全文获取类型
收费全文 | 173篇 |
免费 | 4篇 |
专业分类
化学 | 95篇 |
力学 | 11篇 |
数学 | 10篇 |
物理学 | 61篇 |
出版年
2022年 | 2篇 |
2021年 | 2篇 |
2020年 | 1篇 |
2019年 | 2篇 |
2018年 | 8篇 |
2016年 | 6篇 |
2015年 | 2篇 |
2014年 | 1篇 |
2013年 | 6篇 |
2012年 | 4篇 |
2011年 | 12篇 |
2010年 | 2篇 |
2009年 | 6篇 |
2008年 | 6篇 |
2007年 | 9篇 |
2006年 | 15篇 |
2005年 | 10篇 |
2004年 | 9篇 |
2003年 | 6篇 |
2002年 | 7篇 |
2001年 | 3篇 |
2000年 | 8篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1996年 | 4篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1986年 | 2篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 3篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1970年 | 1篇 |
排序方式: 共有177条查询结果,搜索用时 15 毫秒
91.
Gioia Lobbia G Hanna JV Pellei M Pettinari C Santini C Skelton BW White AH 《Dalton transactions (Cambridge, England : 2003)》2004,(6):951-958
Gold derivatives [Au(Tpx)(PR3)](Tpx = Tp, hydrotris(pyrazol-1-yl)borate or Tp*, hydrotris(3,5-dimethylpyrazol-1-yl)borate; R = Ph or tBu) and [Au(pzTp)(PR3)x](pzTp = tetrakis(pyrazol-1-yl)borate, x = 1 or 2, R = Ph or tBu) have been synthesised and characterized both in solution (1H- and 31P[1H]-NMR) and in the solid state (IR, single crystal X-ray structure analysis, 31P CPMAS). 31P [1H] NMR solution data suggest greater stability of the tetrakis(pyrazolyl)borate relative to those of tris(pyrazolyl)borate. All compounds are fluxional at room temperature. In order to compare [Au(Tp*)(PPh3)] with analogous coinage metal adducts we have synthesized and structurally characterized [Cu(Tp*)(PPh3)] x PPh3 and [Ag(Tp*)(PPh3)] x 2MeCN. In [Au(Tp*)(PPh3)] the gold atom adopts a distorted tetrahedral geometry with 2.181(5) and 2.37(2) angstroms (cf. 2.166(6), 2.098(1) in [Cu(Tp*)PPh3], 2.156(2), 2.075(7) in [Cu(Tp*)(PPh3)] x PPh3; and in [Ag(Tp*)PPh3] x MeCN 2.347(12), 2.35(5) angstroms). There are three independent [Au(Tp*)(PPh3)] molecules in the asymmetric unit of the structure with their PAu...B axes lying on the cell diagonal of a cubic P213 cell, two with the same chirality aligned opposed in direction to the third which is of opposite chirality. A number of Cu, Ag and Au complexes containing scorpionate ligands have also been investigated by 31P cross-polarization magic-angle-spinning (CPMAS) NMR spectroscopy. 相似文献
92.
93.
Antonello Santini Carlo Pedone Ettore Benedetti Carlo Silipo Antonio Vittoria Giuseppe Caliendo Giovanni Greco 《Structural chemistry》1994,5(3):183-188
(Z)-2-(2-phenylbenzylidene)-3-quinuclidinone, C20H19NO,M
r
=300.47D crystallizes in the monoclinicP21/c space group witha = 6.9809(2) Å,b=19.0523(2) Å,c = 11.7733(1) Å,=100.92(2)°,V=1537.5(3) Å3,Z=4,D
c
= 1.298 g/cm3,D
x
=1.29 g/cm3 (flotation). Diffractometric data, using CuK radiation,=1.54178 Å, were collected on plate-like crystals. The structure, solved by direct methods was refined to a final R value of 0.037 for the 2645 observed reflections withF
o
>3.0(F
o
). The molecule shows a trans conformation around the double bond. The quinuclidine and the diphenyl moieties present deformations in their geometric and conformational parameters due to the need of releasing intramolecular strains and/or nonbonded interactions. 相似文献
94.
The algebraic properties of exactly solvable evolution equations in one spatial and one temporal dimensions have been well studied. In particular, the factorization of certain operators, called recursion operators, establishes the bi-Hamiltonian nature of all these equations. Recently, we have presented the recursion operator and the bi-Hamiltonian formulation of the Kadomtsev-Petviashvili equation, a two spatial dimensional analogue of the Korteweg-deVries equation. Here we present the general theory associated with recursion operators for bi-Hamiltonian equations in two spatial and one temporal dimensions. As an application we show that general classes of equations, which include the Kadomtsev-Petviashvili and the Davey-Stewartson equations, possess infinitely many commuting symmetries and infinitely many constants of motion in involution under two distinct Poisson brackets. Furthermore, we show that the relevant recursion operators naturally follow from the underlying isospectral eigenvalue problems. 相似文献
95.
E. Benavidez L. Santini E. Brandaleze 《Journal of Thermal Analysis and Calorimetry》2011,103(2):485-493
Mold fluxes develop important functions during steel continuous casting process. To obtain a free-defect product the melting
rate of mold flux is an important property to be controlled. The melting rate depends on the reactivity of carbonaceous material
added to these powders as carbon source. In this article, the decomposition kinetic of two carbonaceous materials added to
mold flux: petroleum coke and synthetic graphite, was analyzed. By measuring mass loss at different heating rates the decomposition
reaction was determined on both types of materials. Applying several kinetic models of non-isothermal decomposition, the average
activation energy E = 48 kJ/mol to mold powder with 15 wt% coke and E = 67 kJ/mol to one with 15 wt% graphite was determined. A first order of reaction (n = 1) associated to the decomposition process was assumed to both types of materials. The lower activation energy presented
by mold powder-15 wt% petroleum coke indicated a higher reactivity of this material. A higher level of variation of E and n values with decomposition degree and temperature observed in the powder with petroleum coke was associated to a less thermally
stable material along with a more complex degradation process. 相似文献
96.
Pellei M Papini G Trasatti A Giorgetti M Tonelli D Minicucci M Marzano C Gandin V Aquilanti G Dolmella A Santini C 《Dalton transactions (Cambridge, England : 2003)》2011,40(38):9877-9888
New nitroimidazole and glucosamine conjugated heteroscorpionate ligands, namely 2,2-bis(3,5-dimethyl-1H-pyrazol-1-yl)-N-(2-(2-methyl-5-nitro-1H-imidazol-1-yl)ethyl)acetamide (L(MN)) and 1,3,4,6-tetra-O-acetyl-2-{[bis(3,5-dimethyl-1H-pyrazol-1-yl)acetyl]amino}-2-deoxy-β-D-glucopyranose (L(DAC)), respectively, were synthesized by direct coupling of preformed side chain acid and amine components. The related copper(II) complexes {[(L(MN))(2)Cu]Cl(2)}, and {[(L(DAC))(2)Cu]Cl(2)} have been prepared from the reaction of CuCl(2)*2H(2)O with L(MN) or L(DAC) ligand in methanol solution. Single crystal structural characterization was undertaken for the L(MN) ligand. In the absence of a coordinated metal core, the overall arrangement of the ligand is determined by some loose intra- and inter-molecular nonbonding contacts. X-Ray Absorption Spectroscopy (XAS) has been used to probe the local structure of the two copper(II) complexes, {[(L(MN))(2)Cu]Cl(2)} and {[(L(DAC))(2)Cu]Cl(2)}. The EXAFS analysis has permitted the identification of the local environment of the copper site. Copper interacts with 2 units of ligand in both complexes, and it is found to be 6-fold coordinated. Its local structure is described by four Cu-N and two Cu-O interactions to form a pseudo-octahedron core, with a 0.14 ? lengthening of the Cu-O bond length in the case of L(DAC) complex with respect to the L(MN) one, likely due to the higher steric hindrance of the glucosamine moiety. The XANES analysis agrees with these results, also confirming the Cu(II) formal copper oxidation state for both complexes. The new copper(II) complexes {[(L(MN))(2)Cu]Cl(2)} and {[(L(DAC))(2)Cu]Cl(2)} as well as the corresponding uncoordinated ligands were evaluated for their cytotoxic activity towards a panel of several human tumour cell lines. The results reported here indicate that both copper(II) complexes show similar spectra of cytotoxicity and very low resistance factors (RF < 2) against C13* ovarian cancer cells which have acquired resistance to cisplatin. 相似文献
97.
A relation giving a minimum for the irreversible work in quasi-equilibrium processes was derived by Sekimoto et al. [K. Sekimoto, S. Sasa, J. Phys. Soc. Japan 66 (1997) 3326] in the framework of stochastic energetics. This relation can also be written as a type of “uncertainty principle” in such a way that the precise determination of the Helmholtz free energy through the observation of the work 〈W〉 requires an indefinitely large experimental time Δt. In the present article, we extend this relation to the case of quasi-steady processes by using the concept of non-equilibrium Helmholtz free energy. We give a formulation of the second law for these processes that extends that presented by Sekimoto [K. Sekimoto, Prog. Theoret. Phys. Suppl. No. 130 (1998) 17] by a term of the first order in the inverse of the experimental time. As an application of our results, two possible experimental situations are considered: stretching of a RNA molecule and the drag of a dipolar particle in the presence of a gradient of electric force. 相似文献
98.
Giuseppe Failla Adolfo Santini Massimiliano Zingales 《Archive of Applied Mechanics (Ingenieur Archiv)》2013,83(2):253-272
Classical foundation models such as the Pasternak and the Reissner models have been recently reformulated within the framework of non-local mechanics, by using the gradient theory of elasticity. To contribute to the research effort in this field, this paper presents a two-dimensional foundation model built by using a mechanically based non-local elasticity theory, recently proposed by the authors. The foundation is thought of as an ensemble of soil column elements resting on an elastic base. It is assumed that each column element is acted upon by a local Winkler-like reaction force exerted by the elastic base, by contact shear forces and volume forces due, respectively, to adjacent and non-adjacent column elements. As in the Pasternak model, the contact shear forces involve the second-order derivative of the column element displacement. The volume forces are non-local forces assumed to depend (1) on the relative displacement between the interacting column elements through power-law distance-decaying attenuation functions and (2) on the product between the volumes of the interacting column elements. As a result, the equilibrium equations are fractional differential equations, for which a numerical solution can be readily found based on the finite difference method. Solutions are built for different foundation shapes and loading conditions. 相似文献
99.
Adaptive large neighborhood search (ALNS) is a useful framework for solving difficult combinatorial optimisation problems. As a metaheuristic, it consists of some components that must be tailored to the specific optimisation problem that is being solved, while other components are problem independent. The literature is sparse with respect to studies that aim to evaluate the relative merit of different alternatives for specific problem independent components. This paper investigates one such component, the move acceptance criterion in ALNS, and compares a range of alternatives. Through extensive computational testing, the alternative move acceptance criteria are ranked in three groups, depending on the performance of the resulting ALNS implementations. Among the best variants, we find versions of criteria based on simulated annealing, threshold acceptance, and record-to-record travel, with a version of the latter being consistently undominated by the others. Additional analyses focus on the search behavior, and multiple linear regression is used to identify characteristics of search behavior that are associated with good search performance. 相似文献
100.
Santini CM Hatton TA Hammond PT 《Langmuir : the ACS journal of surfaces and colloids》2006,22(18):7487-7498
The solution behavior of spherical dendrimers as well as hybrid-linear dendritic diblock copolymers has been extensively studied, and the size, shape, and ability of these polymers to encapsulate small molecules have led to their comparison with traditional micelles. We have recently reported the synthesis of a new dendritic copolymer architecture, the linear-dendritic rod diblock copolymer, and in this work, we examine the solution behavior of these unique polymers in methanol at 25 degrees C, using dynamic light scattering and intrinsic viscosity measurements. The diblock copolymers consist of a linear poly(ethylene oxide)-poly(ethylene imine) diblock copolymer backbone around which poly(amido amine) branches have been divergently synthesized from the poly(ethylene imine) block. The hydrodynamic radii and the viscometric radii of the polymers were found to increase slowly with increasing generation up to generation 3.5; however, after generation 3.5, the radii were found to increase very rapidly. This increase can be explained by an elongation of the dendritic block into a more rodlike configuration and a corresponding breakdown of the spherical approximation used to calculate the radii. The intrinsic viscosity of the amine and ester terminated polymers was found to follow two very different trends at low generation; however, at higher generations, they followed similar, yet slightly different, curves with the values for the amine terminated polymers only a little larger than those of the ester terminated polymers. At low generations, the chemistry of the end groups and its interaction with the solvent were found to be more important, whereas at higher generations, the highly branched nature of the dendritic block was the more important factor. For the ester terminated polymers, a maximum in the intrinsic viscosity occurred at generation 1.5. Since this maximum occurred at a much lower generation number than is traditionally seen for spherical dendrimers, new scaling relations for the intrinsic viscosity of dendritic rod polymers were developed and were found to support this observation. A minimum in the intrinsic viscosity was also observed at generation 3.5 for the ester terminated polymers and a minimum or leveling off in the intrinsic viscosity at generation 4.0 was found for the amine terminated polymers, which can be attributed to the transitioning of the polymers to a more elongated, rodlike shape and the increased influence of the shape factor on the intrinsic viscosity. 相似文献