全文获取类型
收费全文 | 546篇 |
免费 | 109篇 |
国内免费 | 96篇 |
专业分类
化学 | 714篇 |
晶体学 | 3篇 |
力学 | 16篇 |
综合类 | 3篇 |
物理学 | 15篇 |
出版年
2023年 | 12篇 |
2022年 | 9篇 |
2021年 | 16篇 |
2020年 | 35篇 |
2019年 | 30篇 |
2018年 | 16篇 |
2017年 | 27篇 |
2016年 | 39篇 |
2015年 | 39篇 |
2014年 | 40篇 |
2013年 | 60篇 |
2012年 | 69篇 |
2011年 | 40篇 |
2010年 | 22篇 |
2009年 | 43篇 |
2008年 | 50篇 |
2007年 | 33篇 |
2006年 | 34篇 |
2005年 | 27篇 |
2004年 | 35篇 |
2003年 | 28篇 |
2002年 | 7篇 |
2001年 | 4篇 |
2000年 | 5篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 8篇 |
1995年 | 4篇 |
1994年 | 2篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1989年 | 1篇 |
1986年 | 1篇 |
1984年 | 1篇 |
排序方式: 共有751条查询结果,搜索用时 15 毫秒
1.
通过三点弯动态冲击实验和数值模拟方法,研究了分支交错层状仿生复合材料的动态断裂韧性。首先设计并制备了分支交错层状仿贝壳复合材料试样,即将一种脆性刚性材料和一种橡胶类材料分别作为复合材料的硬质层和软胶层;随后采用改进的分离式Hopkinson压杆装置进行了三点弯冲击实验;接着讨论了初始冲击速度、硬质材料长宽比、软质材料层厚度对复合材料试样动态断裂行为的影响;最后采用ABAQUS有限元数值模拟,研究了不同宽度和不同冲击方向对复合材料试样动态断裂韧性和裂纹扩展的影响。结果表明:随着冲击速度和硬质材料长宽比增加、软胶层厚度减小,裂纹越倾向于沿直线扩展,反之,裂纹越倾向于绕过硬质材料沿着软胶层呈折线扩展;试样的峰值动载荷和起裂时间也随之增大。有限元模拟结果表明:随着结构总宽度的增大,试样断裂韧性增加,裂纹倾向于绕过硬质材料沿着软胶层扩展;采用实验设计的冲击方向时,试样的断裂韧性高于其他方向。 相似文献
2.
A Scalable Biomimetic Synthesis of Resveratrol Dimers and Systematic Evaluation of their Antioxidant Activities 下载免费PDF全文
Bryan S. Matsuura Mitchell H. Keylor Bo Li YuXuan Lin Shelby Allison Prof. Dr. Derek A. Pratt Prof. Dr. Corey R. J. Stephenson 《Angewandte Chemie (International ed. in English)》2015,54(12):3754-3757
An efficient synthetic route to the resveratrol oligomers quadrangularin A and pallidol is reported. It features a scalable biomimetic oxidative dimerization that proceeds in excellent yield and with complete regioselectivity. A systematic evaluation of the natural products and their synthetic precursors as radical‐trapping antioxidants has revealed that, contrary to popular belief, this mode of action is unlikely to account for their observed biological activity. 相似文献
3.
4.
5.
Bio‐Inspired Transition Metal–Organic Hydride Conjugates for Catalysis of Transfer Hydrogenation: Experiment and Theory 下载免费PDF全文
Alex McSkimming Dr. Bun Chan Dr. Mohan M. Bhadbhade Dr. Graham E. Ball Prof. Stephen B. Colbran 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):2821-2834
Taking inspiration from yeast alcohol dehydrogenase (yADH), a benzimidazolium (BI+) organic hydride‐acceptor domain has been coupled with a 1,10‐phenanthroline (phen) metal‐binding domain to afford a novel multifunctional ligand ( L BI+) with hydride‐carrier capacity ( L BI++H?? L BIH). Complexes of the type [Cp*M( L BI)Cl][PF6]2 (M=Rh, Ir) have been made and fully characterised by cyclic voltammetry, UV/Vis spectroelectrochemistry, and, for the IrIII congener, X‐ray crystallography. [Cp*Rh( L BI)Cl][PF6]2 catalyses the transfer hydrogenation of imines by formate ion in very goods yield under conditions where the corresponding [Cp*Ir( L BI)Cl][PF6] and [Cp*M(phen)Cl][PF6] (M=Rh, Ir) complexes are almost inert as catalysts. Possible alternatives for the catalysis pathway are canvassed, and the free energies of intermediates and transition states determined by DFT calculations. The DFT study supports a mechanism involving formate‐driven Rh?H formation (90 kJ mol?1 free‐energy barrier), transfer of hydride between the Rh and BI+ centres to generate a tethered benzimidazoline (BIH) hydride donor, binding of imine substrate at Rh, back‐transfer of hydride from the BIH organic hydride donor to the Rh‐activated imine substrate (89 kJ mol?1 barrier), and exergonic protonation of the metal‐bound amide by formic acid with release of amine product to close the catalytic cycle. Parallels with the mechanism of biological hydride transfer in yADH are discussed. 相似文献
6.
Synthesis of a pH‐Sensitive Hetero[4]Rotaxane Molecular Machine that Combines [c2]Daisy and [2]Rotaxane Arrangements 下载免费PDF全文
Philip Waelès Benjamin Riss‐Yaw Dr. Frédéric Coutrot 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(20):6837-6845
The synthesis of a novel pH‐sensitive hetero[4]rotaxane molecular machine through a self‐sorting strategy is reported. The original tetra‐interlocked molecular architecture combines a [c2]daisy chain scaffold linked to two [2]rotaxane units. Actuation of the system through pH variation is possible thanks to the specific interactions of the dibenzo‐24‐crown‐8 (DB24C8) macrocycles for ammonium, anilinium, and triazolium molecular stations. Selective deprotonation of the anilinium moieties triggers shuttling of the unsubstituted DB24C8 along the [2]rotaxane units. 相似文献
7.
Hierarchical‐Structured Anatase‐Titania/Cellulose Composite Sheet with High Photocatalytic Performance and Antibacterial Activity 下载免费PDF全文
Dr. Yan Luo Prof. Dr. Jianguo Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2568-2575
Bulk hierarchical anatase‐titania/cellulose composite sheets were fabricated by subjecting an ultrathin titania gel film pre‐deposited filter paper to a solvo‐co‐hydrothermal treatment by using titanium butoxide as the precursor to grow anatase‐titania nanocrystallites on the cellulose nanofiber surfaces. The titanium butoxide specie is firstly absorbed onto the nanofibers of the cellulose substance through a solvothermal process, which was thereafter hydrolyzed and crystallized upon the subsequent hydrothermal treatment, leading to the formation of fine anatase‐titania nanoparticles with sizes of 2–5 nm uniformly anchored on the cellulose nanofibers. The resulting anatase‐titania/cellulose composite sheet shows a significant photocatalytic performance towards degradation of a methylene blue dye, and introduction of silver nanoparticles into the composite sheet yields an Ag‐NP/anatase‐titania/cellulose composite material possessing excellent antibacterial activity against both Gram‐positive and Gram‐negative bacteria. 相似文献
8.
Toward Functional Type III [Fe]‐Hydrogenase Biomimics for H2 Activation: Insights from Computation 下载免费PDF全文
Kevin A. Murray Dr. Matthew D. Wodrich Prof. Dr. Xile Hu Prof. Dr. Clémence Corminboeuf 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(10):3987-3996
The chemistry of [Fe]‐hydrogenase has attracted significant interest due to its ability to activate molecular hydrogen. The intriguing properties of this enzyme have prompted the synthesis of numerous small molecule mimics aimed at activating H2. Despite considerable effort, a majority of these compounds remain nonfunctional for hydrogenation reactions. By using a recently synthesized model as an entry point, seven biomimetic complexes have been examined through DFT computations to probe the influence of ligand environment on the ability of a mimic to bind and split H2. One mimic, featuring a bidentate diphosphine group incorporating an internal nitrogen base, was found to have particularly attractive energetics, prompting a study of the role played by the proton/hydride acceptor necessary to complete the catalytic cycle. Computations revealed an experimentally accessible energetic pathway involving a benzaldehyde proton/hydride acceptor and the most promising catalyst. 相似文献
9.
刺激响应型微胶囊由于具有独有的高稳定性、多功能性、膜结构的可调性、以及对不同芯材的运送能力,在药物封装和释放、人造细胞、催化、化学传感器等领域具有广阔的应用前景。本文综述了近年来不同刺激响应型复合微胶囊的可控释放的研究进展,包括温敏型、pH响应型、磁响应型、生物响应型、电响应型,以及光响应型微胶囊,根据释放机理的不同着重对光响应型微胶囊的释放过程进行了总结,并对微胶囊可控释放在未来的发展趋势进行了展望。 相似文献
10.
Inside Cover: Bio‐Inspired Transition Metal–Organic Hydride Conjugates for Catalysis of Transfer Hydrogenation: Experiment and Theory (Chem. Eur. J. 7/2015) 下载免费PDF全文