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   990篇
  免费   14篇
  国内免费   3篇
化学   588篇
晶体学   5篇
力学   22篇
数学   143篇
物理学   249篇
  2020年   8篇
  2019年   7篇
  2018年   8篇
  2017年   6篇
  2016年   17篇
  2015年   13篇
  2014年   11篇
  2013年   57篇
  2012年   42篇
  2011年   53篇
  2010年   20篇
  2009年   24篇
  2008年   21篇
  2007年   33篇
  2006年   34篇
  2005年   28篇
  2004年   27篇
  2003年   24篇
  2002年   35篇
  2001年   17篇
  2000年   28篇
  1999年   16篇
  1998年   13篇
  1997年   8篇
  1996年   17篇
  1995年   22篇
  1994年   18篇
  1993年   11篇
  1992年   12篇
  1991年   6篇
  1990年   23篇
  1989年   15篇
  1988年   17篇
  1987年   8篇
  1986年   21篇
  1985年   22篇
  1984年   16篇
  1983年   9篇
  1982年   12篇
  1981年   15篇
  1980年   15篇
  1979年   16篇
  1978年   16篇
  1977年   15篇
  1976年   12篇
  1975年   22篇
  1974年   20篇
  1973年   21篇
  1971年   8篇
  1968年   6篇
排序方式: 共有1007条查询结果,搜索用时 15 毫秒
181.
Additive efficiency decomposition in two-stage DEA   总被引:1,自引:0,他引:1  
Kao and Hwang (2008) [Kao, C., Hwang, S.-N., 2008. Efficiency decomposition in two-stage data envelopment analysis: An application to non-life insurance companies in Taiwan. European Journal of Operational Research 185 (1), 418–429] develop a data envelopment analysis (DEA) approach for measuring efficiency of decision processes which can be divided into two stages. The first stage uses inputs to generate outputs which become the inputs to the second stage. The first stage outputs are referred to as intermediate measures. The second stage then uses these intermediate measures to produce outputs. Kao and Huang represent the efficiency of the overall process as the product of the efficiencies of the two stages. A major limitation of this model is its applicability to only constant returns to scale (CRS) situations. The current paper develops an additive efficiency decomposition approach wherein the overall efficiency is expressed as a (weighted) sum of the efficiencies of the individual stages. This approach can be applied under both CRS and variable returns to scale (VRS) assumptions. The case of Taiwanese non-life insurance companies is revisited using this newly developed approach.  相似文献   
182.
Several Ge(II) and Ge(IV) compounds were investigated as possible reagents for the electrodeposition of Ge from liquid CH(3)CN and CH(2)F(2) and supercritical CO(2) containing as a co-solvent CH(3)CN (scCO(2)) and supercritical CH(2)F(2) (scCH(2)F(2)). For Ge(II) reagents the most promising results were obtained using [NBu(n)(4)][GeCl(3)]. However the reproducibility was poor and the reduction currents were significantly less than the estimated mass transport limited values. Deposition of Ge containing films was possible at high cathodic potential from [NBu(n)(4)][GeCl(3)] in liquid CH(3)CN and supercritical CO(2) containing CH(3)CN but in all cases they were heavily contaminated by C, O, F and Cl. Much more promising results were obtained using GeCl(4) in liquid CH(2)F(2) and supercritical CH(2)F(2). In this case the reduction currents were consistent with mass transport limited reduction and bulk electrodeposition produced amorphous films of Ge. Characterisation by XPS showed the presence of low levels of O, F and C, XPS confirmed the presence of Ge together with germanium oxides, and Raman spectroscopy showed that the as deposited amorphous Ge could be crystallised by the laser used in obtaining the Raman measurements.  相似文献   
183.
A series of endohedral and exohedral amine-functionalized ligands were synthesized and used in the construction of supramolecular D(2h) rhomboids and a D(6h) hexagon. These supramolecular polygons were obtained via self-assembly of 120° dipyridyl donors with 180° or 120° diplatinum precursors when combined in 1:1 ratios. Steady-state absorption and emission spectra were collected for each ligand and metallacycle. Density functional theory (DFT) and time-dependent DFT calculations were employed to probe the nature of the observed optical transitions for the rhomboids. The emissive properties of these bis(phosphine) organoplatinum metallacycles arise from ligand-centered transitions involving π-type molecular orbitals with modest contributions from metal-based atomic orbitals. The D(2h) rhomboid self-assembled from 2,6-bis(4-pyridylethynyl)aniline and a 60° organoplatinum(II) acceptor has a low-energy excited state in the visible region and emits above 500 nm, properties which greatly differ from those of the parent 2,6-bis(4-pyridylethynyl)aniline ligand.  相似文献   
184.
TL Adamson  FA Eusebio  CB Cook  JT Labelle 《The Analyst》2012,137(18):4179-4187
Self-monitoring of blood glucose is the standard of care in management of hyperglycemia among patients with diabetes mellitus. To increase the sensitivity and specificity of current devices, a novel method of detecting glucose using electrochemical impedance spectroscopy (EIS) technology is explored. The enzyme glucose oxidase (GOx) was fixed to gold electrodes and a sine wave of sweeping frequencies was induced using a wide range of concentrations of glucose. Each frequency in the impedance sweep was analyzed for the highest response and R-squared value. The frequency with both factors optimized is specific for the glucose-GOx binding interaction and was determined to be 1.17 kHz in purified solutions in both higher and lower ranges of glucose. The correlation between the impedance response and concentration at the low range of detection (0-100 mg dL(-1) of glucose) was determined to be 3.53 ohm/ln (mg dL(-1)) with an R-squared value of 0.90 with a 39 mg dL(-1) lower limit of detection. The same frequency of 1.17 kHz was verified in whole blood under the same glucose range. The above data confirm that EIS offers a new method of glucose detection as an alternative to current technology in use by patients. Additionally, the unique frequency response of individual markers allows for modulation of signals so that several other markers important in the management of diabetes could be measured with a single sensor.  相似文献   
185.
The fragmentation behavior of the 2+ and 3+ charge states of eleven different phosphorylated tau peptides was studied using collision-induced dissociation (CID), electron transfer dissociation (ETD) and metastable atom-activated dissociation (MAD). The synthetic peptides studied contain up to two known phosphorylation sites on serine or threonine residues, at least two basic residues, and between four and eight potential sites of phosphorylation. CID produced mainly b-/y-type ions with abundant neutral losses of the phosphorylation modification. ETD produced c-/z-type ions in highest abundance but also showed numerous y-type ions at a frequency about 50% that of the z-type ions. The major peaks observed in the ETD spectra correspond to the charge-reduced product ions and small neutral losses from the charge-reduced peaks. ETD of the 2+ charge state of each peptide generally produced fewer backbone cleavages than the 3+ charge state, consistent with previous reports. Regardless of charge state, MAD achieved more extensive backbone cleavage than CID or ETD, while retaining the modification(s) in most cases. In all but one case, unambiguous modification site determination was achieved with MAD. MAD produced 15-20% better sequence coverage than CID and ETD for both the 2+ and 3+ charge states and very different fragmentation products indicating that the mechanism of fragmentation in MAD is unique and complementary to CID and ETD.  相似文献   
186.
It has been found that hydrogels may be formed by microwave irradiation of aqueous solutions containing appropriate combinations of polymers. This new method of hydrogel synthesis yields sterile hydrogels without the use of monomers, eliminating the need for the removal of unreacted species from the final product. Results for two particularly successful combinations, poly(vinyl alcohol) with either poly(acrylic acid) or poly(methylvinylether‐alt‐maleic anhydride), are presented. Irradiation using temperatures of 100–150 °C was found to yield hydrogels with large equilibrium swelling degrees of 500–1000 g g−1. Material leached from both types of hydrogel shows little cytotoxicity towards HT29 cells.  相似文献   
187.
Mechanisms for the reaction of thiophene and 2-methylthiophene with molecular oxygen on both the triplet and singlet potential energy surfaces (PESs) have been investigated using ab initio methods. Geometries of various stationary points involved in the complex reaction routes are optimized at the MP2/6-311++G(d, p) level. The barriers and energies of reaction for all product channels were refined using single-point calculations at the G4MP2 level of theory. For thiophene, CCSD(T) single point energies were also determined for comparison with the G4MP2 energies. Thiophene and 2-methylthiophene were shown to react with O(2) via two types of mechanisms, namely, direct hydrogen abstraction and addition/elimination. The barriers for reaction with triplet oxygen are all significantly large (i.e., >30 kcal mol(-1)), indicating that the direct oxidation of thiophene by ground state oxygen might be important only in high temperature processes. Reaction of thiophene with singlet oxygen via a 2 + 4 cycloaddition leading to endoperoxides is the most favorable channel. Moreover, it was found that alkylation of the thiophene ring (i.e., methyl-substituted thiophene) is capable of lowering the barrier height for the addition pathway. The implication of the current theoretical results may shed new light on the initiation mechanisms for combustion of asphaltenes.  相似文献   
188.
A novel and concise synthesis of optically active tryptophan derivatives was developed via a palladium-catalyzed heteroannulation reaction of substituted o-iodoanilines with an internal alkyne. The required internal alkyne 14a or 25 was prepared in greater than 96% de via alkylation of the Sch?llkopf chiral auxiliary 19 employing diphenyl phosphate as the leaving group. The Sch?llkopf chiral auxiliary was chosen here for the preparation of L-tryptophans would be available from D-valine while the D-isomers required for natural product total synthesis would originate from the inexpensive L-valine (300-g scale). Applications of the palladium-catalyzed heteroannulation reaction were extended to the first asymmetric synthesis of L-isotryptophan 38 and L-benz[f]tryptophan 39. More importantly, the optically pure 6-methoxy-D-tryptophan 62 was prepared by this protocol on a large scale (>300 g). This should permit entry into many ring-A oxygenated indole alkaloids when coupled with the asymmetric Pictet-Spengler reaction. In addition, an improved total synthesis of tryprostatin A (9a) was accomplished in 43% overall yield employing this palladium-mediated process.  相似文献   
189.
Section 1 is a brief introduction. Section 2 contains the basic definitions of quasimanuals, weights, and operational logics. The linear spaceW of all weights on a quasimanualA is introduced and given a norm.W with this norm is seen to be a Banach space. The subspaceV ofW generated by the positive cone ofW is given the base norm and is also shown to be an Archimedian ordered Banach space with an additive norm. In Section 3 normal linear functionals onV * are defined in analogy with normal linear functionals onw * algebras. The spaceV is shown to be the set of normal functionals onV * and we showV to be the unique partially ordered Banach space with a closed generating cone which is predual toV *. Next, weakly compact subsets ofW are characterized in terms of eventwise convergence. This is the Hahn-Vitali-Saks theorem of classical measure theory in this noncommutative setting; several weak compactness results are drawn from this and compared with their classical counterparts. Section 4 introduces the ultraweak topology forV * in analogy with the same for the trace class operators on Hubert space. Here the condition for a compact base for the cone ofV is examined and shown to be a poor and unnecessary hypothesis in many circumstances. Many connections with the existent literature are made and throughout the paper there are many examples and open questions.  相似文献   
190.
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