全文获取类型
收费全文 | 17919篇 |
免费 | 3031篇 |
国内免费 | 2260篇 |
专业分类
化学 | 13512篇 |
晶体学 | 212篇 |
力学 | 978篇 |
综合类 | 142篇 |
数学 | 1686篇 |
物理学 | 6680篇 |
出版年
2024年 | 32篇 |
2023年 | 319篇 |
2022年 | 396篇 |
2021年 | 568篇 |
2020年 | 761篇 |
2019年 | 729篇 |
2018年 | 653篇 |
2017年 | 569篇 |
2016年 | 872篇 |
2015年 | 820篇 |
2014年 | 1003篇 |
2013年 | 1387篇 |
2012年 | 1553篇 |
2011年 | 1629篇 |
2010年 | 1126篇 |
2009年 | 1128篇 |
2008年 | 1253篇 |
2007年 | 1134篇 |
2006年 | 1007篇 |
2005年 | 877篇 |
2004年 | 710篇 |
2003年 | 597篇 |
2002年 | 640篇 |
2001年 | 464篇 |
2000年 | 350篇 |
1999年 | 372篇 |
1998年 | 307篇 |
1997年 | 271篇 |
1996年 | 244篇 |
1995年 | 212篇 |
1994年 | 185篇 |
1993年 | 154篇 |
1992年 | 150篇 |
1991年 | 139篇 |
1990年 | 108篇 |
1989年 | 85篇 |
1988年 | 63篇 |
1987年 | 61篇 |
1986年 | 56篇 |
1985年 | 47篇 |
1984年 | 28篇 |
1983年 | 26篇 |
1982年 | 26篇 |
1981年 | 21篇 |
1980年 | 16篇 |
1979年 | 7篇 |
1976年 | 6篇 |
1975年 | 8篇 |
1974年 | 7篇 |
1957年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 18 毫秒
941.
Qumei Jin Fengyu Qu Jingjie Jiang Yan Dong Wei Guo Huiming Lin 《Journal of Sol-Gel Science and Technology》2013,66(3):466-471
A novel dual-drug delivery system based on mesoporous-macroporous silica/polyelectrolytes-SBA-15 has been synthesized. The structure and composition of these materials were characterized by powder X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and N2 adsorption–desorption measurements. In this system, water-soluble metformin hydrochloride and fat-soluble ibuprofen were used as model drugs to study the controlled release behavior. The pH-controlled release of individual drugs was obtained by the primary release of metformin hydrochloride from polyelectrolytes-SBA-15 in acid condition and the predominant release of ibuprofen from MMC in alkaline environment. The results show that the polyelectrolytes-SBA-15/mesoporous-macroporous silica can be used as dual-drug release system and the individual drug can be controlled release with the change of pH value of the environment. 相似文献
942.
Dr. Cunku Dong Prof. Xin Li Wei Zhao Pengfei Jin Xiujuan Fan Prof. Jingyao Qi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(30):10046-10056
A unique one‐dimensional (1D) sandwich single‐walled TiO2 nanotube (STNT) is proposed as a photoanode nanomaterial with perfect morphology and large specific surface area. We have thoroughly examined the elementary photoelectronic processes occurring at the porphyrin dye/STNT hetero‐interface in dye‐sensitized solar cells (DSSCs) by theoretical simulation. It is desirable to investigate the interfacial photoelectronic processes to elucidate the electron transfer and transport mechanism in 1D STNT‐based DSSCs. We have found that the photoexcitation and interfacial charge separation mechanism can be described as follows. A ground‐state electron of the dye molecule (localized around the electron donor) is first promoted to the excited state (distributed electron donor), and then undergoes ultrafast injection into the conduction band of the STNT, leaving a hole around the oxidized dye. Significantly, the injected electron in the conduction band is transported along the STNT by means of Ti 3d orbitals, offering a unidirectional electron pathway toward the electrode for massive collection without the observation of trap states. Our study not only provides theoretical guidelines for the modification of TiO2 nanotubes as a photoanode material, but also opens a new perspective for the development of a novel class of TiO2 nanotubes with high power‐generation efficiency. 相似文献
943.
Wangdong Zeng Dr. Masatoshi Ishida Sangsu Lee Young Mo Sung Dr. Zebing Zeng Yong Ni Prof. Chunyan Chi Prof. Dongho Kim Prof. Jishan Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16814-16824
A p‐quinodimethane (p‐QDM)‐bridged porphyrin dimer 1 has been prepared for the first time. An unexpected Michael addition reaction took place when we attempted to synthesize compound 1 by reaction of the cross‐conjugated keto‐linked porphyrin dimers 8 a and 8 b with alkynyl/aryl Grignard reagents. Alternatively, compound 1 could be successfully prepared by intramolecular Friedel–Crafts alkylation of the diol‐linked porphyrin dimer 14 with concomitant oxidation in air. Compound 1 shows intense one‐photon absorption (OPA, λmax=955 nm, ε=45400 M ?1 cm?1) and a large two‐photon absorption (TPA) cross‐section (σ(2)max=2080 GM at 1800 nm) in the near‐infrared (NIR) region due to its extended π‐conjugation and quinoidal character. It also exhibits a short singlet excited‐state lifetime of 25 ps. The cyclic voltammogram of 1 displays multiple redox waves with a small electrochemical energy gap of 0.86 eV. The ground‐state geometry, electronic structure, and optical properties of 1 have been further studied by density functional theory (DFT) calculations and compared with those of the keto‐linked dimer 8 b . This research has revealed that incorporation of a p‐QDM unit into the porphyrin framework had a significant impact on its optical and electronic properties, leading to a novel NIR OPA and TPA chromophore. 相似文献
944.
945.
Shuwen Li Zhengping Dong Honglei Yang Shujing Guo Galian Gou Ren Ren Zhejun Zhu Prof. Jun Jin Jiantai Ma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(7):2384-2391
A new catalyst consisting of ionic liquid (IL)‐functionalized carbon nanotubes (CNTs) obtained through 1,3‐dipolar cycloaddition support‐enhanced electrocatalytic Pd nanoparticles (Pd@IL(Cl?)‐CNTs) was successfully fabricated and applied in direct ethanol alkaline fuel cells. The morphology, structure, component and stability of Pd@IL(Cl?)‐CNTs were systematic characterized by transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM), Raman spectra, thermogravimetric analysis (TGA) and X‐ray diffraction (XRD). The new catalyst exhibited higher electrocatalytic activity, better tolerance and electrochemical stability than the Pd nanoparticles (NPs) immobilized on CNTs (Pd@CNTs), which was ascribed to the effects of the IL, larger electrochemically active surface area (ECSA), and greater processing performance. Cyclic voltammograms (CVs) at various scan rates illustrated that the oxidation behaviors of ethanol at all electrodes were controlled by diffusion processes. The investigation of the different counteranions demonstrated that the performance of the IL‐CNTs hybrid material was profoundly influenced by the subtly varied structures of the IL moiety. All the results indicated that the Pd@IL(Cl?)‐CNTs catalyst is an efficient anode catalyst, which has potential applications in direct ethanol fuel cells and the strategy of IL functionalization of CNTs could be available to prepare other carbonaceous carrier supports to enhance the dispersivity, stability, and catalytic performance of metal NPs as well. 相似文献
946.
Gadolinium(III)‐Hydroxy Ladders Trapped in Succinate Frameworks with Optimized Magnetocaloric Effect
Yan‐Cong Chen Fu‐Sheng Guo Prof. Dr. Yan‐Zhen Zheng Jun‐Liang Liu Ji‐Dong Leng Róbert Tarasenko Prof. Dr. Martin Orendáč Dr. Jan Prokleška Prof. Dr. Vladimír Sechovský Prof. Dr. Ming‐Liang Tong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13504-13510
Two kinds of inorganic gadolinium(III)‐hydroxy “ladders”, [2×n] and [3×n], were successfully trapped in succinate (suc) coordination polymers, [Gd2(OH)2(suc)2(H2O)]n ? 2n H2O ( 1 ) and [Gd6(OH)8(suc)5(H2O)2]n ? 4n H2O ( 2 ), respectively. Such coordination polymers could be regarded as alternating inorganic–organic hybrid materials with relatively high density. Magnetic and heat capacity studies reveal a large cryogenic magnetocaloric effect (MCE) in both compounds, namely (ΔH=70 kG) 42.8 J kg?1 K?1 for complex 1 and 48.0 J kg?1 K?1 for complex 2 . The effect of the high density is evident, which gives very large volumetric MCEs up to 120 and 144 mJ cm?3 K?1 for complexes 1 and 2 , respectively. 相似文献
947.
Iulius I. E. Markovits Dr. Wilhelm A. Eger Dr. Shuang Yue Dr. Mirza Cokoja Christian J. Münchmeyer Bo Zhang Dr. Ming‐Dong Zhou Dr. Alexander Genest Prof. Dr. János Mink Prof. Dr. Shu‐Liang Zang Prof. Dr. Notker Rösch Prof. Dr. Fritz E. Kühn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(19):5972-5979
Imidazolium‐based ionic liquids that contain perrhenate anions are very efficient reaction media for the epoxidation of olefins with H2O2 as an oxidant, thus affording cyclooctene in almost quantitative yields. The mechanism of this reaction does not follow the usual pathway through peroxo complexes, as is the case with long‐known molecular transition‐metal catalysts. By using in situ Raman, FTIR, and NMR spectroscopy and DFT calculations, we have shown that the formation of hydrogen bonds between the oxidant and perrhenate activates the oxidant, thereby leading to the transfer of an oxygen atom onto the olefin demonstrating the special features of an ionic liquid as a reaction environment. The influence of the imidazolium cation and the oxidant (aqueous H2O2, urea hydrogen peroxide, and tert‐butyl hydrogen peroxide) on the efficiency of the epoxidation of cis‐cyclooctene were examined. Other olefinic substrates were also used in this study and they exhibited good yields of the corresponding epoxides. This report shows the potential of using simple complexes or salts for the activation of hydrogen peroxide, owing to the interactions between the solvent medium and the active complex. 相似文献
948.
Qian Lei Yawen Wei Dinesh Talwar Prof. Chao Wang Prof. Dong Xue Prof. Jianliang Xiao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(12):4021-4029
Reductive amination of various ketones and aldehydes by transfer hydrogenation under aqueous conditions has been developed, by using cyclometallated iridium complexes as catalysts and formate as hydrogen source. The pH value of the solution is shown to be critical for a high catalytic chemoselectivity and activity, with the best pH value being 4.8. In comparison with that in organic solvents, the reductive amination in an aqueous phase is faster, and the molar ratio of the substrate to the catalyst (S/C) can be set as high as 1×105, the highest S/C value ever reported in reductive amination reactions. The catalyst is easy to access and the reaction is operationally simple, allowing a wide range of ketones and aldehydes to react with various amines in high yields. The protocol provides a practical and environmental friendly new method for the synthesis of amine compounds. 相似文献
949.
Dr. Hong‐Dong Hao Dr. Sergio Wittlin Prof. Dr. Yikang Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(23):7605-7619
Perhydrolysis of a sterically congested multifunctional epoxide was achieved in ethereal H2O2 with the aid of a recently developed Mo catalyst. The resulting hydroperoxide cyclized to give a 1,2,4‐trioxane, which could be readily elaborated into qinghaosu and a range of novel analogues. Some of the compounds with two such trioxane moieties showed in vitro antimalarial activity comparable to or even better than that of artesunate or chloroquine. 相似文献
950.
Chengzhou Zhu Shaojun Guo Prof. Shaojun Dong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):1104-1111
We have demonstrated a rapid and general strategy to synthesize novel three‐dimensional PdPt bimetallic alloy nanosponges in the absence of a capping agent. Significantly, the as‐prepared PdPt bimetallic alloy nanosponges exhibited greatly enhanced activity and stability towards ethanol/methanol electrooxidation in an alkaline medium, which demonstrates the potential of applying these PdPt bimetallic alloy nanosponges as effective electrocatalysts for direct alcohol fuel cells. In addition, this simple method has also been applied for the synthesis of AuPt, AuPd bimetallic, and AuPtPd trimetallic alloy nanosponges. The as‐synthesized three‐dimensional bimetallic/trimetallic alloy nanosponges, because of their convenient preparation, well‐defined sponge‐like network, large‐scale production, and high electrocatalytic performance for ethanol/methanol electrooxidation, may find promising potential applications in various fields, such as formic acid oxidation or oxygen reduction reactions, electrochemical sensors, and hydrogen‐gas sensors. 相似文献