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   1101篇
  免费   38篇
  国内免费   4篇
化学   835篇
晶体学   8篇
力学   26篇
数学   153篇
物理学   121篇
  2023年   12篇
  2022年   19篇
  2021年   50篇
  2020年   19篇
  2019年   25篇
  2018年   15篇
  2017年   12篇
  2016年   42篇
  2015年   23篇
  2014年   43篇
  2013年   78篇
  2012年   61篇
  2011年   103篇
  2010年   47篇
  2009年   38篇
  2008年   77篇
  2007年   74篇
  2006年   61篇
  2005年   69篇
  2004年   65篇
  2003年   33篇
  2002年   34篇
  2001年   6篇
  2000年   13篇
  1999年   10篇
  1998年   7篇
  1997年   9篇
  1996年   15篇
  1995年   12篇
  1994年   5篇
  1993年   8篇
  1992年   7篇
  1991年   5篇
  1990年   3篇
  1989年   7篇
  1988年   4篇
  1987年   8篇
  1986年   3篇
  1984年   1篇
  1982年   1篇
  1981年   4篇
  1980年   1篇
  1979年   2篇
  1977年   3篇
  1976年   2篇
  1975年   1篇
  1974年   2篇
  1973年   1篇
  1944年   1篇
  1940年   1篇
排序方式: 共有1143条查询结果,搜索用时 15 毫秒
51.
In the present study, we investigate the structures of glucosylated curcumin derivatives with DFT at B3LYP/6‐31G* level. A conformational analysis is performed in order to determine the conformational minimum (GS) and rotational transition state (TS) of curcumin derivatives and then their electronic features are evaluated. HOMO and LUMO frontier orbitals and maps of electron density potential (MEPs) are plotted and compared. In order to correlate their predicted spectroscopic properties with IR, UV–vis and NMR experimental data we extended the theoretical study on electronic properties to different solvents (H2O, MeOH, ACN, DMSO). The main finding is that the curcuminic core maintains the same geometrical and electronic structures in all compounds miming the metal coordination capability showed by curcumin. Therefore, we may confirm that the presence of glucose does not affect the electronic properties of the derivatives. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   
52.
53.
We studied the electronic and conductance properties of two thiophene–curcuminoid molecules, 2‐thphCCM ( 1 ) and 3‐thphCCM ( 2 ), in which the only structural difference is the position of the sulfur atoms in the thiophene terminal groups. We used electrochemical techniques as well as UV/Vis absorption studies to obtain the values of the HOMO–LUMO band gap energies, showing that molecule 1 has lower values than 2 . Theoretical calculations show the same trend. Self‐assembled monolayers (SAMs) of these molecules were studied by using electrochemistry, showing that the interaction with gold reduces drastically the HOMO–LUMO gap in both molecules to almost the same value. Single‐molecule conductance measurements show that molecule 2 has two different conductance values, whereas molecule 1 exhibits only one. Based on theoretical calculations, we conclude that the lowest conductance value, similar in both molecules, corresponds to a van der Waals interaction between the thiophene ring and the electrodes. The one order of magnitude higher conductance value for molecule 2 corresponds to a coordinate (dative covalent) interaction between the sulfur atoms and the gold electrodes.  相似文献   
54.
The most intriguing feature of metal–metal bonds in inorganic compounds is an apparent lack of correlation between the bond order and the bond length. In this study, we combine a variety of literature data obtained by quantum chemistry and our results based on the empirical bond valence model (BVM), to confirm for the first time the existence of a normal exponential correlation between the effective bond order (EBO) and the length of the metal–metal bonds. The difference between the EBO and the formal bond order is attributed to steric conflict between the (TM)n cluster (TM=transition metal) and its environment. This conflict, affected mainly by structural type, should cause high lattice strains, but electron redistribution around TM atoms, evident from the BVM calculations, results in a full or partial strain relaxation.  相似文献   
55.
Turing reaction–diffusion systems have been used to model pattern formation in several areas of developmental biology. Previous biomathematical Turing system models employed static domains which failed to incorporate the growth that inherently occurs as an organism develops. To address this shortcoming, we incorporate an exponentially growing domain into a Turing system, allowing one to more realistically model biological pattern formation. This Turing system can generate patterns on an exponentially growing domain in any of the eleven coordinate systems in which the Helmholtz equation is separable, making the system incredibly flexible and giving one the capability to mathematically model pattern formation on a geometrically diverse group of domains. Linear stability analysis is employed to generate mathematical conditions which ensure such a system can generate patterns. We apply the exponentially growing Turing system to a prolate spheroidal domain and conduct numerical simulations to investigate the system’s pattern-generating behavior. We find that the addition of growth to a Turing system causes a significant change in the pattern-generating behavior of the system. While a static domain Turing system converges to a final pattern, an exponentially growing domain Turing system produces transient patterns that continually evolve and increase in complexity over time.  相似文献   
56.
We propose a two-lattice method for direct determination of the recoilless fraction using a single room-temperature transmission Mössbauer measurement. The method is first demonstrated for the case of iron and metallic glass two-foil system and is next generalized for the case of physical mixtures of two powders. We further apply this method to determine the recoilless fraction of hematite and magnetite particles. Finally, we provide direct measurement of the recoilless fraction in nanohematite and nanomagnetite with an average particle size of 19nm. A list of values obtained for the recoilless fraction in various materials using the two-lattice method is given.  相似文献   
57.
In this article the adsorption of 3-methylthiophene on planar and nanoparticle Au surfaces is investigated. The resulting systems are compared with a benchmark system based on 1-decanethiol. The characterization data collected evidence the formation of a packed 3-methylthiophene SAM on the planar surface. In particular, spectroscopic investigations suggest that 3-methylthiophene aromatic system is not adsorbed on the surface through the pi-electron system but rather through the S atom alone. On the other hand, the behavior of 3-methylthiophene on nanoparticle surfaces is notably different from that of the alkanethiol. Only a limited fraction of the surface of Au nanoparticles results to be actually coated after purification; this notwithstanding, the nanoparticle growth seems to be strongly influenced by the presence of such a labile encapsulating agent.  相似文献   
58.
Photoemission from the two outermost ionizations [highest occupied molecular orbitals (HOMO and HOMO-1)] of Mg(eta(5)-C(5)H(5))(2) has been studied with synchrotron radiation in the gas phase. Strong oscillations in the HOMO-1/HOMO ratio, qualitatively similar to those well-known for fullerenes, are found. Excellent agreement with the experimental ratio is provided by accurate cross section calculations both at the density-functional theory and time-dependent density-functional theory level, indicating that a many electron response has a minor role for this effect. A comparison with the calculated values for other metal sandwich compounds indicate that the presence of oscillations is a widespread phenomenon, and a potential source of interesting information on the structural and electronic properties of the target molecule.  相似文献   
59.
We consider the problem of finding positive solutions of Δu+λu+uq=0 in a bounded, smooth domain Ω in , under zero Dirichlet boundary conditions. Here q is a number close to the critical exponent 5 and 0<λ<λ1. We analyze the role of Green's function of Δ+λ in the presence of solutions exhibiting single and multiple bubbling behavior at one point of the domain when either q or λ are regarded as parameters. As a special case of our results, we find that if , where λ∗ is the Brezis-Nirenberg number, i.e., the smallest value of λ for which least energy solutions for q=5 exist, then this problem is solvable if q>5 and q−5 is sufficiently small.  相似文献   
60.
Efficient enantioselective Cu-catalyzed allylic alkylations of aromatic and aliphatic allylic phosphates bearing di- and trisubstituted olefins are disclosed. Enantioselective C-C bond forming reactions are promoted in the presence of 10 mol % readily available chiral amino acid-based ligand (5 steps, 40% overall yield synthesis) and 5 mol % (CuOTf)2 x C6H6. Reactions deliver tertiary and quaternary stereogenic carbon centers regioselectively and in 78-96% ee. Data regarding the effect of variations in ligand structure on the efficiency and enantioselectivity of the alkylation process, as well as a mechanistic working model, are presented. The suggested model involves a dual role for the chiral Cu complex: association of the Cu(I) center to the olefin is facilitated by a two-point binding between the carbonyl of the ligand's amide terminus and the P=O of the substrate.  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