全文获取类型
收费全文 | 546篇 |
免费 | 15篇 |
专业分类
化学 | 372篇 |
晶体学 | 2篇 |
力学 | 24篇 |
数学 | 85篇 |
物理学 | 78篇 |
出版年
2023年 | 3篇 |
2022年 | 8篇 |
2021年 | 25篇 |
2020年 | 17篇 |
2019年 | 16篇 |
2018年 | 12篇 |
2017年 | 10篇 |
2016年 | 12篇 |
2015年 | 18篇 |
2014年 | 15篇 |
2013年 | 20篇 |
2012年 | 32篇 |
2011年 | 28篇 |
2010年 | 20篇 |
2009年 | 30篇 |
2008年 | 32篇 |
2007年 | 38篇 |
2006年 | 31篇 |
2005年 | 25篇 |
2004年 | 21篇 |
2003年 | 10篇 |
2002年 | 15篇 |
2001年 | 5篇 |
2000年 | 3篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1996年 | 7篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1992年 | 4篇 |
1991年 | 4篇 |
1990年 | 3篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1984年 | 6篇 |
1983年 | 6篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1975年 | 2篇 |
1974年 | 7篇 |
1973年 | 3篇 |
1972年 | 3篇 |
1971年 | 4篇 |
1968年 | 2篇 |
排序方式: 共有561条查询结果,搜索用时 31 毫秒
21.
Juan Saulo Gonzlez‐Gonzlez Itzia I. Padilla‐Martínez Efrn V. García‐Bez Olivia Franco‐Hernndez Francisco J. Martínez‐Martínez 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(1):66-69
In the title compound, C24H36N6O6·C2H6OS, the carbonyl groups are in an antiperiplanar conformation, with O=C—C=O torsion angles of 178.59 (15) and −172.08 (16)°. An intramolecular hydrogen‐bonding pattern is depicted by four N—H...O interactions, which form two adjacent S(5)S(5) motifs, and an N—H...N interaction, which forms an S(6) ring motif. Intermolecular N—H...O hydrogen bonding and C—H...O soft interactions allow the formation of a meso‐helix. The title compound is the first example of a helical 1,2‐phenylenedioxalamide. The oxalamide traps one molecule of dimethyl sulfoxide through N—H...O hydrogen bonding. C—H...O soft interactions give rise to the two‐dimensional structure. 相似文献
22.
Dr. Nicolas Menard Prof. Dr. Olivia Reinaud Dr. Benoit Colasson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(2):642-653
A biomimetic strategy for the monofunctionalization of a calix[6]arene core is described. It is based on host–guest chemistry (mimicking the Michaelis–Menten adduct in enzymes) and allows the finely tuned pre‐organization of the substrate (an alkyne) with respect to the reactant (three azido groups introduced at the calixarene large rim). It is shown that the thermal Huisgen reaction implemented in this work proceeds under very mild conditions with total regioselectivity of the cycloaddition process. The scope of the reaction was explored and the results suggest that such a supramolecular strategy is quite versatile and could be applied to the selective functionalization of other cavitands bearing different recognition patterns. A detailed structural, thermodynamic, and kinetic study is also reported, highlighting interesting biomimetic features: The importance of the host–guest adduct strength, the high sensitivity of the reaction to the pre‐organization of the reactive partners (alkyne vs. azide), and a significant impact of the embedment on the transition state. The self‐coordination of the monofunctionalized products was also studied and an “endo/exo” switch of the internal side‐chain could be triggered by adding competitive ligands. 相似文献
23.
Rosana A. Gonalves Rosimara P. Toledo Nirav Joshi Olivia M. Berengue 《Molecules (Basel, Switzerland)》2021,26(8)
Over the last two decades, oxide nanostructures have been continuously evaluated and used in many technological applications. The advancement of the controlled synthesis approach to design desired morphology is a fundamental key to the discipline of material science and nanotechnology. These nanostructures can be prepared via different physical and chemical methods; however, a green and ecofriendly synthesis approach is a promising way to produce these nanostructures with desired properties with less risk of hazardous chemicals. In this regard, ZnO and TiO2 nanostructures are prominent candidates for various applications. Moreover, they are more efficient, non-toxic, and cost-effective. This review mainly focuses on the recent state-of-the-art advancements in the green synthesis approach for ZnO and TiO2 nanostructures and their applications. The first section summarizes the green synthesis approach to synthesize ZnO and TiO2 nanostructures via different routes such as solvothermal, hydrothermal, co-precipitation, and sol-gel using biological systems that are based on the principles of green chemistry. The second section demonstrates the application of ZnO and TiO2 nanostructures. The review also discusses the problems and future perspectives of green synthesis methods and the related issues posed and overlooked by the scientific community on the green approach to nanostructure oxides. 相似文献
24.
Karen Rodríguez-Villar Lilin Ypez-Mulia Miguel Corts-Gines Jacobo David Aguilera-Perdomo Edgar A. Quintana-Salazar Kevin Samael Olascoaga Del Angel Francisco Corts-Benítez Juan Francisco Palacios-Espinosa Olivia Soria-Arteche Jaime Prez-Villanueva 《Molecules (Basel, Switzerland)》2021,26(8)
Indazole is an important scaffold in medicinal chemistry. At present, the progress on synthetic methodologies has allowed the preparation of several new indazole derivatives with interesting pharmacological properties. Particularly, the antiprotozoal activity of indazole derivatives have been recently reported. Herein, a series of 22 indazole derivatives was synthesized and studied as antiprotozoals. The 2-phenyl-2H-indazole scaffold was accessed by a one-pot procedure, which includes a combination of ultrasound synthesis under neat conditions as well as Cadogan’s cyclization. Moreover, some compounds were derivatized to have an appropriate set to provide structure-activity relationships (SAR) information. Whereas the antiprotozoal activity of six of these compounds against E. histolytica, G. intestinalis, and T. vaginalis had been previously reported, the activity of the additional 16 compounds was evaluated against these same protozoa. The biological assays revealed structural features that favor the antiprotozoal activity against the three protozoans tested, e.g., electron withdrawing groups at the 2-phenyl ring. It is important to mention that the indazole derivatives possess strong antiprotozoal activity and are also characterized by a continuous SAR. 相似文献
25.
Jean Claude Didelot Tomani Olivier Bonnet Alain Nyirimigabo William Deschamps Alembert Tiabou Tchinda Olivia Jansen Allison Ledoux Marie Jeanne Mukazayire Luc Vanhamme Michel Frdrich Raymond Muganga Jacob Souopgui 《Molecules (Basel, Switzerland)》2021,26(9)
Malaria remains one of the leading causes of death in sub-Saharan Africa, ranked in the top three infectious diseases in the world. Plants of the Eriosema genus have been reported to be used for the treatment of this disease, but scientific evidence is still missing for some of them. In the present study, the in vitro antiplasmodial activity of the crude extract and compounds from Eriosema montanum Baker f. roots were tested against the 3D7 strain of Plasmodium falciparum and revealed using the SYBR Green, a DNA intercalating compound. The cytotoxicity effect of the compounds on a human cancer cell line (THP-1) was assessed to determine their selectivity index. It was found that the crude extract of the plant displayed a significant antiplasmodial activity with an IC50 (µg/mL) = 17.68 ± 4.030 and a cytotoxic activity with a CC50 (µg/mL) = 101.5 ± 12.6, corresponding to a selective antiplasmodial activity of 5.7. Bioactivity-guided isolation of the major compounds of the roots’ crude extract afforded seven compounds, including genistein, genistin and eucomic acid. Under our experimental conditions, using Artemisinin as a positive control, eucomic acid showed the best inhibitory activity against the P. falciparum 3D7, a well-known chloroquine-sensitive strain. The present results provide a referential basis to support the traditional use of Eriosema species in the treatment of malaria. 相似文献
26.
Picolinamides as Effective Ligands for Copper‐Catalysed Aryl Ether Formation: Structure–Activity Relationships,Substrate Scope and Mechanistic Investigations 下载免费PDF全文
Carlo Sambiagio Dr. Rachel H. Munday Prof. Stephen P. Marsden Prof. A. John Blacker Dr. Patrick C. McGowan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(52):17606-17615
The use of picolinic acid amide derivatives as an effective family of bidentate ligands for copper‐catalysed aryl ether synthesis is reported. A fluorine‐substituted ligand gave good results in the synthesis of a wide range of aryl ethers. Even bulky phenols, known to be very challenging substrates, were shown to react with aryl iodides with excellent yields using these ligands. At the end of the reaction, the first examples of end‐of‐life Cu species were isolated and identified as CuII complexes with several of the anionic ligands tested. A preliminary mechanistic investigation is reported that suggests that the substituents on the ligands might have a crucial role in determining the redox properties of the metal centre and, consequently, its efficacy in the coupling process. An understanding of these effects is important for the development of new efficient and tunable ligands for copper‐based chemistry. 相似文献
27.
Helen R. Thomas Alexander J. Marsden Dr. Marc Walker Dr. Neil R. Wilson Dr. Jonathan P. Rourke 《Angewandte Chemie (International ed. in English)》2014,53(29):7613-7618
The treatment of graphene oxide (GO) with potassium thioacetate followed by an aqueous work‐up yields a new material via the ring‐opening of the epoxide groups. The new material is a thiol‐functionalized GO (GO‐SH) which is able to undergo further functionalization. Reaction with butyl bromide gives another new material, GO‐SBu, which shows significantly enhanced thermal stability compared to both GO and GO‐SH. The thiol‐functionalized GO material showed a high affinity for gold, as demonstrated by the selective deposition of a high density of gold nanoparticles. 相似文献
28.
Xavier Cattoën Achraf Noureddine Jonas Croissant Nirmalya Moitra Kristýna Bürglová Jana Hodačová Olivia de los Cobos Martine Lejeune Fabrice Rossignol Delphine Toulemon Sylvie Bégin-Colin Benoît P. Pichon Laurence Raehm Jean-Olivier Durand Michel Wong Chi Man 《Journal of Sol-Gel Science and Technology》2014,70(2):245-253
The combination of the copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction with sol–gel processing enables the versatile preparation of sol–gel materials under different shapes with targeted functionalities through a diversity-oriented approach. In this account, the development of the CuAAC reaction under anhydrous conditions for the synthesis of sol–gel precursors and for the assembling of magnetic nanoparticles on self-assembled monolayers is related, as well as the use of the classical CuAAC methodologies for the functionalization of mesoporous silica nanoparticles and microdots arrays. Coupling CuAAC and Sol–Gel will result in simplified preparations of multifunctional materials with controlled morphologies. 相似文献
29.
Guangcan Xu Sbastien Leloux Pinglu Zhang Jorge Meijide Surez Yongmin Zhang Etienne Derat Mickaël Mnand Olivia Bistri‐Aslanoff Sylvain Roland Tom Leyssens Olivier Riant Matthieu Sollogoub 《Angewandte Chemie (International ed. in English)》2020,59(19):7591-7597
The encapsulation of copper inside a cyclodextrin capped with an N‐heterocyclic carbene (ICyD) allowed both to catch the elusive monomeric (L)CuH and a cavity‐controlled chemoselective copper‐catalyzed hydrosilylation of α,β‐unsaturated ketones. Remarkably, (α‐ICyD)CuCl promoted the 1,2‐addition exclusively, while (β‐ICyD)CuCl produced the fully reduced product. The chemoselectivity is controlled by the size of the cavity and weak interactions between the substrate and internal C?H bonds of the cyclodextrin. 相似文献
30.
We describe the development, fabrication, and characterization of a novel two‐electrode nanosensor contained within the tip of a needle‐like probe. This sensor consists of two, vertically aligned, carbon structures which function as individual electrodes. One of the carbon structures was modified by silver electrodeposition and chlorination to enable it to function as a pseudo‐reference electrode. Performance of this pseudo‐reference electrode was found to be comparable to that of commercially available Ag/AgCl reference electrodes. The unmodified carbon structure was employed as a working electrode versus the silver‐plated carbon structure to form a two‐electrode sensor capable of characterizing redox‐active analytes. The nanosensor was demonstrated to be capable of electrochemically characterizing the redox behavior of para‐aminophenol (PAP) in both bulk solutions and microenvironments. PAP was also measured in cell lysate to show that the nanosensor can detect small concentrations of analyte in heterogenous environments. As the working and reference electrodes are contained within a single nanoprobe, there was no requirement to position external electrodes within the electrochemical cell enabling analysis within very small domains. Due to the low‐cost manufacturing process, this nanoprobe has the potential to become a unique and widely accessible tool for the electrochemical characterization of microenvironments. 相似文献