全文获取类型
收费全文 | 3805篇 |
免费 | 874篇 |
国内免费 | 488篇 |
专业分类
化学 | 4389篇 |
晶体学 | 43篇 |
力学 | 13篇 |
综合类 | 31篇 |
数学 | 10篇 |
物理学 | 681篇 |
出版年
2024年 | 6篇 |
2023年 | 54篇 |
2022年 | 100篇 |
2021年 | 173篇 |
2020年 | 243篇 |
2019年 | 186篇 |
2018年 | 159篇 |
2017年 | 177篇 |
2016年 | 271篇 |
2015年 | 310篇 |
2014年 | 367篇 |
2013年 | 474篇 |
2012年 | 357篇 |
2011年 | 373篇 |
2010年 | 271篇 |
2009年 | 272篇 |
2008年 | 257篇 |
2007年 | 202篇 |
2006年 | 191篇 |
2005年 | 162篇 |
2004年 | 109篇 |
2003年 | 98篇 |
2002年 | 52篇 |
2001年 | 40篇 |
2000年 | 33篇 |
1999年 | 16篇 |
1998年 | 23篇 |
1997年 | 24篇 |
1996年 | 33篇 |
1995年 | 29篇 |
1994年 | 20篇 |
1993年 | 15篇 |
1992年 | 15篇 |
1991年 | 15篇 |
1990年 | 11篇 |
1989年 | 7篇 |
1988年 | 9篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1979年 | 2篇 |
排序方式: 共有5167条查询结果,搜索用时 31 毫秒
181.
Shashank Tripathi Achu Chandran Tilak Joshi Anil Kumar Ajay Dhar 《Liquid crystals》2013,40(9):1255-1262
In this article, a newly synthesised ferroelectric liquid crystal (FLC) material, namely LAHS 22, has been characterised. The characterisation of the FLC material has been performed using dielectric relaxation spectroscopy, differential scanning calorimetry and polarisation optical microscopy. We observed an enhancement in the dielectric and electro-optical properties of the FLC material by incorporating gold nanoparticles (GNPs)-decorated multiwalled carbon nanotubes (MWCNTs). The GNPs-decorated MWCNTs cause an increment in dielectric dispersion (up to kHz), absorption, spontaneous polarisation and rotational viscosity of the FLC material. The pure and GNPs-decorated MWCNTs doped FLC cells were analysed by means of various dielectric spectroscopic and optical measurements. The observed enhancement in the dielectric and electro-optical properties of the FLC material has also been studied with concentration of GNPs-decorated MWCNTs in FLC material. The GNPs-decorated MWCNTs/FLC composites are not only of fundamental importance, but also useful materials for device applications such as liquid crystal displays and memory devices. 相似文献
182.
J. Albaiges 《International journal of environmental analytical chemistry》2013,93(9):671-680
Inorganic mercury ions (Hg2+) in laboratory prepared solutions were determined with a screen-printed carbon electrode (SPCE) coated with a polyaniline-methylene blue (PANI-MB) polymer layer. The structure and properties of the PANI-MB polymer layer were compared to that of normal polyaniline (PANI) in order to elucidate the structure of the PANI-MB layer. The electrically-conducting polymers were prepared by electrochemical polymerisation of monomer solutions of aniline, and mixed solutions of aniline with methylene blue onto respective screen-printed carbon electrodes (SPCEs). Scanning Electron Microscopy (SEM) analyses of the SPCE polymer coated electrodes have shown that nanostructured materials have formed with the diameters of the PANI nanoclusters and PANI-MB nanorods at approximately 200 nm. Anodic stripping voltammetry (ASV) was used to evaluate a solution composed of 1 × 10?6 M Hg2+, in the presence of the SPCE/PANI-MB polymer sensor electrode. The Hg2+ ions were determined as follows: (i) pre-concentration and reduction on the modified electrode surface and (ii) subsequent stripping from the electrode surface during the positive potential sweep. The experimental conditions optimised for Hg2+ determination included the supporting electrolyte concentration and the accumulation time. The results obtained have shown that the SPCE/PANI-MB polymer sensor electrode operates optimally at a pH 2, with the supporting electrolyte concentration at 0.5 M HCl. A linear calibration curve was found to be in the range of 1 × 10?8 M to 1 × 10?5 M Hg2+ after 120 s of pre-concentration. The detection limit was calculated and found to be 54.27 ± 3.28 µg L?1 of Hg2+. The results have also shown that a conducting polymer modified SPCE sensor electrode can be used as an alternative transducer for the voltammetric stripping and analysis of inorganic Hg2+ ions. 相似文献
183.
Tao Wang Shuai Shi Dr. Mie Højer Vilhelmsen Tuo Zhang Dr. Matthias Rudolph Prof. Dr. A. Stephen K. Hashmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(37):12512-12516
New and chemoselective gold(I)‐catalyzed transformations of 1‐(arylethynyl)‐7‐oxabicyclo[4.1.0]‐ heptan‐2‐ones were developed. Two completely different products—6,7‐dihydrobenzofuran‐4(5H)‐ones and benzofurans—could be obtained from the same starting material. The selectivity is determined by the ligand of the gold catalyst: triphenylphosphine delivers 6,7‐dihydrobenzofuran‐4(5H)‐ones, and 1,3‐bis(diisopropylphenyl)imidazol‐2‐ylidene leads to benzofurans. Eleven examples of each case are provided. The mechanistic suggestions for the pathways to both product types are supported by isotope labeling experiments. 相似文献
184.
Dr. Zhao‐Yang Fei Bo Sun Liang Zhao Prof. Wei‐Jie Ji Prof. Chak‐Tong Au 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(20):6480-6487
Gold nanoparticles (3–4 nm) were deposited on Mn3O4 nanocrystallites with three distinct morphologies (cubic, hexagonal, and octahedral). The resulting structures were characterized, and their activities for benzene combustion were evaluated. The dominant exposed facets for the three kinds of Mn3O4 polyhedrons show the activity order: (103)≈(200)>(101). A similar activity order was derived for the interfaces between the Au and the Mn3O4 facet: Au/(200)≈Au/(103)>Au/(101). The metal–support interactions between the Au nanoclusters and specific facets of the Mn3O4 polyhedrons lead to a unique interfacial synergism in which the electronic modification of the Au nanoparticles and the morphology of the Mn3O4 substrate have a joint effect that is responsible for a significant enhancement in the catalytic activity of the Au/Mn3O4 system. 相似文献
185.
Dr. Tania Lasanta Prof. Dr. José M. López‐de‐Luzuriaga Dr. Miguel Monge Dr. M. Elena Olmos David Pascual 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(15):4754-4766
Heteronuclear complexes {[Hg(R)2][Au(R′)(PMe3)]2}n (R=R′=C6Cl2F3 ( 3 ); R=R′=C6F5 ( 4 ); R=C6Cl2F3, R′=C6F5 ( 5 ); R=C6F5, R′=C6Cl2F3 ( 6 )) were prepared by the treatment of the corresponding organomercury compounds, [Hg(C6X5)2], with two equivalents of [Au(C6X5)(PMe3)]. Their crystal structures, as determined by using X‐ray diffraction methods, display Au???Hg interactions. Although only compound 4 and 5 show luminescence in the solid state, all of these compounds quench the fluorescence of naphthalene in solution. Solution studies of these derivatives suggest a cooperative effect of the gold(I) center in switching on the quenching capabilities of the [Hg(C6X5)2] synthon with naphthalene. Theoretical studies confirmed the quenching ability of the organomercury species in the presence of gold. 相似文献
186.
Akira Kawashima Prof. Dr. Takayuki Nakanishi Prof. Dr. Tamaki Shibayama Prof. Dr. Seiichi Watanabe Prof. Dr. Koji Fujita Prof. Dr. Katsuhisa Tanaka Prof. Dr. Hitoshi Koizumi Prof. Dr. Koji Fushimi Prof. Dr. Yasuchika Hasegawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14438-14445
Remarkable magneto‐optical properties of a new isolator material, that is, europium sulfide nanocrystals with gold (EuS–Au nanosystem), has been demonstrated for a future photo‐information technology. Attachment of gold particles that exhibit surface plasmon resonance leads to amplification of the magneto‐optical properties of the EuS nanocrystals. To construct the EuS–Au nanosystems, cubic EuS and spherical Au nanocrystals have been joined by a variety of organic linkers, that is, 1,2‐ethanedithiol (EDT), 1,6‐hexanedithiol (HDT), 1,10‐decanedithiol (DDT), 1,4‐bisethanethionaphthalene (NpEDT), or 1,4‐bisdecanethionaphthalene (NpDDT) . Formation of these systems was observed by XRD, TEM, and absorption spectra measurements. The magneto‐optical properties of the EuS–Au nanosystem have been characterized by using Faraday rotation spectroscopy. The Faraday rotation angle of the EuS–Au nanosystem is dependent on the Au particle size and interparticle distance between EuS and Au nanocrystals. Enhancement of the Faraday rotation of EuS–Au nanosystems was observed. The spin configuration in the excited state of the EuS–Au nanosystem was also investigated using photo‐assisted electron paramagnetic resonance. 相似文献
187.
Dr. Libo Du Siqingaowa Suo Guangqing Wang Dr. Hongying Jia Prof. Dr. Ke Jian Liu Prof. Dr. Baolu Zhao Prof. Dr. Yang Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1281-1287
The enhanced antioxidant activity of surface‐functionalized gold nanoparticles (AuNPs) synthesized by self‐assembly has attracted great attention, but little is known about the mechanism behind the enhanced activity. To address this challenge, the antioxidant activity of Au@PEG3SA (i.e., surface‐functionalization of spherical AuNPs with the antioxidant salvianic acid A) was used as an example to illustrate the mechanism of the enhanced activity. Evaluation of the antioxidant activity was performed in a radical‐scavenging reaction between Au@PEG3SA and 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) radical. As expected, the rate constant for the reaction of Au@PEG3SA with DPPH was about nine times greater than that for the salvianic acid A monomer. A comparative analysis of the spectral characteristics of Au@PEG3SA and the salvianic acid A monomer further imply that the enhancement of the antioxidative reaction kinetics may be ascribed to the variation in the transition state for the DPPH‐radical scavenging reaction through π–π stacking interactions between and among adjacent groups on the surface of Au@PEG3SA. On the other hand, the kinetic enhancement of Au@PEG3SA on reactive‐oxygen‐species (ROS) scavenging can be observed in living cells and in vivo, which possibly provides new insight for the bioapplication of self‐assembly of surface‐functionalized AuNPs. 相似文献
188.
Xinjian Yang Zhen Liu Zhenhua Li Fang Pu Prof. Dr. Jinsong Ren Prof. Dr. Xiaogang Qu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(31):10388-10394
Hydrophobicity has been an obstacle that hinders the use of many anticancer drugs. A critical challenge for cancer therapy concerns the limited availability of effective biocompatible delivery systems for most hydrophobic therapeutic anticancer drugs. In this study, we have developed a targeted near‐infrared (NIR)‐regulated hydrophobic drug‐delivery platform based on gold nanorods incorporated within a mesoporous silica framework (AuMPs). Upon application of NIR light, the photothermal effect of the gold nanorods leads to a rapid rise in the local temperature, thus resulting in the release of the entrapped drug molecules. By integrating chemotherapy and photothermotherapy into one system, we have studied the therapeutic effects of camptothecin‐loaded AuMP‐polyethylene glycol‐folic acid nanocarrier. Results revealed a synergistic effect in vitro and in vivo, which would make it possible to enhance the therapeutic effect of hydrophobic drugs and decrease drug side effects. Studies have shown the feasibility of using this nanocarrier as a targeted and noninvasive remote‐controlled hydrophobic drug‐delivery system with high spatial/temperal resolution. Owing to these advantages, we envision that this NIR‐controlled, targeted drug‐delivery method would promote the development of high‐performance hydrophobic anticancer drug‐delivery system in future clinical applications. 相似文献
189.
Cristina García‐Simón Marc Garcia‐Borràs Dr. Laura Gómez Dr. Isaac Garcia‐Bosch Dr. Sílvia Osuna Prof. Marcel Swart Dr. Josep M. Luis Prof. Concepció Rovira Prof. Manuel Almeida Dr. Inhar Imaz Prof. Daniel Maspoch Dr. Miquel Costas Dr. Xavi Ribas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1445-1456
The metal‐directed supramolecular synthetic approach has paved the way for the development of functional nanosized molecules. In this work, we report the preparation of the new nanocapsule 3? (CF3SO3)8 with a A4B2 tetragonal prismatic geometry, where A corresponds to the dipalladium hexaazamacrocyclic complex Pd‐1 , and B corresponds to the tetraanionic form of palladium 5,10,15,20‐tetrakis(4‐carboxyphenyl)porphyrin ( 2 ). The large void space of the inner cavity and the supramolecular affinity for guest molecules towards porphyrin‐based hosts converts this nanoscale molecular 3D structure into a good candidate for host–guest chemistry. The interaction between this nanocage and different guest molecules has been studied by means of NMR, UV/Vis, ESI‐MS, and DOSY experiments, from which highly selective molecular recognition has been found for anionic, planar‐shaped π guests with association constants (Ka) higher than 109 M ?1, in front of non‐interacting aromatic neutral or cationic substrates. DFT theoretical calculations provided insights to further understand this strong interaction. Nanocage 3? (CF3SO3)8 can not only strongly host one single molecule of M(dithiolene)2 complexes (M=Au, Pt, Pd, and Ni), but also can finely tune their optical and redox properties. The very simple synthesis of both the supramolecular cage and the building blocks represents a step forward for the development of polyfunctional supramolecular nanovessels, which offer multiple applications as sensors or nanoreactors. 相似文献
190.
Dr. Srijit Biswas Dr. Christian Dahlstrand Rahul A. Watile Dr. Marcin Kalek Prof. Dr. Fahmi Himo Prof. Dr. Joseph S. M. Samec 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(52):17939-17950
Gold(I)‐chloride‐catalyzed synthesis of α‐sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols showed a wide substrate scope with respect to both propargylic alcohols and aryl thiols. Primary and secondary aromatic propargylic alcohols generated α‐sulfenylated aldehydes and ketones in 60–97 % yield. Secondary aliphatic propargylic alcohols generated α‐sulfenylated ketones in yields of 47–71 %. Different gold sources and ligand effects were studied, and it was shown that gold(I) chloride gave the highest product yields. Experimental and theoretical studies demonstrated that the reaction proceeds in two separate steps. A sulfenylated allylic alcohol, generated by initial regioselective attack of the aryl thiol on the triple bond of the propargylic alcohol, was isolated, evaluated, and found to be an intermediate in the reaction. Deuterium labeling experiments showed that the protons from the propargylic alcohol and aryl thiol were transferred to the 3‐position, and that the hydride from the alcohol was transferred to the 2‐position of the product. Density functional theory (DFT) calculations showed that the observed regioselectivity of the aryl thiol attack towards the 2‐position of propargylic alcohol was determined by a low‐energy, five‐membered cyclic protodeauration transition state instead of the strained, four‐membered cyclic transition state found for attack at the 3‐position. Experimental data and DFT calculations supported that the second step of the reaction is initiated by protonation of the double bond of the sulfenylated allylic alcohol with a proton donor coordinated to gold(I) chloride. This in turn allows for a 1,2‐hydride shift, generating the final product of the reaction. 相似文献