全文获取类型
收费全文 | 34683篇 |
免费 | 8214篇 |
国内免费 | 1392篇 |
专业分类
化学 | 39799篇 |
晶体学 | 307篇 |
力学 | 412篇 |
数学 | 1762篇 |
物理学 | 2009篇 |
出版年
2023年 | 1篇 |
2022年 | 2篇 |
2021年 | 134篇 |
2020年 | 1206篇 |
2019年 | 2559篇 |
2018年 | 993篇 |
2017年 | 628篇 |
2016年 | 3339篇 |
2015年 | 3494篇 |
2014年 | 3386篇 |
2013年 | 3973篇 |
2012年 | 2826篇 |
2011年 | 2012篇 |
2010年 | 2761篇 |
2009年 | 2738篇 |
2008年 | 2237篇 |
2007年 | 1631篇 |
2006年 | 1330篇 |
2005年 | 1514篇 |
2004年 | 1334篇 |
2003年 | 1234篇 |
2002年 | 1931篇 |
2001年 | 1330篇 |
2000年 | 1255篇 |
1999年 | 336篇 |
1998年 | 27篇 |
1997年 | 23篇 |
1996年 | 4篇 |
1995年 | 3篇 |
1994年 | 8篇 |
1993年 | 4篇 |
1992年 | 3篇 |
1991年 | 5篇 |
1990年 | 1篇 |
1989年 | 7篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1970年 | 1篇 |
1967年 | 1篇 |
1904年 | 1篇 |
1902年 | 1篇 |
1897年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Elemental Sulfur Disproportionation in the Redox Condensation Reaction between o‐Halonitrobenzenes and Benzylamines 下载免费PDF全文
Dr. Thanh Binh Nguyen Dr. Ludmila Ermolenko Dr. Pascal Retailleau Dr. Ali Al‐Mourabit 《Angewandte Chemie (International ed. in English)》2014,53(50):13808-13812
The disproportionation of elemental sulfur at moderate temperatures is investigated in the redox condensation involving o‐halonitrobenzenes 1 and benzylamines 2 . As a redox moderator, elemental sulfur plays the dual role of both electron donor and acceptor, generating its lowest and highest oxidation states: S?2 (sulfide equivalent) in benzothiazole 3 and S+6 (sulfate equivalent) in sulfamate 4 , and filling the electron gap of the global redox condensation process. Along with this process, a cascade of reactions of reduction of the nitro group of 1 , oxidation of the aminomethyl group of 2 , metal‐free aromatic halogen substitution, and condensation finally led to 2‐arylbenzothiazoles 3 . 相似文献
992.
Marcileia Zanatta Dr. Anne‐Lise Girard Nathalia M. Simon Prof. Gunter Ebeling Prof. Hubert K. Stassen Prof. Paolo R. Livotto Prof. Francisco P. dos Santos Prof. Jairton Dupont 《Angewandte Chemie (International ed. in English)》2014,53(47):12817-12821
1‐n‐Butyl‐2,3‐dimethylimidazolium (BMMI) ionic liquids (ILs) associated with different anions undergo H/D exchange preferentially at 2‐Me group of the imidazolium in deuterated solvents. This process is mainly related to the existence of ion pairs rather than the anion basicity. The H/D exchange occurs in solvents (CDCl3 and MeCN for instance) in which intimate contact ion pairs are present and the anion possesses a labile H in its structure, such as hydrogen carbonate and prolinate. In D2O, separated ion pairs are formed and the H/D exchange does not occur. A plausible catalytic cycle is that the IL behaves as a neutral base in the course of all H/D exchange processes. NMR experiments, density functional calculations, and molecular dynamics simulations corroborate these hypotheses. 相似文献
993.
Simultaneous In Situ Quantification of Two Cellular Lipid Pools Using Orthogonal Fluorescent Sensors 下载免费PDF全文
Dr. Shu‐Lin Liu Dr. Ren Sheng Matthew J. O'Connor Yang Cui Dr. Youngdae Yoon Svetlana Kurilova Dr. Daesung Lee Dr. Wonhwa Cho 《Angewandte Chemie (International ed. in English)》2014,53(52):14387-14391
Lipids regulate a wide range of biological activities. Since their local concentrations are tightly controlled in a spatiotemporally specific manner, the simultaneous quantification of multiple lipids is essential for elucidation of the complex mechanisms of biological regulation. Here, we report a new method for the simultaneous in situ quantification of two lipid pools in mammalian cells using orthogonal fluorescent sensors. The sensors were prepared by incorporating two environmentally sensitive fluorophores with minimal spectral overlap separately into engineered lipid‐binding proteins. Dual ratiometric analysis of imaging data allowed accurate, spatiotemporally resolved quantification of two different lipids on the same leaflet of the plasma membrane or a single lipid on two opposite leaflets of the plasma membrane of live mammalian cells. This new imaging technology should serve as a powerful tool for systems‐level investigation of lipid‐mediated cell signaling and regulation. 相似文献
994.
Frontispiece: Engineering Catalyst Microenvironments for Metal‐Catalyzed Hydrogenation of Biologically Derived Platform Chemicals 下载免费PDF全文
995.
Dr. Cheng‐Hsien Wu Matthew T. Holden Prof. Lloyd M. Smith 《Angewandte Chemie (International ed. in English)》2014,53(49):13514-13517
A powerful new strategy for the fabrication of high‐density RNA arrays is described. A high‐density DNA array is fabricated by standard photolithographic methods, the surface‐bound DNA molecules are enzymatically copied into their RNA complements from a surface‐bound RNA primer, and the DNA templates are enzymatically destroyed, leaving behind the desired RNA array. The strategy is compatible with 2′‐fluoro‐modified (2′F) ribonucleoside triphosphates (rNTPs), which may be included in the polymerase extension reaction to impart nuclease resistance and other desirable characteristics to the synthesized RNAs. The use and fidelity of the arrays are explored with DNA hybridization, DNAzyme cleavage, and nuclease digestion experiments. 相似文献
996.
Frontispiece: NMR Fingerprints of the Drug‐like Natural‐Product Space Identify Iotrochotazine A: A Chemical Probe to Study Parkinson’s Disease 下载免费PDF全文
997.
Dr. Qing‐Fu Sun Dr. Sota Sato Prof. Dr. Makoto Fujita 《Angewandte Chemie (International ed. in English)》2014,53(49):13510-13513
In the self‐assembly of PdII ions and two different, but similarly shaped, ligands ( 1 and 2 ), neither random mixing nor self‐sorting of the two ligands into two unmixed structures was observed. Instead a mixed, yet sorted, Pd12( 1 )12( 2 )12 cantellated tetrahedron (and its pseudoisomer) was selectively formed, thus revealing a fine example of intramolecular self‐sorting. A case study showed that a homothetic ratio of >2 is necessary to observe cantellated tetrahedra. 相似文献
998.
Andrea Kunfermann Matthias Witschel Boris Illarionov Ren Martin Matthias Rottmann H. Wolfgang Hffken Michael Seet Wolfgang Eisenreich Hans‐Joachim Knlker Markus Fischer Adelbert Bacher Michael Groll Franois Diederich 《Angewandte Chemie (International ed. in English)》2014,53(8):2235-2239
The enzymes of the non‐mevalonate pathway for isoprenoid biosynthesis have been identified as attractive targets with novel modes of action for the development of herbicides for crop protection and agents against infectious diseases. This pathway is present in many pathogenic organisms and plants, but absent in mammals. By using high‐throughput screening, we identified highly halogenated marine natural products, the pseudilins, to be inhibitors of the third enzyme, IspD, in the pathway. Their activity against the IspD enzymes from Arabidopsis thaliana and Plasmodium vivax was determined in photometric and NMR‐based assays. Cocrystal structures revealed that pseudilins bind to an allosteric pocket by using both divalent metal ion coordination and halogen bonding. The allosteric mode of action for preventing cosubstrate (CTP) binding at the active site was elucidated. Pseudilins show herbicidal activity in plant assays and antiplasmodial activity in cell‐based assays. 相似文献
999.
Tetracyanoquinodimethane Reduction by Complexed Guanidinyl‐Functionalized Aromatic Compounds 下载免费PDF全文
Hendrik Herrmann Alexandra Ziesak Ute Wild Simone Leingang David Schrempp Norbert Wagner Prof. Dr. Johannes Beck Dr. Elisabeth Kaifer Prof. Dr. Hubert Wadepohl Prof. Dr. Hans‐Jörg Himmel 《Chemphyschem》2014,15(2):351-365
In this work, we report on the reduction of tetracyanoquinodimethane (TCNQ) with dicationic complexes of guanidinyl‐functionalized aromatic (GFA) electron donors. In contrast to reduction with free GFAs, milder reduction conditions were achieved, and this led to semiconducting materials with extended TCNQ π stacking. The charge on the TCNQ units was estimated from the structural data obtained by single‐crystal X‐ray diffraction analysis and from IR spectroscopic data. The electrical conductivity was studied and the activation energy of the semiconducting materials was estimated from the temperature dependence of the conductivity. 相似文献
1000.
Double‐Wall Carbon Nanotube–Porphyrin Supramolecular Hybrid: Synthesis and Photophysical Studies 下载免费PDF全文
Dr. María Vizuete Dr. María J. Gómez‐Escalonilla Prof. José Luis G. Fierro Dr. Pedro Atienzar Prof. Hermenegildo García Prof. Fernando Langa 《Chemphyschem》2014,15(1):100-108
Double‐wall carbon nanotubes (DWCNTs) with pyridyl units covalently attached to the external wall through isoxazolino linkers and carboxylic groups that have been esterified by pentyl chains are synthesized. The properties of these modified DWCNTs are then compared with an analogous sample based on single‐wall carbon nanotubes (SWCNTs). Raman spectroscopy shows the presence of characteristic radial breathing mode vibrations, confirming that the samples partly retain the integrity of the nanotubes in the case of DWCNTs, including the internal and external nanotubes. Quantification of the pyridyl content for both samples (DWCNT and SWCNT derivatives) is based on X‐ray photoelectron spectroscopy and thermogravimetric profiles, showing very similar substituent load. Both pyridyl‐containing nanotubes (DWCNTs and SWCNTs) form a complex with zinc porphyrin (ZnP), as evidenced by the presence of two isosbestic points in the absorption spectra of the porphyrin upon addition of the pyridyl‐functionalized nanotubes. Supramolecular complexes based on pyridyl‐substituted DWCNTs and SWCNTs quench the emission and the triplet excited state identically, through an energy‐transfer mechanism based on pre‐assembly of the ground state. Thus, the presence of the intact inner wall in DWCNTs does not influence the quenching behavior, with respect to SWCNTs, for energy‐transfer quenching with excited ZnP. These results sharply contrast with previous ones referring to electron‐transfer quenching, in which the double‐wall morphology of the nanotubes has been shown to considerably reduce the lifetime of charge separation, owing to faster electron mobility in DWCNTs compared to SWCNTs. 相似文献