全文获取类型
收费全文 | 467篇 |
免费 | 15篇 |
国内免费 | 7篇 |
专业分类
化学 | 361篇 |
晶体学 | 2篇 |
力学 | 10篇 |
数学 | 53篇 |
物理学 | 63篇 |
出版年
2023年 | 2篇 |
2022年 | 1篇 |
2021年 | 6篇 |
2020年 | 4篇 |
2019年 | 6篇 |
2018年 | 6篇 |
2017年 | 3篇 |
2016年 | 5篇 |
2015年 | 13篇 |
2014年 | 16篇 |
2013年 | 23篇 |
2012年 | 35篇 |
2011年 | 35篇 |
2010年 | 12篇 |
2009年 | 13篇 |
2008年 | 33篇 |
2007年 | 38篇 |
2006年 | 32篇 |
2005年 | 47篇 |
2004年 | 36篇 |
2003年 | 26篇 |
2002年 | 27篇 |
2001年 | 3篇 |
2000年 | 8篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1996年 | 1篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1990年 | 7篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1970年 | 1篇 |
1929年 | 1篇 |
排序方式: 共有489条查询结果,搜索用时 15 毫秒
91.
Lindquist WB 《Journal of colloid and interface science》2006,296(2):655-668
We show that arc menisci configuration under primary drainage in capillary tube cross sections and, by extension, in throats in the void structure of rock and soil, can be understood in terms of the computational geometry theory of medial axis analysis. The solution for arc meniscus configuration is developed for cross sections of arbitrary, simply connected polygonal shape at both entry- and over-pressure values during primary drainage for arbitrary values of wetting angle. Using this solution technique, we have obtained highly accurate solutions of entry pressure arc meniscus radius for over 21,500 throats obtained from analysis of computed tomography images in a suite of 4 Fontainebleau core samples ranging from 7.5 to 22% porosity. We show that the ratio A/P, of throat area to throat perimeter, is an excellent predictor of entry pressure meniscus radius (and hence entry pressure) for primary drainage for real pores, while inscribed radius and area equivalent radius over-predict entry pressure meniscus radius by factors of 1.5-3, and are consequently poor predictors. 相似文献
92.
Anti-markovnikov N-H and O-H additions to electron-deficient olefins catalyzed by well-defined Cu(I) anilido, ethoxide, and phenoxide systems 总被引:1,自引:0,他引:1
The monomeric Cu(I) complexes (IPr)Cu(Z) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, Z = NHPh, OEt, or OPh) react with YH (Y = PhNH, PhCH2NH, EtO, or PhO) to catalytically add Y-H bonds across the C=C bond of electron-deficient olefins to yield anti-Markovnikov organic products. Catalytic activity has been observed for olefins CH2C(H)(X) with X = CN, C(O)Me, or CO2Me as well as crotononitrile. Preliminary studies implicate an intermediate in which the C-Y bond forms through a nucleophilic addition pathway. 相似文献
93.
Two new charge-scaling methods for efficient modeling of the solvated macromolecular environment in hybrid QM/MM calculations of biological reactions are presented. The methods are extensions of the variational electrostatic projection (VEP) method, and allows a subset of atomic charges in the external environment to be adjusted to mimic, in the active dynamical region, the electrostatic potential and field due to the large surrounding macromolecule and solvent. The method has the advantages that it offers improved accuracy, does not require the use of a three-dimensional grid or auxiliary set of fitting points, and requires only minor molecular simulation code modifications. The VEP-cs and VEP-RVM+cs methods are able to attain very high accuracy (relative force errors of 10(-7) or better with appropriate choice of control parameters), and take advantage of a recently introduced set of high-order discretization schemes and Gaussian exponents for boundary element solvation and VEP methods. The methods developed here serve as potentially powerful tools in the arsenal of computational techniques used in multiscale computational modeling problems. 相似文献
94.
Workie DW Dardzinski BJ Graham TB Laor T Bommer WA O'Brien KJ 《Magnetic resonance imaging》2004,22(9):1201-1210
Improved management of arthritis requires a reliable, quantifiable, noninvasive method to monitor the degree of inflammation and therapeutic response during the early phase of the disease. For this purpose, the uptake of Gd-DTPA in the distal femoral physis and synovium in children with juvenile rheumatoid arthritis (JRA) was evaluated with a two-compartment pharmacokinetic model and dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI). Employing a two-compartment pharmacokinetic model, the theoretical signal enhancement from Gd-DTPA enhanced dynamic 3D gradient-recalled echo (GRE) images was shown to have a simple linear relationship with tissue concentration independent of flip angle. The signal-enhancement patterns for each individual knee were found to be characterized by three pharmacokinetic parameters: k(ep) (min(-1)), the rate constant; k(el) (min(-1)), the elimination rate constant; and E(R) (min(-1)), the initial enhancement rate, which is proportional to the transfer constant K(trans) (min(-1)). Characteristic patterns were observed in the image signal intensity-time course. The initial enhancement rate, E(R), in regions of interest (ROIs) was found to have a wide range of variation: 5 to 38 min(-1) over the distal femoral physis and 1 to 10 min(-1) in the synovium. The E(R) of the synovium was correlated with the E(R) of the distal femoral physis (P<.05). In addition, the E(R) of the synovium was correlated to the clinical outcome measures of knee swelling. Further investigation is needed to determine whether wide variations in the pharmacokinetic parameters reflect the degree of disease activity, and whether there are changes in response to therapy. This method can also be applied in adults with rheumatoid arthritis (RA) and other disorders where T(1)-weighted contrast is used (breast cancer, brain tumors). 相似文献
95.
Deng J Farmer-Creely CE Viers BD Esker AR 《Langmuir : the ACS journal of surfaces and colloids》2004,20(7):2527-2530
A trisilanol derivative of polyhedral oligomeric silsesquioxane (POSS), trisilanolisobutyl-POSS, has recently been reported to form stable monolayers at the air/water interface. This paper explores the mono- and multilayer properties of another POSS derivative, trisilanolcyclohexyl-POSS, with pi-A isotherm and Brewster angle microscopy measurements. Results show that with continuously increasing surface concentration via symmetrical compression, trisilanolcyclohexyl-POSS amphiphiles at the air/water interface undergo a series of phase transitions from traditional Langmuir monolayers (one-POSS-molecule thick) to unique rodlike hydrophobic aggregates in multilayer films (approximately eight-POSS-molecules thick) that are dramatically different from "collapsed" morphologies seen in other systems. Stable and hydrophobic rodlike structure formation on water is presumably due to trisilanolcyclohexyl-POSS' unique molecular structure and strong tendency to form intermolecular hydrogen bonds in the solid state. This result is consistent with existing POSS/polymer composite research, which shows that POSS molecules tend to aggregate and crystallize into lamellar nanocrystals. 相似文献
96.
Brent Pohlmann 《Annals of Combinatorics》2012,16(3):609-624
We introduce the notions of boundary vertex, linear equivalence, and effective boundary vertex in the context of Viennot??s heaps of pieces. We prove that in the heap of a fully commutative element in a star reducible Coxeter group, every boundary vertex is linearly equivalent to an effective boundary vertex. 相似文献
97.
Pensini E Yip CM O'Carroll DM Sleep BE 《Langmuir : the ACS journal of surfaces and colloids》2012,28(28):10453-10463
The transport of particles through groundwater systems is governed by a complex interplay of mechanical and chemical forces that are ultimately responsible for binding to geological substrates. To understand these forces in the context of zero valent iron particles used in the remediation of groundwater, atomic force microscopy (AFM)-based force spectroscopy was employed to characterize the interactions between AFM tips modified with either carbonyl iron particles (CIP) or electrodeposited Fe as a function of counterion valency, temperature, particle morphology, and age. The measured interaction forces were always attractive for both fresh and aged CIP and electrodeposited iron, except in 100 mM NaCl, as a consequence of electrostatic attraction between the negatively charged mica and positively charged iron. In 100 mM NaCl, repulsive hydration forces appeared to dominate. Good agreement was found between the experimental data and predictions based on the extended DLVO (XDLVO) theory. The effect of aging on iron particle composition and morphology was assessed by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) revealing that the aged particles comprising a zero valent iron core passivated by a mixture of iron oxides and hydroxides. Force spectroscopy showed that aging caused variations in the adhesive force due to the changes in particle morphology and contact area. 相似文献
98.
Abstract
The protonation of tetraphenylporphyrin followed by spectrophotometric detection of the resulting dihydrogen tetraphenylporphyrin dication has been evaluated as a means to determine micromolar concentrations of strong acids in chloroform. The equilibrium constants for the process are large (>1010 for benzenesulfonic and methanesulfonic acids), but not large enough to ensure stoichiometric conversion to the dication unless only order of magnitude precision is required. The incorporation of a correction term in the stoichiometric approximation, based on a dilution of the analytical sample, yields an acceptable result for these two acids. 相似文献99.
Glenn R. Morello Thomas R. Cundari T. Brent Gunnoe 《Journal of organometallic chemistry》2012,697(1):15-22
Computational methods are used to investigate catalytic hydrophenylation of ethylene using complexes of the type [(Y)M(L)(CH3)(NCMe)]n+ [Y = Mp, n = 1; Y = Tp, n = 0; M = Ru or Os; L = PMe3, PF3, or CO; Mp = tris(pyrazolyl)methane; Tp = hydrido-tris(pyrazolyl)borate]. The conversion of ethylene and benzene to ethylbenzene with [(Y)M(L)(Ph)]n+ as catalyst involves four steps: (1) ethylene coordination, (2) ethylene insertion into the M–Ph bond, (3) benzene coordination, and (4) benzene C–H activation. DFT calculations form the basis to compare stoichiometric benzene C–H activation by [(Y)M(L)(CH3)(NCMe)]n+ complexes to yield methane and [(Y)M(L)(Ph)(NCMe)]n+. In addition, starting from the 16-electron species [(Y)M(L)(Ph)]n+, potential energy surfaces for the formation of ethylbenzene are calculated to reveal the impact of modifications to the scorpionate ligand (Mp or Tp), co-ligand (L) and metal center (M). 相似文献
100.
The near field signal redundancy algorithm for phase-aberration correction is sensitive to tissue motion because several separated transmissions are usually needed to acquire a set of common-midpoint signals. If tissues are moving significantly due to, for example, heart beats, the effects of tissue motion on common-midpoint signals need to be corrected before the phase-aberration profile can be successfully measured. Theoretical analyses in this paper show that the arrival-time difference between a pair of common-midpoint signals due to tissue motion is usually very similar to that between the pair of reciprocal signals acquired using the same two transmissions. Based on this conclusion, an algorithm for correcting tissue-motion effects on the peak position of cross-correlation functions between common-midpoint signals is proposed and initial experimental results are also presented. 相似文献