全文获取类型
收费全文 | 2659篇 |
免费 | 113篇 |
国内免费 | 22篇 |
专业分类
化学 | 1718篇 |
晶体学 | 15篇 |
力学 | 107篇 |
数学 | 491篇 |
物理学 | 463篇 |
出版年
2023年 | 24篇 |
2022年 | 29篇 |
2021年 | 54篇 |
2020年 | 60篇 |
2019年 | 61篇 |
2018年 | 58篇 |
2017年 | 42篇 |
2016年 | 89篇 |
2015年 | 84篇 |
2014年 | 105篇 |
2013年 | 174篇 |
2012年 | 199篇 |
2011年 | 268篇 |
2010年 | 126篇 |
2009年 | 110篇 |
2008年 | 169篇 |
2007年 | 143篇 |
2006年 | 144篇 |
2005年 | 120篇 |
2004年 | 101篇 |
2003年 | 91篇 |
2002年 | 66篇 |
2001年 | 49篇 |
2000年 | 29篇 |
1999年 | 29篇 |
1998年 | 20篇 |
1997年 | 26篇 |
1996年 | 35篇 |
1995年 | 13篇 |
1994年 | 20篇 |
1993年 | 23篇 |
1992年 | 14篇 |
1991年 | 7篇 |
1990年 | 14篇 |
1989年 | 10篇 |
1988年 | 10篇 |
1987年 | 8篇 |
1986年 | 6篇 |
1985年 | 15篇 |
1984年 | 9篇 |
1983年 | 8篇 |
1982年 | 9篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1978年 | 13篇 |
1976年 | 7篇 |
1973年 | 9篇 |
1972年 | 6篇 |
1970年 | 6篇 |
1942年 | 6篇 |
排序方式: 共有2794条查询结果,搜索用时 31 毫秒
101.
Supramolecular Complexes of Multivalent Cholesterol‐Containing Polymers to Solubilize Carbon Nanotubes in Apolar Organic Solvents 下载免费PDF全文
Jules Zeuna Nguendia Weiheng Zhong Alexandre Fleury Guillaume De Grandpré Prof. Armand Soldera Prof. Ribal Georges Sabat Prof. Jerome P. Claverie 《化学:亚洲杂志》2014,9(5):1356-1364
Copolymers of 2‐ethylhexyl acrylate (EHA) and cholesteryloxycarbonyl‐2‐hydroxymethacrylate (CEM) were prepared by reversible addition–fragmentation chain‐transfer (RAFT) polymerization. Supramolecular complexes of these copolymers with carbon nanotubes (CNTs) were soluble in THF, toluene, and isooctane. The colloidal solutions remained stable for months without aggregation. The rationale for the choice of CEM was based on the high adsorption energy of cholesterol on the CNT surface, as computed by DFT calculations. Adsorption isotherms were experimentally measured for copolymers of various architectures (statistical, diblock, and star copolymers), thereby demonstrating that 2–5 cholesterol groups were adsorbed per polymer chain. Once the supramolecular complex had dried, the CNTs could be easily resolubilized in isooctane without the need for high‐power sonication and in the absence of added polymer. Analysis by atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) indicated that the CNTs were devoid of bundles. The supramolecular complexes could also be employed in an inverse emulsion polymerization of 2‐hydroxyethylmethacrylate (HEMA) in isooctane and dodecane, thereby leading to the formation of a continuous polymeric sheath around the CNTs. Thus, this technique leads to the formation of very stable dispersions in non‐polar organic solvents, without altering the fundamental properties of the CNTs. 相似文献
102.
Matteo Velenosi Pasquale Crupi Rocco Perniola Antonio Domenico Marsico Antonella Salerno Herv Alexandre Nicoletta Archidiacono Mario Ventura Maria Francesca Cardone 《Molecules (Basel, Switzerland)》2021,26(4)
Mixed fermentation using Starmerella bacillaris and Saccharomyces cerevisiae has gained attention in recent years due to their ability to modulate the qualitative parameters of enological interest, such as the color intensity and stability of wine. In this study, three of the most important red Apulian varieties were fermented through two pure inoculations of Saccharomyces cerevisiae strains or the sequential inoculation of Saccharomyces cerevisiae after 48 h from Starmerella bacillaris. The evolution of anthocyanin profiles and chromatic characteristics were determined in the produced wines at draining off and after 18 months of bottle aging in order to assess the impact of the different fermentation protocols on the potential color stabilization and shelf-life. The chemical composition analysis showed titratable acidity and ethanol content exhibiting marked differences among wines after fermentation and aging. The 48 h inoculation delay produced wines with higher values of color intensity and color stability. This was ascribed to the increased presence of compounds, such as stable A-type vitisins and reddish/violet ethylidene-bridge flavonol-anthocyanin adducts, in the mixed fermentation. Our results proved that the sequential fermentation of Starmerella bacillaris and Saccharomyces cerevisiae could enhance the chromatic profile as well as the stability of the red wines, thus improving their organoleptic quality. 相似文献
103.
Yuen Cheong Tse Dr. Robert Hein Edward J. Mitchell Zongyao Zhang Prof. Paul D. Beer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(58):14550-14559
Anion receptors employing two distinct sensory mechanisms are rare. Herein, we report the first examples of halogen-bonding porphyrin BODIPY [2]rotaxanes capable of both fluorescent and redox electrochemical sensing of anions. 1H NMR, UV/visible and electrochemical studies revealed rotaxane axle triazole group coordination to the zinc(II) metalloporphyrin-containing macrocycle component, serves to preorganise the rotaxane binding cavity and dramatically enhances anion binding affinities. Mechanically bonded, integrated-axle BODIPY and macrocycle strapped metalloporphyrin motifs enable the anion recognition event to be sensed by the significant quenching of the BODIPY fluorophore and cathodic perturbations of the metalloporphyrin P/P+. redox couple. 相似文献
104.
105.
Dr. Nicholas H. Evans Prof. Paul D. Beer 《Angewandte Chemie (International ed. in English)》2014,53(44):11716-11754
Since the start of this millennium, remarkable progress in the binding and sensing of anions has been taking place, driven in part by discoveries in the use of hydrogen bonding, as well as the previously under‐exploited anion–π interactions and halogen bonding. However, anion supramolecular chemistry has developed substantially beyond anion recognition, and now encompasses a diverse range of disciplines. Dramatic advance has been made in the anion‐templated synthesis of macrocycles and interlocked molecular architectures, while the study of transmembrane anion transporters has flourished from almost nothing into a rapidly maturing field of research. The supramolecular chemistry of anions has also found real practical use in a variety of applications such as catalysis, ion extraction, and the use of anions as stimuli for responsive chemical systems. 相似文献
106.
Synthesis of Highly Functionalized Diaryl Ethers by Copper‐Mediated O‐Arylation of Phenols using Trivalent Arylbismuth Reagents 下载免费PDF全文
Cynthia Crifar Pauline Petiot Tabinda Ahmad Prof. Alexandre Gagnon 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(10):2755-2760
Highly functionalized diaryl ethers were prepared by copper(II) acetate mediated O‐arylation reaction of phenols using trivalent organobismuthanes. The reaction is performed under simple conditions and tolerates a wide diversity of functional groups on the phenol and on the organobismuth reagent. Substoichiometric amounts of catalyst can be used by performing the reaction under an oxygen atmosphere. The N‐arylation of pyridones is also reported. 相似文献
107.
Halotriazolium Axle Functionalised [2]Rotaxanes for Anion Recognition: Investigating the Effects of Halogen‐Bond Donor and Preorganisation 下载免费PDF全文
James M. Mercurio Richard C. Knighton Dr. James Cookson Prof. Paul D. Beer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(37):11740-11749
The anion‐templated synthesis of three novel halogen‐bonding 5‐halo‐1,2,3‐triazolium axle containing [2]rotaxanes is described, and the effects of altering the nature of the halogen‐bond donor atom together with the degree of inter‐component preorganisation on the anion‐recognition properties of the interlocked host investigated. The ability of the bromotriazolium motif to direct the halide‐anion‐templated assembly of interpenetrated [2]pseudorotaxanes was studied initially; bromide was found to be the most effective template. As a consequence, bromide anion templation was used to synthesise the first bromotriazolium axle containing [2]rotaxane, the anion‐binding properties of which, determined by 1H NMR spectroscopic titration experiments, revealed enhanced bromide and iodide recognition relative to a hydrogen‐bonding protic triazolium rotaxane analogue. Two halogen‐bonding [2]rotaxanes with bromo‐ and iodotriazolium motifs integrated into shortened axles designed to increase inter‐component preorganisation were also synthesised. Anion 1H NMR spectroscopic titration experiments demonstrated that these rotaxanes were able to bind halide anions even more strongly, with the iodotriazolium axle integrated rotaxane capable of recognising halides in aqueous solvent media. Importantly, these observations suggest that a halogen‐bonding interlocked host binding domain, in combination with increased inter‐component preorganisation, are requisite design features for a potent anion receptor. 相似文献
108.
Copper‐Catalyzed Propargylic Substitution of Dichloro Substrates: Enantioselective Synthesis of Trisubstituted Allenes and Formation of Propargylic Quaternary Stereogenic Centers 下载免费PDF全文
Dr. Hailing Li Dr. David Grassi Dr. Laure Guénée Prof. Dr. Thomas Bürgi Prof. Dr. Alexandre Alexakis 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16694-16706
An easy and versatile Cu‐catalyzed propargylic substitution process is presented. Using easily prepared prochiral dichloro substrates, readily available Grignard reagents together with catalytic amount of copper salt and chiral ligand, we accessed a range of synthetically interesting trisubstituted chloroallenes. Substrate scope and nucleophile scope are broad, providing generally high enantioselectivity for the desired 1,3‐substitution products. The enantioenriched chloroallenes could be further transformed into the corresponding trisubstituted allenes or terminal alkynes bearing all‐carbon quaternary stereogenic centers, through the copper‐catalyzed enantiospecific 1,1/1,3‐substitutions. The two successive copper‐catalyzed reactions could be eventually combined into a one‐pot procedure and different desired allenes or alkynes were obtained respectively with high enantiomeric excesses. 相似文献
109.
From Enantiopure Hydroxyaldehydes to Complex Heterocyclic Scaffolds: Development of Domino Petasis/Diels–Alder and Cross‐Metathesis/Michael Addition Reactions 下载免费PDF全文
Dr. Alexandre Cannillo Dr. Stéphanie Norsikian Dr. Marie‐Elise Tran Huu Dau Dr. Pascal Retailleau Dr. Bogdan I. Iorga Prof. Jean‐Marie Beau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(38):12133-12143
One‐step assembly of hexahydroisoindole scaffolds by a sequence that combines the Petasis (borono‐Mannich) and Diels–Alder reactions is described. The unique selectivity observed experimentally was confirmed by quantum calculations. The current method is applicable to a broad range of substrates, including free sugars, and holds significant potential to efficiently and stereoselectively build new heterocyclic structures. This easy and fast entry to functionalized polycyclic compounds can be pursued by further transformations, for example, additional ring closure by a cross‐metathesis/Michael addition domino sequence. 相似文献
110.