全文获取类型
收费全文 | 11599篇 |
免费 | 1198篇 |
国内免费 | 425篇 |
专业分类
化学 | 5138篇 |
晶体学 | 27篇 |
力学 | 1110篇 |
综合类 | 32篇 |
数学 | 5000篇 |
物理学 | 1915篇 |
出版年
2023年 | 150篇 |
2022年 | 153篇 |
2021年 | 216篇 |
2020年 | 403篇 |
2019年 | 291篇 |
2018年 | 272篇 |
2017年 | 239篇 |
2016年 | 456篇 |
2015年 | 463篇 |
2014年 | 582篇 |
2013年 | 950篇 |
2012年 | 640篇 |
2011年 | 660篇 |
2010年 | 450篇 |
2009年 | 729篇 |
2008年 | 676篇 |
2007年 | 717篇 |
2006年 | 622篇 |
2005年 | 471篇 |
2004年 | 442篇 |
2003年 | 420篇 |
2002年 | 353篇 |
2001年 | 352篇 |
2000年 | 325篇 |
1999年 | 269篇 |
1998年 | 283篇 |
1997年 | 220篇 |
1996年 | 223篇 |
1995年 | 156篇 |
1994年 | 117篇 |
1993年 | 115篇 |
1992年 | 80篇 |
1991年 | 76篇 |
1990年 | 60篇 |
1989年 | 52篇 |
1988年 | 52篇 |
1987年 | 39篇 |
1986年 | 52篇 |
1985年 | 33篇 |
1984年 | 47篇 |
1983年 | 17篇 |
1982年 | 27篇 |
1981年 | 29篇 |
1980年 | 20篇 |
1979年 | 25篇 |
1978年 | 41篇 |
1977年 | 41篇 |
1976年 | 40篇 |
1975年 | 15篇 |
1974年 | 15篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
981.
Martí S Andrés J Moliner V Silla E Tuñón I Bertrán J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(4):984-991
In this paper a deeper insight into the chorismate-to prephenate-rearrangement, catalyzed by Bacillus subtilis chorismate mutase, is provided by means of a combination of statistical quantum mechanics/molecular mechanics simulation methods and hybrid potential energy surface exploration techniques. The main aim of this work is to present an estimation of the preorganization and reorganization terms of the enzyme catalytic rate enhancement. To analyze the first of these, we have studied different conformational equilibria of chorismate in aqueous solution and in the enzyme active site. Our conclusion is that chorismate mutase preferentially binds the reactive conformer of the substrate--that presenting a structure similar to the transition state of the reaction to be catalyzed--with shorter distances between the carbon atoms to be bonded and more diaxial character. With respect to the reorganization effect, an energy decomposition analysis of the potential energies of the reactive reactant and of the reaction transition state in aqueous solution and in the enzyme shows that the enzyme structure is better adapted to the transition structure. This means not only a more negative electrostatic interaction energy with the transition state but also a low enzyme deformation contribution to the energy barrier. Our calculations reveal that the structure of the enzyme is responsible for stabilizing the transition state structure of the reaction, with concomitant selection of the reactive form of the reactants. This is, the same enzymatic pattern that stabilizes the transition structure also promotes those reactant structures closer to the transition structure (i.e., the reactive reactants). In fact, both reorganization and preorganization effects have to be considered as the two faces of the same coin, having a common origin in the effect of the enzyme structure on the energy surface of the substrate. 相似文献
982.
The palladium-catalyzed cyclization–allylation reaction of ortho-azido propynylbenzenes 1 and allyl methyl carbonate 2d gives the corresponding allylated quinolines in moderate to good yields. The reaction of 1-azido-2-(2-propynyl)benzene 1a proceeds smoothly with 10 mol % Pd(PPh3)4 and 5 equiv K3PO4 or NaOAc in DMF at 100 °C to afford 3,4-diallylquinoline 3a in 69% yield in the case of R2 = H and 3-allylquinoline 4 in 67% yield in the case of R2 ≠ H. 相似文献
983.
Venkatanarayana Pappula Ramachandra Reddy DonthiriChandra Mohan Darapaneni Adimurthy Subbarayappa 《Tetrahedron letters》2014
Synthesis of β-bromostyrenes from styrene bromohydrins using H-β-zeolite as catalyst under moderate conditions is reported. The catalyst could be regenerated and reused up to three consecutive cycles. 相似文献
984.
多溴联苯的污染来源、分析方法和环境污染特征 总被引:1,自引:0,他引:1
多溴联苯(polybrominated biphenyls,PBBs)是一类曾被广泛使用的溴代阻燃剂,这类化学物质具有半挥发性,能够远距离迁移,可在环境中持久存在,并且能够在生物体内累积和放大,对全球环境和人类健康构成潜在的危害。2009年,《关于持久性有机污染物的斯德哥尔摩公约》新POPs审查委员会将六溴联苯商业产品列入其附件A,禁止六溴联苯的工业生产和使用。因此,近期对环境中多溴联苯的来源、分析方法和污染水平等相关研究引起了广泛的关注。本文介绍了PBBs的基本理化性质和毒性,对作为溴代阻燃剂的PBBs的生产量进行归纳,并提出需要开展深入和广泛研究来认识是否在工业生产过程中存在PBBs的非故意生成和排放,对当前环境中PBBs的分析方法进行了总结,并对PBBs当前的环境污染水平和污染特征进行了简要概述,最后对PBBs相关的未来研究进行了初步展望。 相似文献
985.
Inside Cover: Rational Design of Carboxyl Groups Perpendicularly Attached to a Graphene Sheet: A Platform for Enhanced Biosensing Applications (Chem. Eur. J. 1/2014) 下载免费PDF全文
986.
1,10‐Phenanthroline and Non‐Symmetrical 1,3,5‐Triazine Dipicolinamide‐Based Ligands For Group Actinide Extraction 下载免费PDF全文
Dr. Julia Bisson Dr. Jérémy Dehaudt Dr. Marie‐Christine Charbonnel Dr. Denis Guillaneux Dr. Manuel Miguirditchian Dr. Cécile Marie Nathalie Boubals Guy Dutech Dr. Muriel Pipelier Dr. Virginie Blot Prof. Didier Dubreuil 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7819-7829
The synthesis and evaluation of new extractants for spent nuclear fuel reprocessing are described. New bitopic ligands constituted of phenanthroline and 1,3,5‐triazine cores functionalized by picolinamide groups were designed. Synthetic routes were investigated and optimized to obtain twelve new polyaza‐heterocyclic ligands. In particular, an efficient and versatile methodology was developed to access non‐symmetric 2‐substituted‐4,6‐di(6‐picolin‐2‐yl)‐1,3,5‐triazines from the 1,3,5‐triazapentadiene precursor in the presence of anhydride reagents. Extraction studies showed the ability of both ligand series to extract and separate actinides selectively at different oxidation states (UVI, NpV,VI, AmIII, CmIII, and PuIV) from an acidic solution (3 M HNO3). Phenanthroline‐based ligands show the most promising efficiency for use in the group actinide extraction (GANEX) process due to a higher number of donor nitrogen atoms and a suitable pre‐organization of the dipicolinamide‐1,10‐phenanthroline architecture. 相似文献
987.
Stereoelectronic Basis for the Kinetic Resolution of N‐Heterocycles with Chiral Acylating Reagents 下载免费PDF全文
Sheng‐Ying Hsieh Benedikt Wanner Dr. Philip Wheeler Prof. Dr. André M. Beauchemin Prof. Dr. Tomislav Rovis Prof. Dr. Jeffrey W. Bode 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7228-7231
The kinetic resolution of N‐heterocycles with chiral acylating agents reveals a previously unrecognized stereoelectronic effect in amine acylation. Combined with a new achiral hydroxamate, this effect makes possible the resolution of various N‐heterocycles by using easily prepared reagents. A transition‐state model to rationalize the stereochemical outcome of this kinetic resolution is also proposed. 相似文献
988.
Air‐Stable Solid Aryl and Heteroaryl Organozinc Pivalates: Syntheses and Applications in Organic Synthesis 下载免费PDF全文
Sophia M. Manolikakes Mario Ellwart Dr. Christos I. Stathakis Prof. Dr. Paul Knochel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(38):12289-12297
A wide range of air‐stable, solid, polyfunctional aryl and heteroarylzinc pivalates were efficiently prepared by either magnesium insertion or Hal/Mg exchange followed by transmetalation with Zn(OPiv)2 (OPiv=pivalate). By reducing the amount of LiCl the air stability could be significantly enhanced compared with previously prepared reagents. An alternative route is directed magnesiation using TMPMgCl ? LiCl (TMP=2,2,6,6‐tetramethylpiperidyl) followed by transmetalation with Zn(OPiv)2 or, for very sensitive substrates, direct zincation by using TMPZnOPiv. These zinc reagents not only show excellent stability towards air, but they also undergo a broad range of C?C bond‐formation reactions, such as allylation and carbocupration reactions, as well as addition to aldehydes and 1,4‐addition reactions. Acylation reactions can be performed by using an excess of TMSCl to overcome side reactions of the omnipresent pivalate anion. 相似文献
989.
Development of a New Benzylating Reagent Spontaneously Releasing Benzyl Cation Equivalents at Room Temperature 下载免费PDF全文
Dr. Kohei Yamada Yuichi Tsukada Yukiko Karuo Dr. Masanori Kitamura Prof. Dr. Munetaka Kunishima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(38):12274-12278
A new O‐benzylating reagent, that is, 4‐(4,6‐diphenoxy‐1,3,5‐triazin‐2‐yl)‐4‐benzylmorpholinium trifluoromethanesulfonate (DPT‐BM), has been developed. Benzyl cation equivalents are generated from DPT‐BM by dissolving the compound in a solvent at room temperature under non‐acidic conditions. The benzylation of various alcohols by using a combination of DPT‐BM and magnesium oxide provided the benzyl ethers in good yields. 相似文献
990.
Design of Ratiometric Fluorescent Probes Based on Arene–Metal‐Ion Interactions and Their Application to CdII and Hydrogen Sulfide Imaging in Living Cells 下载免费PDF全文
Ippei Takashima Miyuki Kinoshita Ryosuke Kawagoe Saika Nakagawa Prof. Dr. Manabu Sugimoto Prof. Dr. Itaru Hamachi Prof. Dr. Akio Ojida 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2184-2192
Non‐coordinative interactions between a metal ion and the aromatic ring of a fluorophore can act as a versatile sensing mechanism for the detection of metal ions with a large emission change of fluorophores. We report the design of fluorescent probes based on arene–metal‐ion interactions and their biological applications. This study found that various probes having different fluorophores and metal binding units displayed significant emission redshift upon complexation with metal ions, such as AgI, CdII, HgII, and PbII. X‐ray crystallography of the complexes confirmed that the metal ions were held in close proximity to the fluorophore to form an arene–metal‐ion interaction. Electronic structure calculations based on TDDFT offered a theoretical basis for the sensing mechanism, thus showing that metal ions electrostatically modulate the energy levels of the molecular orbitals of the fluorophore. A fluorescent probe was successfully applied to the ratiometric detection of the uptake of CdII ions and hydrogen sulfide (H2S) in living cells. These results highlight the utility of interactions between arene groups and metal ions in biological analyses. 相似文献