全文获取类型
收费全文 | 696篇 |
免费 | 139篇 |
国内免费 | 104篇 |
专业分类
化学 | 504篇 |
晶体学 | 17篇 |
力学 | 34篇 |
综合类 | 16篇 |
数学 | 65篇 |
物理学 | 303篇 |
出版年
2024年 | 1篇 |
2023年 | 4篇 |
2022年 | 6篇 |
2021年 | 8篇 |
2020年 | 24篇 |
2019年 | 14篇 |
2018年 | 13篇 |
2017年 | 12篇 |
2016年 | 23篇 |
2015年 | 29篇 |
2014年 | 31篇 |
2013年 | 52篇 |
2012年 | 65篇 |
2011年 | 62篇 |
2010年 | 52篇 |
2009年 | 49篇 |
2008年 | 60篇 |
2007年 | 44篇 |
2006年 | 37篇 |
2005年 | 31篇 |
2004年 | 28篇 |
2003年 | 47篇 |
2002年 | 56篇 |
2001年 | 51篇 |
2000年 | 33篇 |
1999年 | 30篇 |
1998年 | 16篇 |
1997年 | 8篇 |
1996年 | 5篇 |
1995年 | 7篇 |
1994年 | 2篇 |
1993年 | 4篇 |
1992年 | 5篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1989年 | 3篇 |
1987年 | 2篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1980年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1966年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有939条查询结果,搜索用时 33 毫秒
31.
Raul Aguayo Felipe Arias Alvaro Cañete Carolina Zuñiga Enrique A. Castro Paulina Pavez José G. Santos 《国际化学动力学杂志》2013,45(3):202-211
The reactions of the title compounds with phenoxides, secondary alicyclic (SA) amines, and pyridines, in 44 wt% ethanol–water, at 25°C and an ionic strength of 0.2 M, were subjected to kinetic and product studies. From analytical techniques (HPLC and NMR), two pathways were detected (nucleophilic attack at the phosphoryl center and at the C‐1 aromatic carbon) for the reactions of all the nucleophiles with the phosphate ( 2 ) and for the pyridinolysis of the thionophosphate ( 1 ). Only aromatic nucleophilic substitution was found for the reactions of 1 with phenoxides and SA amines. For the dual reactions, the nucleophilic rate constants (kN) were separated in two terms: $k_{\rm N}^{\rm P}$ and $k_{\rm N}^{{\rm Ar}}$, which are the rate constants for the corresponding electrophilic centers. The absence of a break in the Brønsted‐type plots for the attack at P is consistent with concerted mechanisms. The Brønsted slopes, βAr 0.32–0.71, for the attack at the aromatic C‐1, are in agreement with stepwise mechanisms where formation of a Meisenheimer complex is the rate‐determining step. © 2013 Wiley Periodicals, Inc. Int J Chem Kinet 45: 202–211, 2013 相似文献
32.
A highly efficient and environmental-benign oxidation by dioxygen (or air) as the sole oxidant was first applied for the conversion of 2-imidazoline-5-carboxylic derivatives to imidazole-5-carboxylic derivatives in very good and excellent yields. The substituent effect on 2-imidazoline ring was investigated. This protocol was also suitable for the synthesis of 2-imidazoles in relatively large scale. 相似文献
33.
A novel technique utilizing the adsorptive potential of immobilized multi‐walled carbon nanotubes (I‐MWCNT) in hollow fiber liquid‐phase microextraction (HF‐LPME) was developed for the determination of diuretics in urine. In this study, the potential of carbon nanotubes as a sorbent for three‐phase liquid‐phase microextraction of diuretics from urine samples was evaluated. Analysis was performed using liquid chromatography‐tandem mass spectrometry (LC‐MS/MS). A novel method was applied to detect acetazolamide (AAA), chlorothiazide (CTA), hydrochlorothiazide (HCT), hydroflumethiazide (HFT), clopamide (CA), trichlormethiazide (TCM), althiazide (AT) and bendroflumethiazide (BFT) in urine. Two‐step extractions using different times and temperatures for each step were adopted. Parameters influencing the extraction efficiency, including the extraction solvent, sample pH, salt concentration, extraction time and extraction temperature were systematically optimized. Under the resulting optimal extraction conditions, this method showed good linearity over an analytes concentration range of 1 to 1000 ng/mL, high extraction repeatability with relative standard deviations of less than 6%, and low detection limits (0.09 to 0.51 ng/mL). The application of the methods to the determination of diuretics in real samples was tested by analyzing urine samples of patient. 相似文献
34.
The interactions between potassium perfluorooctanesulfonate (PFOS) and bovine serum albumin (BSA) were studied by fluorescence spectroscopy. The association constants between PFOS and BSA were obtained by fluorescence enhancing and fluorescence quenching respectively. Furthermore, fluorescence quenching was studied at different temperatures, and the binding constant was also determined by the method of fluorescence quenching. According to the thermodynamic parameters, the main binding force could be judged. The experimental results revealed that BSA and PFOS had strong interactions. The mechanism of quenching belonged to dynamic quenching and the main sort of binding force was hydrophobic force. IR-spectra proved the interaction changed the conformation of BSA. 相似文献
35.
Gold (Au) nanoparticle arrays with tunable morphology and optical characteristics were synthesized by in-situ self-assembly process that occurred on the surface of aniline-modified polystyrene (PS) microspheres. The method can be used to control the growth of both single and aggregated Au nanoparticle arrays on PS microsphere surface. This method could also be adapted for synthesis of other noble metals hybrid materials, which opens exciting opportunities for their practical applications. 相似文献
36.
Yuangang Liu Yuesheng Tong Shibin Wang Qiongjia Deng Aizheng Chen 《Journal of Sol-Gel Science and Technology》2013,67(1):66-76
Different divalent metal ions (Ba2+, Sr2+, Ca2+, Zn2+) were selected as crosslinkers. The mechanical properties, cytocompatibility, histocompatibility, cell proliferation and long-term cultivation were investigated. The resulting microcapsules had good sphericity, smooth surface and particle size distribution of 300–400 μm. Sr2+ microcapsules exhibited a better mechanical strength. The molecular weights cut-off of all membranes were between 24 and 67 kDa. All microcapsules had no cytotoxicity. After intraperitoneal transplantation, the recovered microcapsules still maintained good mechanical strength and morphology with no fibrosis or macrophage aggregation phenomena. The microencapsulated PC12 cells showed no significant variation after recultivation following microcapsule breaking. The cell activity sequence of different microcapsules after 72 h was as follows: bare control cell >Sr2+ > Ca2+ > Ba2+ > Zn2+. After 9 weeks’ in vitro culture, the cell survival rate was higher than 80 %. This paper will be of scientific interests for the basic research and clinical application of alginate/chitosan microcapsules embedded with drugs or cells. 相似文献
37.
Meng Li Hong‐Ye Bai Zu‐Lin Da Xu Yan Chao Chen Jin‐Hui Jiang Wei‐Qiang Fan Wei‐Dong Shi 《Crystal Research and Technology》2015,50(3):244-249
CaFe2O4/MgFe2O4 nanowires with heterostructure had been successfully synthesized by electrospinning method. The obtained samples were systematically characterized by scanning electron microscopy (SEM), X‐Ray diffraction (XRD), UV–Vis diffuse reflectance spectra (UV‐Vis DR) and Environment scanning electron microscopy (ESEM). The novel CaFe2O4/MgFe2O4 nanowires exhibit an enhanced photocatalytic activity for degrading of tetracycline (TC) under visible light. Compared with bare CaFe2O4 or MgFe2O4 samples, the prepared CaFe2O4/MgFe2O4 (Ca:Mg:Fe = 3:2:10) composited nanowires show the best photocatalytic performance with a degradation efficiency of 40% after 150 min reaction time. This enhancement is attributed to the heterostructure of CaFe2O4/MgFe2O4 nanowires, which effectively repress the recombination of photo‐generated electrons and holes. Based on heterostructure and energy band positions, the enhancement of mechanism under visible‐light enhances the photocatalytic activity. 相似文献
38.
Yao Xiao Yan‐Fang Zhu Wei Xiang Zhen‐Guo Wu Yong‐Chun Li Jing Lai Shi Li Enhui Wang Zu‐Guang Yang Chun‐Liu Xu Ben‐He Zhong Xiao‐Dong Guo 《Angewandte Chemie (International ed. in English)》2020,59(4):1491-1495
Demands for large‐scale energy storage systems have driven the development of layered transition‐metal oxide cathodes for room‐temperature rechargeable sodium ion batteries (SIBs). Now, an abnormal layered‐tunnel heterostructure Na0.44Co0.1Mn0.9O2 cathode material induced by chemical element substitution is reported. By virtue of beneficial synergistic effects, this layered‐tunnel electrode shows outstanding electrochemical performance in sodium half‐cell system and excellent compatibility with hard carbon anode in sodium full‐cell system. The underlying formation process, charge compensation mechanism, phase transition, and sodium‐ion storage electrochemistry are clearly articulated and confirmed through combined analyses of in situ high‐energy X‐ray diffraction and ex situ X‐ray absorption spectroscopy as well as operando X‐ray diffraction. This crystal structure engineering regulation strategy offers a future outlook into advanced cathode materials for SIBs. 相似文献
39.
Jiajia Ru Ting He Binjie Chen Yutong Feng Lianhai Zu Zhijun Wang Qiaobao Zhang Tianzi Hao Ruijin Meng Renchao Che Chi Zhang Jinhu Yang 《Angewandte Chemie (International ed. in English)》2020,59(34):14621-14627
Weak van der Waals interactions between interlayers of two‐dimensional layered materials result in disabled across‐interlayer electron transfer and poor layered structural stability, seriously deteriorating their performance in energy applications. Herein, we propose a novel covalent assembly strategy for MoS2 nanosheets to realize unique MoS2/SnS hollow superassemblies (HSs) by using SnS nanodots as covalent linkages. The covalent assembly based on all‐inorganic and carbon‐free concept enables effective across‐interlayer electron transfer, facilitated ion diffusion kinetics, and outstanding mechanical stability, which are evidenced by experimental characterization, DFT calculations, and mechanical simulations. Consequently, the MoS2/SnS HSs exhibit superb rate performance and long cycling stability in lithium‐ion batteries, representing the best comprehensive performance in carbon‐free MoS2‐based anodes to date. Moreover, the MoS2/SnS HSs also show excellent sodium storage performance in sodium‐ion batteries. 相似文献
40.
Ma Lijiao Xu Ye Zu Yunfei Liao Qing Xu Bowei An Cunbin Zhang Shaoqing Hou Jianhui 《中国科学:化学(英文版)》2020,63(1):21-27
In order to meet the requirements for making organic solar cells(OSCs) through solution printing techniques, great efforts have been devoted into developing high performance OSCs with relatively thicker active layers. In this work, a thick-film(300 nm)ternary OSC with a power conversion efficiency of 14.3% is fabricated by introducing phenyl-C_(61)-butyric-acid-methyl ester(PC_(61)BM) into a PBDB-T-2Cl:BTP-4 F host blend. The addition of PC_(61)BM is found to be helpful for improving the hole and electron mobilities, and thus facilitates charge transport as well as suppresses charge recombination in the active layers, leading to the improved efficiencies of OSCs with relatively thicker active layers. Our results demonstrate the feasibility of employing fullerene derivative PC_(61)BM to construct a high-efficiency thick-film ternary device, which would promote the development of thick layer ternary OSCs to fulfill the requirements of future roll to roll production. 相似文献