全文获取类型
收费全文 | 541篇 |
免费 | 12篇 |
国内免费 | 103篇 |
专业分类
化学 | 554篇 |
晶体学 | 3篇 |
力学 | 5篇 |
综合类 | 1篇 |
数学 | 12篇 |
物理学 | 81篇 |
出版年
2023年 | 31篇 |
2022年 | 13篇 |
2021年 | 10篇 |
2020年 | 7篇 |
2019年 | 4篇 |
2018年 | 8篇 |
2017年 | 12篇 |
2016年 | 9篇 |
2015年 | 13篇 |
2014年 | 7篇 |
2013年 | 38篇 |
2012年 | 31篇 |
2011年 | 38篇 |
2010年 | 31篇 |
2009年 | 46篇 |
2008年 | 32篇 |
2007年 | 34篇 |
2006年 | 20篇 |
2005年 | 24篇 |
2004年 | 16篇 |
2003年 | 5篇 |
2002年 | 11篇 |
2001年 | 17篇 |
2000年 | 15篇 |
1999年 | 11篇 |
1998年 | 13篇 |
1997年 | 9篇 |
1996年 | 11篇 |
1995年 | 12篇 |
1994年 | 8篇 |
1993年 | 14篇 |
1992年 | 13篇 |
1991年 | 9篇 |
1990年 | 11篇 |
1989年 | 6篇 |
1988年 | 5篇 |
1987年 | 10篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 1篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 8篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 11篇 |
1976年 | 4篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1972年 | 2篇 |
排序方式: 共有656条查询结果,搜索用时 250 毫秒
1.
Jing Cao Tong Mou Bingbao Mei Pengfei Yao Ce Han Xue Gong Ping Song Prof. Zheng Jiang Prof. Thomas Frauenheim Prof. Jianping Xiao Prof. Weilin Xu 《Angewandte Chemie (International ed. in English)》2023,62(43):e202310973
Full understanding to the origin of the catalytic performance of a supported nanocatalyst from the points of view of both the active component and support is significant for the achievement of high performance. Herein, based on a model electrocatalyst of single-iridium-atom-doped iron (Fe)-based layered double hydroxides (LDH) for oxygen evolution reaction (OER), we reveal the first completed origin of the catalytic performance of such supported nanocatalysts. Specially, besides the activity enhancement of Ir sites by LDH support, the stability of surface Fe sites is enhanced by doped Ir sites: DFT calculation shows that the Ir sites can reduce the activity and enhance the stability of the nearby Fe sites; while further finite element simulations indicate, the stability enhancement of distant Fe sites could be attributed to the much low concentration of OER reactant (hydroxyl ions, OH−) around them induced by the much fast consumption of OH− on highly active Ir sites. These new findings about the interaction between the main active components and supports are applicable in principle to other heterogeneous nanocatalysts and provide a completed understanding to the catalytic performance of heterogeneous nanocatalysts. 相似文献
2.
Xiao-Gang Yang Ji-Rui Zhang Xu-Ke Tian Jian-Hua Qin Xin-Ya Zhang Lu-Fang Ma 《Angewandte Chemie (International ed. in English)》2023,62(7):e202216699
The development of efficient enzyme immobilization to promote their recyclability and activity is highly desirable. Zeolitic imidazolate framework-8 (ZIF-8) has been proved to be an effective platform for enzyme immobilization due to its easy preparation and biocompatibility. However, the intrinsic hydrophobic characteristic hinders its further development in this filed. Herein, a facile synthesis approach was developed to immobilize pepsin (PEP) on the ZIF-8 carrier by using Ni2+ ions as anchor (ZIF-8@PEP-Ni). By contrast, the direct coating of PEP on the surface of ZIF-8 (ZIF-8@PEP) generated significant conformational changes. Electrochemical oxygen evolution reaction (OER) was employed to study the catalytic activity of immobilized PEP. The ZIF-8@PEP-Ni composite attains remarkable OER performance with an ultralow overpotential of only 127 mV at 10 mA cm−2, which is much lower than the 690 and 919 mV overpotential values of ZIF-8@PEP and PEP, respectively. 相似文献
3.
Dr. Yunqin Zhang Leilei Wang Qingli Zhou Zuoshan Li Dan Li Caixia Yin Prof. Xiufang Wang Prof. Guozhi Xiao 《Angewandte Chemie (International ed. in English)》2023,62(22):e202301351
Lipopolysaccharides from Bacteroides vulgatus represent interesting targets for the treatment of inflammatory bowel diseases. However, efficient access to long, branched and complex lipopolysaccharides remains challenging. Herein, we report the modular synthesis of a tridecasaccharide from Bacteroides vulgates through an orthogonal one-pot glycosylation strategy based on glycosyl ortho-(1-phenylvinyl)benzoates, which avoids the issues of thioglycoside-based one-pot synthesis. Our approach also features: 1) 5,7-O-di-tert-butylsilylene-directed glycosylation for stereoselective construction of the α-Kdo linkage; 2) hydrogen-bond-mediated aglycone delivery for the stereoselective formation of β-mannosidic bonds; 3) remote anchimeric assistance for stereoselective assembly of the α-fucosyl linkage; 4) several orthogonal one-pot synthetic steps and strategic use of orthogonal protecting groups to streamline oligosaccharide assembly; 5) convergent [1+6+6] one-pot synthesis of the target. 相似文献
4.
《Arabian Journal of Chemistry》2023,16(4):104531
Nitroxynil(NIT) is a commonly used anti-liver fluke drug for cattle and sheep, Its solubility is closely related to its preparation. In this work, the molar solubility of NIT in nine pure solvents (methanol, ethanol, 1,2-propanediolethyl, isopropanol, ethyl acetate, acetonitrile, n-butanol, phemethylol) and two kinds of binary mixtures with different ratio(ethanol + phemethylol; ethanol + acetonitrile) was determined by shake flask method over the temperature from 278.15 ~ 323.15 K at atmosphere pressure. Results show that the solubility of NIT in all tested solvents was increased with raised temperature. In mono-solvents, the mole fraction solubility of NIT was highest in phemethylol and the solubility order is: phemethylol > acetonitrile > ethyl acetate > methanol > n-butanol > ethanol > 1,2-propanediolethyl > isopropanol > water. In binary solvents, the mole fraction solubility increased with increasing ratio of phemethylol/acetonitrile. In mono-solvents, the modified Apelblat equation, λh equation, Van't Hoff model were applied to correlate the solubility data. In binary solvents, the modified Apelblat equation, λh equation, GSM model and Jouyban-Acree model were to correlate the solubility data. Solubility order of NIT in nine pure solvent and two binary solvent systems were analysed by using the Hansen solubility parameter (HSP). Activity coefficient was to access the solute–solvent molecular interactions. In addition, the dissolution of NIT is an endothermic and entropy-friendly process, since thermodynamic parameters such as enthalpy, entropy, and apparent standard Gibbs free energy are all greater than zero. The results will supply some essential data on recrystallization process, purification and formulation development of NIT in pharmaceutical applications. 相似文献
5.
准确理解金属大环配合物(如N4-Fe2+)体系的氧化还原化学性能,对氧还原反应(ORR)电催化剂的基础研究和合理设计具有重要意义.本文采用微波法将三种不同酞菁铁类金属大环配合物吸附在碳纳米管上,分别记为(NH2)4FePc@CNTs,(t-Bu)4FePc@CNTs和FePc@CNTs,考察了取代基对Fe3+/Fe2+氧化还原电位的影响,以及碱性介质中的氧还原反应催化活性.结果表明,FePc@CNTs,(t-Bu)4FePc@CNTs和(NH2)4FePc@CNTs的ORR起始电位分别为0.98,0.96和0.96 V,而半波电位(E1/2)由高到低的顺序为FePc@CNTs(E1/2=0.91 V),(t-Bu)4FePc@CNTs(E1/2=0.87 V),(NH2)4FePc@CNTs(E1/2=0.83 V).与20%Pt/C(E1/2=0.85 V)相比,FePc@CNTsFePc@CNTs具有优异的ORR性能.在活性、稳定性和耐甲醇性方面,FePc@CNTs复合材料比其他复合材料表现出更高的ORR性能.研究发现,FePc上的供电子基团可以显著改变N4-Fe2+活性位点的电子云密度,增加dz 2轨道(HOMO)的能量,并观察到Fe2+/Fe3+氧化还原电位显著向阴极方向移动.结果表明,取代基的高电子贡献能力降低了HOMO和LUMO(O2的杂轨道*-轨道)之间的电子耦合,从而降低了氧还原催化活性.因此,FePc框架外围的供电子基团对ORR不利.本文阐明了取代基电子效应-金属大环配合物氧化还原电位与ORR催化性能之间的关系,为ORR催化剂活性中心的构建和调控提供了借鉴. 相似文献
6.
In this paper, a new predictive model is proposed for prediction of gas hydrate formation conditions in the presence of single and mixed electrolytes and solutions containing both electrolyte and a polar inhibitor such as monoethylene glycol (MEG), diethylene glycol (DEG) and triethylene glycol (TEG). The proposed model is based on the γ–φ approach, which uses modified Patel–Teja equation of state (VPT EOS) for characterizing the vapor phase, the solid solution theory by van der Waals and Platteeuw for modeling the hydrate phase, the non-electrolyte NRTL-NRF local composition model and Pitzer–Debye–Huckel equation as short-range and long-range contributions to calculate water activity in single electrolyte solutions. Also, the Margules equation was used to determine the activity of water in solutions containing polar inhibitor (glycols). The model predictions are in acceptable agreement with experimental data. For single electrolyte solutions, the model predictions are similar to available models, while for mixtures of electrolytes and mixtures of electrolytes and inhibitors, the proposed model gives significantly better predictions. In addition, the absolute average deviation of hydrate formation pressures (AADP) for 144 experimental data in solutions containing single electrolyte is 5.86% and for 190 experimental data in mixed electrolytes solutions is 5.23%. Furthermore, the proposed model has an AADP of 14.13%, 5.82% and 5.28% in solutions containing (Electrolyte + MEG), (Electrolyte + DEG) and (Electrolyte + TEG), respectively. 相似文献
7.
采用化学共还原法合成了聚乙烯吡咯烷酮保护的Pt/Cu双金属纳米颗粒(BNPs),并采用紫外可见吸收光谱、透射电子显微镜、高分辨透射电子显微镜等对所合成的Pt/Cu BNPs进行了表征。研究了化学组成对Pt/Cu BNPs催化Na BH4水解制氢性能的影响。结果表明,所制备的Pt/Cu BNPs平均粒径为1.8~2.3nm,其催化活性远高于单金属Pt和Cu NPs的活性,其中Pt90Cu10BNP的催化活性最高,其在30℃的条件下,催化Na BH4制氢的活性可达6570mol-H2·mol-cat-1·h-1,约为相同粒径的Pt单金属NP的1.6倍。密度泛函理论的计算结果表明,Pt/Cu BNPs优异的催化性能可归因于电荷转移效应,Pt原子与Cu原子之间发生的电子转移使得Pt原子带负电而Cu原子带正电,荷电的Pt和Cu原子成为催化反应的活性中心。 相似文献
8.
Recognising everyday activities including information about the context requires to handle large state spaces. The usage of wearable sensors like six degree of freedom accelerometers increases complexity even more. Common approaches are unable to maintain an accurate belief state within such complex domains. We show how marginal filtering can overcome limitations of standard particle filtering and efficiently infer the context of actions. Symbolic models of human behaviour are used to recognise activities in two different settings with different state space sizes. Based on these scenarios we compare the marginal filter to the standard particle filter. An evaluation shows that the marginal filter performs comparably in small state spaces but outperforms the particle filter in large state spaces. 相似文献
9.
西气东输工程中卫黄河穿越隧道长1197.77m,高4.3m,宽5.6m。隧道入口高于黄河水位28m,出口高于黄河水位45m。隧道顶板高程为1130m。位于黄河水下100m。隧道场地围岩为寒武系磨盘井组灰绿色、银灰色浅变质中厚层细粒长石石英砂岩、千枚状板岩、绢云母化千枚岩。围岩为弱风化Ⅲ~Ⅳ类岩石。透水率为4~67Lu,纵波波速为500~3300m.s-1。BQ为300~400。变形模量为6.11~9.22GPa。泊松比(μ)0.14~0.24。内摩擦角(ψ)为42.1°~44.7°。地下水为基岩裂隙水。含水层为寒武系浅变质岩,受大气降水渗入补给,单井涌水量为1.0~50m3.d-1。隧道轴线穿越区岩体较完整—较破碎,未有全新活动断层。隧道位置选择和开挖深度设计是可行的。施工和长期运营是安全的。 相似文献
10.