation to give various biaryl structures, this question becomes pressing. Since some of these reactions proceed only in the presence of non‐oxidizing Lewis acids and some only in the presence of certain oxidants, the authors venture the hypothesis that, depending on the electronic structure of the substrates and the nature of the “catalyst”, two different mechanisms can operate. One involves the intermediacy of a radical cation and the other the formation of a sigma complex between the acid and the substrate. The goal of this Review is to encourage further mechanistic studies hopefully leading to an in‐depth understanding of this phenomenon. 相似文献
148.
149.
Ugo Bussy Illa Tea Véronique Ferchaud-Roucher Michel Krempf Virginie Silvestre Nicolas Galland Denis Jacquemin Moa Andresen-Bergström Ulrik Jurva Mohammed Boujtita 《Analytica chimica acta》2013
The coupling between an electrochemical cell (EC) and a mass spectrometer (MS) is a useful screening tool (EC-MS) to study the oxidative transformation pathways of various electroactive species. For that purpose, we showed that the EC-MS method, carried out in the presence and absence of isotope 18O labeled water leads not only to a fast identification of oxidation products but also leads to a fast elucidation of the mechanism pathway reaction. We examined herein the case of the electrochemical hydrolysis of activated aromatic ether. Acebutolol (β-blockers) was selected herein as model of activated aromatic ether, and its electrochemical oxidation was examined in both the presence and absence of isotope 18O labeled water. To elucidate electrochemical hydrolysis pathway reaction: O-dealkylation or O-dealkoxylation, our approach was used to prove its applicability. The electrochemical oxidation mechanism was then elucidated showing an O-dealkoxylation reaction. In addition, density functional theory (DFT) calculations fully support the experimental conclusions. 相似文献
150.
Li‐Jun Yang Kun Jiang Jun‐Jie Tan Shi‐Jin Qu Hong‐Feng Luo Chang‐Heng Tan Da‐Yuan Zhu 《Helvetica chimica acta》2013,96(1):119-123
Chemical investigation on the stem and root of Melicope pteleifolia afforded three new prenylated benzene metabolites as racemic mixtures, named pteleifolins A–C ( 1 – 3 , resp.). Their gross structures were elucidated on the basis of spectroscopic analysis, especially 2D‐NMR experiments. An enantiomer resolution of (±)‐ 1 using chiral HPLC was performed, and the absolute configuration of the enantiomers were determined to be (+)‐(S)‐ 1 and (?)‐(R)‐ 1 by means of circular‐dichroism analysis. 相似文献