首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   4512篇
  免费   744篇
  国内免费   328篇
化学   1484篇
晶体学   41篇
力学   1415篇
综合类   60篇
数学   724篇
物理学   1860篇
  2024年   4篇
  2023年   46篇
  2022年   104篇
  2021年   184篇
  2020年   220篇
  2019年   133篇
  2018年   153篇
  2017年   166篇
  2016年   229篇
  2015年   153篇
  2014年   244篇
  2013年   352篇
  2012年   263篇
  2011年   301篇
  2010年   244篇
  2009年   268篇
  2008年   220篇
  2007年   228篇
  2006年   218篇
  2005年   214篇
  2004年   171篇
  2003年   183篇
  2002年   137篇
  2001年   108篇
  2000年   135篇
  1999年   102篇
  1998年   104篇
  1997年   98篇
  1996年   73篇
  1995年   72篇
  1994年   76篇
  1993年   73篇
  1992年   52篇
  1991年   47篇
  1990年   43篇
  1989年   25篇
  1988年   26篇
  1987年   18篇
  1986年   14篇
  1985年   21篇
  1984年   8篇
  1983年   7篇
  1982年   13篇
  1981年   3篇
  1980年   4篇
  1979年   6篇
  1978年   4篇
  1976年   2篇
  1971年   4篇
  1957年   6篇
排序方式: 共有5584条查询结果,搜索用时 19 毫秒
41.
Based on the thermo-electro-elastic coupling theory, the mathematical model for a surface heated piezoelectric semiconductor (PS) plate is developed in the time domain. Applying the direct and inverse Laplace transformations to the established model, the mechanical and electrical responses are investigated. The comparison between the analytical solution and the finite element method (FEM) is conducted, which illustrates the validity of the derivation. The calculated results show that the maximum values of the mechanical and electrical fields appear at the heating surface. Importantly, the perturbation carriers tend to concentrate in the zone near the heating surface under the given boundary conditions. It can also be observed that the heating induced elastic wave leads to jumps for the electric potential and perturbation carrier density at the wavefront. When the thermal relaxation time is introduced, all the field quantities become smaller because of the thermal lagging effect. Meanwhile, it can be found that the thermal relaxation time can describe the smooth variation at the jump position. Besides, for a plate with P-N junction, the effect of the interface position on the electrical response is studied. The effects of the initial carrier density on the electrical properties are discussed in detail. The conclusions in this article can be the guidance for the design of PS devices serving in thermal environment.  相似文献   
42.
Herein, polydopamine-coated Fe3O4 spheres were synthesized using a very simple, easy, cost-effective, efficient, and fast method. First, magnetic nanoparticles (Fe3O4) were synthesized and were followed by accommodating polydopamine on the surface of the prepared Fe3O4. The prepared polydopamine-coated Fe3O4 spheres were utilized as a sorbent in magnetic solid phase extraction of gemfibrozil and warfarin (as the model analytes). The extracted model analytes were desorbed by a suitable organic solvent and were analyzed by high-performance liquid chromatography. Under optimized condition, the linearity of the method was in the range of 0.1–200.0 μg/L for the selected analytes in water. The limits of detection were calculated to be in the range of 0.026–0.055 μg/L for warfarin and gemfibrozil, respectively. The limits of quantification were calculated to be in the range of 0.089–0.185 μg/L. The inter-day and intra-day relative standard deviations were determined to be in the range of 1.4%–3.3% in three concentrations in order to calculate the method precision. Furthermore, the enrichment factors were found to be 78 and 81 for warfarin and gemfibrozil, respectively. Moreover, the calculated absolute recoveries were between 78% and 81%. The obtained recoveries indicated that the method was useful and applicable in complicated real samples.  相似文献   
43.
Plants in the genus Erythrina is a potential source of chemical constituents, one of which is flavonoids, which have diverse bioactivities. To date, literature on the flavonoids from the genus Erythrina has only highlighted the phytochemical aspects, so this review article will discuss isolation techniques and strategies for the first time. More than 420 flavonoids have been reported in the Erythrina genus, which are grouped into 17 categories. These flavonoid compounds were obtained through isolation techniques and strategies using polar, semi-polar, and non-polar solvents. Various chromatographic techniques have been developed to isolate flavonoids using column flash chromatography, quick column chromatography, centrifugally accelerated thin-layer chromatography, radial chromatography, medium-pressure column chromatography, semi-preparative high-performance liquid chromatography, and preparative high-performance liquid chromatography. Chromatographic processes for isolating flavonoids can be optimized using multivariate statistical applications such as response surface methodology with central composite design, Box–Behnken design, Doehlert design, and mixture design.  相似文献   
44.
陈熙  李莉  张文治  宋强  李奕萱 《无机化学学报》2015,31(10):1971-1980
在不同的制备条件下,通过微波水热两步法获得了一系列Ag2S/ZnO光催化剂,采用X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见漫反射吸收光谱(UV-Vis/DRS)、扫描电子显微镜(SEM)和N2吸附-脱附等测试手段对产物结构和形貌进行了表征。结果表明,产物以六方纤锌矿ZnO为主,其晶型结构并未随着反应温度和Ag2S物质的量的增加而改变。Ag2S的引入显著增强了光催化剂在可见光区的吸收,使吸收边带发生红移,同时抑制了ZnO(001)晶面的生长。另外,所得产物的形貌随着Ag2S物质的量的增加从爆米花状转变为少量的柱体颗粒,且BET比表面积经过复合后明显减小。以罗丹明B为目标降解物,研究并比较了一系列Ag2S/ZnO光催化剂对罗丹明B的光降解性能。结果表明,nAg2S/nZnO=1:10时,光催化剂在紫外光、可见光和模拟日光的照射下具有最好的光催化效果,优于目前应用最广泛的市售P25。另外,所制备的光催化材料Ag2S/ZnO经4次循环使用后,其降解效率没有明显下降,表明该催化材料具有一定的光催化稳定性。经捕获实验研究发现,在Ag2S/ZnO的光催化反应中空穴起主要作用,并根据绝对电负性估算了复合材料Ag2S/ZnO的能带位置,据此提出了可能的光催化反应机理。  相似文献   
45.
Three (donor–π–acceptor)+ systems with a methyl pyridinium or quinolinium as the electron‐deficient group, a dimethyl amino as the electron‐donor group, and an ethylene or butadiene group as the spacer have been investigated in a joint spectroscopic and TD‐DFT computational study. A negative solvatochromism has been revealed in the absorption spectra, which implies a solution color change, and interpreted by considering the variation in the permanent dipole moment modulus and orientation upon photoexcitation. The fluorescence efficiency decreases upon increasing solvent polarity, in agreement with the excited‐state optimized geometries (planar in low‐polarity media and twisted in high‐polarity media). Femtosecond transient absorption has revealed the occurrence of a fast photoinduced intramolecular charge transfer (ICT) and the molecular factors that determine an efficient ICT. Considering the crucial role of the ICT in tuning the nonlinear optical (NLO) properties, these compounds can be considered promising NLO materials.  相似文献   
46.
The C‐nucleoside based on the hydroxyquinoline ligand (Hq) is complementary to itself and forms stable Hq–Hq pairs in double‐stranded DNA. These artificial Hq–Hq pairs may serve as artificial electron carriers for long‐range photoinduced electron transfer in DNA, as elucidated by a combination of gel electrophoretic analysis of irradiated samples and time‐resolved transient absorption spectroscopy. For this study, the Hq–Hq pair was combined with a DNA‐based donor–acceptor system consisting of 6‐N,N‐dimethylaminopyrene conjugated to 2′‐deoxyuridine as photoinducible electron donor, and methyl viologen attached to the 2′‐position of uridine as electron acceptor. The Hq radical anion was identified in the time‐resolved measurements and strand cleavage products support its role as an intermediate charge carrier. Hence, the Hq–Hq pair significantly enhances the electron hopping capability of DNA compared to natural DNA bases over long distances while keeping the self‐assembly properties as the most attractive feature of DNA as a supramolecular architecture.  相似文献   
47.
A thermally responsive boronate affinity chromatographic material, which showed thermal sensitivity, had been successfully applied for the enrichment and separation of cis‐diol‐containing compounds, and the capture and release process could be facilitated by adjusting the temperature. However, in this system, the pH of the mobile phase must be higher than 9.8, and alkaline media can lead to the degradation of labile compounds; the use of silica beads also limits its use. In this study, thermally responsive boronate affinity chromatographic material, namely poly(N‐isopropylacrylamide‐co‐N‐acryloyl‐3‐aminophenylboronic acid) grafted silica, was successfully prepared by atom transfer radical polymerization. Its structure was confirmed by IR spectroscopy and the graft ratio was 20.8%, determined by thermogravimetric analysis. Furthermore, the capture/release of adenosine, a cis‐diol, was performed from pH 5.0–9.0 and 10–50°C. The elution of adenosine was remarkably retarded at decreased temperatures and adenosine could be captured completely at 10°C at pH values of 5.0–9.0. The enrichment of adenosine could be achieved by simply changing the temperature from 10 to 50°C. Therefore, this material not only improved the stability of the silica, but was also suitable for the capture of oxidation‐sensitive biological analytes. Moreover, it could be used for the enrichment of cis‐diol‐containing compounds in LC with MS.  相似文献   
48.
Microbial fuel cells (MFCs) have been extensively studied as self-powered toxicity biosensors; however, their applications are limited by the relatively poor toxicity responses. The toxicity responses are known to be related to the factors such as the resistance of species to toxicants, the bioavailability of toxicants and the type of sensing elements. Accordingly, some strategies have already been proposed to enhance the toxicity responses in the past several years, including the external resistance tuning, quorum sensing effect, shear stress control, nutrient level control, electrode material choice, sensing element choice, and cell configuration design. This work introduces and discusses these strategies, and the suggestion for future work is also provided finally.  相似文献   
49.
Recently, porous photocatalytically active block copolymer membranes were introduced, based on heterogenized molecular catalysts. Here, we report the integration of the photosensitizer, i. e., the light absorbing unit in an intermolecular photocatalytic system into block copolymer membranes in a covalent manner. We study the resulting structure and evaluate the orientational mobility of the photosensitizer as integral part of the photocatalytic system in such membranes. To this end we utilize transient absorption anisotropy, highlighting the temporal reorientation of the transition dipole moment probed in a femtosecond pump-probe experiment. Our findings indicate that the photosensitizer is rigidly bound to the polymer membrane and shows a large heterogeneity of absolute anisotropy values as a function of location probed within the matrix. This reflects the sample inhomogeneity arising from different protonation states of the photosensitizer and different intermolecular interactions of the photosensitizers within the block copolymer membrane scaffold.  相似文献   
50.
Melanin-like nanomaterials have found application in a large variety of high economic and social impact fields as medicine, energy conversion and storage, photothermal catalysis and environmental remediation. These materials have been used mostly for their optical and electronic properties, but also for their high biocompatibility and simplicity and versatility of preparation. Beside this, their chemistry is complex and it yields structures with different molecular weight and composition ranging from oligomers, to polymers as well as nanoparticles (NP). The comprehension of the correlation of the different compositions and morphologies to the optical properties of melanin is still incomplete and challenging, even if it is fundamental also from a technological point of view. In this minireview we focus on scientific papers, mostly recent ones, that indeed examine the link between composition and structural feature and photophysical and photochemical properties proposing this approach as a general one for future research.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号