全文获取类型
收费全文 | 590篇 |
免费 | 27篇 |
国内免费 | 41篇 |
专业分类
化学 | 203篇 |
晶体学 | 2篇 |
力学 | 36篇 |
数学 | 126篇 |
物理学 | 291篇 |
出版年
2025年 | 5篇 |
2024年 | 5篇 |
2023年 | 33篇 |
2022年 | 12篇 |
2021年 | 12篇 |
2020年 | 20篇 |
2019年 | 17篇 |
2018年 | 13篇 |
2017年 | 15篇 |
2016年 | 15篇 |
2015年 | 18篇 |
2014年 | 37篇 |
2013年 | 42篇 |
2012年 | 30篇 |
2011年 | 42篇 |
2010年 | 41篇 |
2009年 | 45篇 |
2008年 | 44篇 |
2007年 | 46篇 |
2006年 | 29篇 |
2005年 | 18篇 |
2004年 | 16篇 |
2003年 | 13篇 |
2002年 | 9篇 |
2001年 | 9篇 |
2000年 | 4篇 |
1999年 | 13篇 |
1998年 | 7篇 |
1997年 | 11篇 |
1996年 | 6篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 3篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1980年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有658条查询结果,搜索用时 0 毫秒
61.
β-nucleated long chain branched (LCB) polypropylene random copolymers (PPRs) were prepared via reactive extrusion by introducing β nucleating agent (NA), dicumyl peroxide (DCP) and various contents of 1, 6-Hexanediol diacrylate (HDDA) into PPR. Results of Fourier infrared spectroscopy (FTIR) and the rheological properties demonstrate the existence of LCB polypropylene. Mechanical properties including impact strength, tensile strength and elongation at break were studied. The crystal structure, morphology and crystallization behavior were investigated via wide-angle X-ray diffraction (WAXD), polarized light microscopy (PLM) and differential scanning calorimetry (DSC). Non-isothermal crystallization kinetics using the Jeziorny method was also studied. The results show an increased LCB degree with increasing HDDA amount. For the sample with a moderate LCB level, synergistic toughening effect of NA and LCB is achieved without deterioration of yield strength or elongation at break, partially because of its higher β-phase content and much smaller spherulite size. It exhibits the minimum values of Tc and Zc1, and the maximum values of t1/2 and n1 in the primary stage of crystallization, regardless of the cooling rate, indicating a slower crystallization rate and more complicated nucleation and crystal growth model. 相似文献
62.
Boyi Fu;Guangming Wang;Jiuyang Li;Junbo Li;Xun Li;Xiaoya Zhao;Shuhui Ding;Guoping Yan;Qianqian Yan;Kaka Zhang; 《中国化学》2024,42(11):1237-1246
Kasha's exciton model proposes that T1 energy levels of organic compounds are insensitive to molecular aggregation and microenvironment change because of negligible small transition dipole moments of T1 states. This model holds true in most organic systems till now. Here we report the fabrication of twisted organic phosphors with intramolecular charge transfer characters and flexible molecular structures. When doped into different organic matrices, the twisted phosphor adopts different conformation, exhibits distinct phosphorescence colors and T1 energy levels, which violates Kasha's exciton model in organic system. Given that the change of phosphorescence colors and maxima can be readily distinguished by human eyes and conventional instrument, the twisted phosphors would be exploited as a new type of molecular probe, which would exhibit potential application in optical sensing and stimuli-responsive systems. 相似文献
63.
Chengxia Miao;Hongfeng Zhuang;Yating Wen;Feng Han;Qing-Feng Yang;Lei Yang;Zhen Li;Chungu Xia; 《European journal of organic chemistry》2019,2019(19):3012-3021
Thioethers as important building blocks have been usually found in organic synthesis. Herein, a series of long chained acid-functionalized ionic liquids derived from pyrrolidine were applied for the thiolation of alcohols to synthesize different compounds containing thioether structures. This kind of ionic liquids exhibited higher efficiency than general ionic liquids based on imidazole, providing up to 99 % yield with [BsCtP][OTf] as the catalyst at room temperature for 0.25 h. The results indicated that the activities of the ionic liquids have relationship with the side chain length of ionic liquids based on pyrrolidine, anions and cations. The catalytic system had wide substrate scope and was applicable for the reaction of aromatic primary and secondary alcohols and thiols including aliphatic and aromatic thiols, benzothiazole-2-thiols and benzooxazole-2-thiols. Besides, there was no obvious change in activity of the catalyst after six runs. Thus, the catalytic system exhibited good recyclability. Additionally, carbocations should be the key intermediate and several functionalized groups of the ionic liquids have synergetic effect for the thiolation. 相似文献
64.
Antonio Doménech María Teresa Doménech‐Carbó Trinidad Pasies María del Carmen Bouzas 《Electroanalysis》2012,24(10):1945-1955
Two complementary models to describe the long‐term corrosion of silver‐copper coins, based on potential rate laws for smooth corrosion and those combined with diffusive law, for gross corrosion, are proposed. Theoretical kinetics can be tested using signatures of copper and silver corrosion products using the voltammetry of immobilized particles technique. The method is applied to silver coins minted during the 13th–14th centuries from the Libertad street hoard in Valencia (Spain) using non‐invasive one‐touch graphite pencil sampling. Voltammetric features yield functional dependences in agreement with the proposed model potentially useful for distinguishing between different mints. 相似文献
65.
This communication presents a study on the simultaneous determination of thermolabile N-methylcarbamate and organophosphorus insecticides in cereal products by gas chromatography-mass spectrometry. The thermal stability of the multiple insecticides was evaluated with conventional hot splitless injection and on-column injection. The results obtained by GC-MS with these two injection techniques were compared in terms of the recovery, the limit of detection, the limit of qualification, and the reproducibility. With on-column injection, the pesticide recoveries in cereal samples were better than 82%, with relative standard deviations lower than 5.4%. The limits of qualification for most insecticides were in the range of 0.009-0.08 mg/kg, i. e. lower than the maximum residue limits established for insecticides in cereal products by the European Union. The long-term stability using on-column injection for analysis of insecticides in real samples was evaluated and normal chromatographic performance could be obtained within 50 analyses. The results revealed that it was possible for application of on-column injection in the analysis of thermolabile multiple insecticides in food sample after comprehensive sample clean-up, despite the highly contaminated nature of the column system. 相似文献
66.
Cold represents one of the major abiotic factors influencing plant growth and development worldwide. We analysed the long-term responsiveness of an Iranian spring wheat (cv. Kohdasht) to cold from a proteomic point of view, in order to unravel the molecular mechanisms helping a cold-sensitive cultivar to survive exposure to suboptimal temperatures. Plants were grown at 20 or 4°C until entering the reproductive stage and a cross-comparison on the leaf proteomes was performed. Quantitative analyses on protein alterations occurring upon low-temperature exposure showed a reinforcement in ascorbate recycling (dehydroascorbate reductase, ascorbate peroxidase) and protein processing (proteasome subunit, cysteine proteinase), as well as the accumulation of the enzyme devoted to tetrapyrrole resynthesis (glutamate semialdehyde aminomutase). In contrast, among proteins down-regulated after cold stress, we could identify some key Krebs cycle enzymes (isocitrate dehydrogenase, malate dehydrogenase), together with many photosynthesis-related proteins (oxygen-evolving complex proteins, ATP synthase subunits, ferredoxin NADPH oxidoreductase and some Calvin cycle enzymes). Physiological and biochemical parameters (such as shoot apex dissection, chlorophyll, proline and sugar content determination) sustained proteomics findings allowing the present research to contribute to the current knowledge on these long-term responses, which may be crucial to stress adaptation under field conditions. 相似文献
67.
Todd B. Kreutzian Khalid S. A. Seraj Larry G. Anderson Donald C. Zapien 《Electroanalysis》2007,19(23):2479-2482
In this work, long optical path length thin‐layer electrochemical cell was constructed using indium‐tin oxide on glass as the electrode material. Iron release from ferritin adsorbed on the electrode was induced by applying a negative potential sweep in the presence of 1,10‐phenanthroline. The usefulness of spectroelectrochemistry as a means of determining the quantity of iron released from an adsorbed layer of ferritin is demonstrated. 相似文献
68.
Osamu Sato Shinya Hayami Zhong-ze Gu Kazuyuki Takahashi Rie Nakajima Akira Fujishima 《Phase Transitions》2013,86(7-8):779-785
Photo-illumination effects have been measured for the compound [Co III-LS (tmpda)(3,6-DBSQ)(3,6-DBCat)]. When the aforementioned compound was illuminated at 5 K, the magnetization value increased from w eff = 1.87 to 2.03 w B . The absorption spectra after illumination show that the absorption band at around 730 nm, which is characteristic of the [Co II-HS (tmpda)(3,6-DBSQ) 2 ] state, increased in intensity and that the charge transfer band from 3,6-DBCat to 3,6-DBSQ at 2500 nm was reduced in intensity. IR spectra show that the C-O stretching peak at 1279 cm m 1 is decreased in intensity. These results confirm that a photo-induced intra-molecular electron transfer, [Co III-LS (tmpda)(3,6-DBSQ)(3,6-DBCat)] to; [Co II-HS (tmpda)(3,6-DBSQ) 2 ], was induced. The lifetime of the metastable state at 5 K was 15 min. Furthermore, it was found that reverse valence tautomerism can be induced by exciting the Co II-HS to 3,6-DBSQ charge transfer band in metastable [Co II-HS (tmpda)(3,6-DBSQ) 2 ]. 相似文献
69.
本文在长波假定下用流体力学线性稳定性理论对大动脉中血液流动求出了一种中性扰动。结果表明,心室或瓣引起的扰动在一定条件下有可能量一种中性扰动,它可以沿着动脉管无变形地传播到动脉远端。这说明也许有可能提供一种通过在远离心脏的某些浅表动脉部位检测这种中性成动以了解心脏的某些功能的新方法。 相似文献
70.
Local fracture resistance (FR) of short (SGF) and discontinuous long glass fibre (LGF) reinforced polypropylene (PP) was predicted using the ‘microstructural efficiency concept’ together with a simulation program for fibre orientation in injection molding. The ‘microstructural efficiency concept’ describes the relation between microstructural parameters such as the fibre content, the fibre aspect ratio and the processing (injection molding) induced layer structure taking also into account the local fibre orientation. The local fibre orientation in injection molding was predicted with the MOLDFLOW®-software. The predicted local FR was compared with the measured one, which was determined by using compact tension samples and linear elastic fracture mechanics (LEFM). The comparison showed, that for SGF-PP good consistence between the predicted and measured FR existed, for LGF-PP the discrepancy was higher. Yet for both materials, the ‘microstructural efficiency concept’ together with the results obtained from the simulation of the fibre orientation can be used for FR prediction of an injection molded workpiece. 相似文献