全文获取类型
收费全文 | 2960篇 |
免费 | 611篇 |
国内免费 | 438篇 |
专业分类
化学 | 2980篇 |
晶体学 | 55篇 |
力学 | 4篇 |
综合类 | 14篇 |
数学 | 3篇 |
物理学 | 591篇 |
无线电 | 362篇 |
出版年
2023年 | 61篇 |
2022年 | 51篇 |
2021年 | 128篇 |
2020年 | 178篇 |
2019年 | 111篇 |
2018年 | 104篇 |
2017年 | 87篇 |
2016年 | 188篇 |
2015年 | 181篇 |
2014年 | 203篇 |
2013年 | 282篇 |
2012年 | 228篇 |
2011年 | 223篇 |
2010年 | 162篇 |
2009年 | 178篇 |
2008年 | 216篇 |
2007年 | 208篇 |
2006年 | 225篇 |
2005年 | 153篇 |
2004年 | 127篇 |
2003年 | 170篇 |
2002年 | 82篇 |
2001年 | 100篇 |
2000年 | 41篇 |
1999年 | 41篇 |
1998年 | 41篇 |
1997年 | 43篇 |
1996年 | 46篇 |
1995年 | 32篇 |
1994年 | 24篇 |
1993年 | 22篇 |
1992年 | 16篇 |
1991年 | 7篇 |
1990年 | 15篇 |
1989年 | 10篇 |
1988年 | 11篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有4009条查询结果,搜索用时 78 毫秒
181.
A new bridging ligand, 2,3‐di(2‐pyridyl)‐5‐phenylpyrazine (dpppzH), has been synthesized. This ligand was designed so that it could bind two metals through a NN‐CNN‐type coordination mode. The reaction of dpppzH with cis‐[(bpy)2RuCl2] (bpy=2,2′‐bipyridine) affords monoruthenium complex [(bpy)2Ru(dpppzH)]2+ ( 12+ ) in 64 % yield, in which dpppzH behaves as a NN bidentate ligand. The asymmetric biruthenium complex [(bpy)2Ru(dpppz)Ru(Mebip)]3+ ( 23+ ) was prepared from complex 12+ and [(Mebip)RuCl3] (Mebip=bis(N‐methylbenzimidazolyl)pyridine), in which one hydrogen atom on the phenyl ring of dpppzH is lost and the bridging ligand binds to the second ruthenium atom in a CNN tridentate fashion. In addition, the RuPt heterobimetallic complex [(bpy)2Ru(dpppz)Pt(C?CPh)]2+ ( 42+ ) has been prepared from complex 12+ , in which the bridging ligand binds to the platinum atom through a CNN binding mode. The electronic properties of these complexes have been probed by using electrochemical and spectroscopic techniques and studied by theoretical calculations. Complex 12+ is emissive at room temperature, with an emission λmax=695 nm. No emission was detected for complex 23+ at room temperature in MeCN, whereas complex 42+ displayed an emission at about 750 nm. The emission properties of these complexes are compared to those of previously reported Ru and RuPt bimetallic complexes with a related ligand, 2,3‐di(2‐pyridyl)‐5,6‐diphenylpyrazine. 相似文献
182.
Patrícia Santiago de Oliveira Patricio Iaci Miranda Pereira Natália Cristina Ferreira da Silva Eliane Ayres Fabiano Vargas Pereira Rodrigo Lambert Oréfice 《European Polymer Journal》2013
Polyurethane waterborne synthesis was performed using a two-step method, commonly referred to as a prepolymer method. Nanocomposites based on waterborne polyurethane and cellulose nanocrystals were prepared by the prepolymer method by altering the mode and step in which the nanofillers were incorporated during the polyurethane formation. The morphology, structural, thermal, and mechanical properties of the resulting nanocomposite films were evaluated by Fourier transform infrared spectroscopy (FTIR), small angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and tensile tests. FTIR results indicated that the degree of interaction between the nanofillers and the WPU through hydrogen bonds could be controlled by the method of cellulose nanocrystal incorporation. Data obtained from SAXS experiments showed that the cellulose nanocrystals as well as the step of the reaction in which they are added influenced the morphology of the polyurethane. The reinforcing effect of CNCs on the nanocomposites depends on their morphology. 相似文献
183.
Rinki Bhadra Vidya Nand Singh Bodh Raj Mehta Pranayee Datta 《Journal of Dispersion Science and Technology》2013,34(9):1202-1207
ZnO nanocrystals are synthesized using the quenching method. The properties of the grown nanocrystals are studied using ultraviolet-vis spectroscopy, x-ray diffraction, photoluminescence, electron diffraction, energy dispersive x-ray spectroscopy, and high resolution transmission electron microscopy. Current-voltage characteristics of the prepared samples are studied for investigating the possible application of the samples as switch and memristor. 相似文献
184.
Viorel Cîrcu Doina Mănăilă-Maximean Constantin Roşu Monica Iliş Yann Molard Florea Dumitraşcu 《Liquid crystals》2013,40(2):123-132
A series of ortho-metallated Pd and Pt complexes containing an imine ligand carrying three alkoxy chains and N-benzoylthiourea derivatives as co-ligands were prepared and their liquid crystalline properties investigated. Their structures were assigned based on elemental analysis, IR and 1H NMR spectroscopy, whereas thermal properties were investigated by differential scanning calotimetry and polarising optical microscopy. All the compounds exhibit monotropic transitions involving nematic and smectic A phases, with the mesomorphic behaviour strongly related to the type of N-benzoylthiourea as well as the metal centre used. The thermally stimulated depolarisation current technique was employed to determine the conduction mechanism, phase transition temperature and the activation energies for one of the ortho-metallated Pd complexes. 相似文献
185.
Janina Möker Ursula Salge-Bartels Joachim Thiem 《Journal of carbohydrate chemistry》2013,32(9):702-710
Syntheses of carbohydrate-functionalized platinum complexes resembling presently employed cytostatics were performed. Mono-allylated sugar substrates obtained in two steps from glucose and galactose were connected with 2-allyl diethyl malonate by cross-metathesis. Following hydrogenation and acidic cleavage of the ester and alkylidene functionalities gave dicarboxylated glycoconjugates, which were transformed into their diammine platinum complexes. The antitumor activities of these platinum complexes were checked by sensitivity testing with 11 lung cancer cell lines. The novel glucose-platinum complex proved to be comparable to the drug carboplatin. 相似文献
186.
Dr. Clive Yik‐Sham Chung Prof. Dr. Vivian Wing‐Wah Yam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(39):13182-13192
Terpyridylplatinum(II)‐based metallosupramolecular triblock copolymers with hydrophilic alkynyl ligands have been synthesised and characterised. As a result of the intrinsic properties of Pluronics, reversible temperature‐induced micellisation occurred at high temperature leading to aggregation of the platinum(II) complex moieties through Pt???Pt and π–π interactions, resulting in significant UV/Vis absorption and near‐infrared (NIR) emission spectral changes. The critical micelle temperatures of the complexes were found to vary from 21 to 30 °C due to differences in the hydrophilicity of the alkynyl ligands and the electrostatic repulsions between the positively charged platinum(II) complex moieties. One of the complexes with pH‐responsive CH2NMe2 groups on the alkynyl ligand was found to show NIR emission that is sensitive to both pH and temperature. Such dual‐responsive behaviour has been ascribed to the modulation of the self‐assembly of the complex moieties by temperature‐induced micellisation and the changes in the hydrophilicity as well as electrostatic interactions upon protonation/deprotonation of the CH2NMe2 groups on the alkynyl ligand. 相似文献
187.
Dr. Ángel J. Jiménez Michael Sekita Dr. Esmeralda Caballero Dr. M. Luisa Marcos Dr. M. Salomé Rodríguez‐Morgade Prof. Dr. Dirk M. Guldi Prof. Tomás Torres 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14506-14514
In a novel electron‐donor–acceptor conjugate, phthalocyanine (Pc) and perylenediimide (PDI) are connected through a trans‐platinum(II) diacetylide linker to yield Pc‐Pt‐PDI 1 . In the ground state, the presence of PtII disrupts the electronic communication between the two electroactive components, as revealed by UV/Vis spectroscopy and electrochemical studies. The photophysical behavior of 1 is compared with that of the corresponding Pc‐PDI electron‐donor–acceptor conjugate 2 in terms of charge separation and charge recombination. The insertion of PtII between Pc and PDI impacts the results in a longer‐lived Pc . +/PDI . ? radical ion‐pair state. In addition, the intermediately formed Pc triplet excited state is formed with higher quantum yields in 1 than in 2 . 相似文献
188.
Ran Choi Dr. Sang‐Il Choi Dr. Chang Hyuck Choi Dr. Ki Min Nam Prof. Seong Ihl Woo Prof. Joon T. Park Prof. Sang Woo Han 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(25):8190-8198
Improving the electrocatalytic activity and durability of Pt‐based catalysts with low Pt content toward the oxygen reduction reaction (ORR) is one of the main challenges in advancing the performance of polymer electrolyte membrane fuel cells (PEMFCs). Herein, a designed synthesis of well‐defined Pd@Pt core–shell nanoparticles (NPs) with a controlled Pt shell thickness of 0.4–1.2 nm by a facile wet chemical method and their electrocatalytic performances for ORR as a function of shell thickness are reported. Pd@Pt NPs with predetermined structural parameters were prepared by in situ heteroepitaxial growth of Pt on as‐synthesized 6 nm Pd NPs without any sacrificial layers and intermediate workup processes, and thus the synthetic procedure for the production of Pd@Pt NPs with well‐defined sizes and shell thicknesses is greatly simplified. The Pt shell thickness could be precisely controlled by adjusting the molar ratio of Pt to Pd. The ORR performance of the Pd@Pt NPs strongly depended on the thickness of their Pt shells. The Pd@Pt NPs with 0.94 nm Pt shells exhibited enhanced specific activity and higher durability compared to other Pd@Pt NPs and commercial Pt/C catalysts. Testing Pd@Pt NPs with 0.94 nm Pt shells in a membrane electrode assembly revealed a single‐cell performance comparable with that of the Pt/C catalyst despite their lower Pt content, that is the present NP catalysts can facilitate low‐cost and high‐efficient applications of PEMFCs. 相似文献
189.
Dr. Xiangheng Niu Prof. Dr. Minbo Lan Dr. Hongli Zhao Dr. Chen Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(29):9534-9541
The investigation of highly efficient catalysts for the electrochemical oxidation of glucose is the most critical challenge to commercialize nonenzymatic glucose sensors, which display a few attractive superiorities including the sufficient stability of their properties and the desired reproducibility of results over enzyme electrodes. Herein we propose a new and very promising catalyst: Pt cubes well‐dispersed on the porous Cu foam, for the the electrochemical oxidation reaction of glucose in neutral media. The catalyst is fabricated in situ on a homemade screen‐printed carbon electrode (SPCE) substrate through initially synthesizing the three‐dimensional (3D) porous Cu foam using a hydrogen evolution assisted electrodeposition strategy, followed by electrochemically reducing the platinic precursor simply and conveniently. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) proofs demonstrate that Pt cubes, with an average size (the distance of opposite faces) of 185.1 nm, highly dispersed on the macro/nanopore integrated Cu foam support can be reproducibly obtained. The results of electrochemical tests indicate that the cubic Pt‐based catalyst exhibits significant enhancement on the catalytic activity towards the electrooxidation of glucose in the presence of chloride ions, providing a specific activity 6.7 times and a mass activity 5.3 times those of commercial Pt/C catalysts at ?0.4 V (vs. Ag/AgCl). In addition, the proposed catalyst shows excellent stability of performance, with only a 2.8 % loss of electrocatalytic activity after 100 repetitive measurements. 相似文献
190.
Dr. Dongpeng Yan Dr. Dejan‐Krešimir Bučar Dr. Amit Delori Bhavnita Patel Dr. Gareth O. Lloyd Prof. William Jones Prof. Xue Duan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(25):8213-8219
Multi‐component organic nanocrystals that are comprised of two or more supramolecular building blocks can be used to extend the design and assembly scope of solid molecular materials. Herein, we report the use of ultrasonication to prepare halogen‐bonded stilbene‐based nano‐cocrystals that exhibit different photoemission properties, including one‐ and two‐phonon emission and fluorescence lifetimes, relative to those of macrodimensional crystals. The structural transformation from nano‐cocrystals into nanocrystals upon heating results in a luminescence red‐shift from greenish blue to yellow. The temperature‐dependent ratiometric luminescence may allow such nano‐cocrystals to be used as fluorescent sensors and thermosensitive materials. 相似文献