全文获取类型
收费全文 | 800篇 |
免费 | 0篇 |
专业分类
化学 | 513篇 |
力学 | 4篇 |
数学 | 1篇 |
物理学 | 282篇 |
出版年
2012年 | 46篇 |
2011年 | 82篇 |
2010年 | 10篇 |
2009年 | 1篇 |
2008年 | 67篇 |
2007年 | 68篇 |
2006年 | 90篇 |
2005年 | 72篇 |
2004年 | 56篇 |
2003年 | 39篇 |
2002年 | 29篇 |
2001年 | 26篇 |
2000年 | 37篇 |
1999年 | 7篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1996年 | 12篇 |
1995年 | 13篇 |
1994年 | 14篇 |
1993年 | 30篇 |
1992年 | 21篇 |
1991年 | 15篇 |
1990年 | 14篇 |
1989年 | 3篇 |
1988年 | 6篇 |
1987年 | 7篇 |
1986年 | 12篇 |
1985年 | 9篇 |
1982年 | 1篇 |
1948年 | 9篇 |
排序方式: 共有800条查询结果,搜索用时 812 毫秒
71.
We probed the local electronic properties of the mixed-valent Co+4-x triangular lattice in NaxCoO2.yH(2)O by 59Co NMR. We observed two distinct types of Co sites for x > or =1/2, but the valence seems averaged out for x approximately 1/3. Local spin fluctuations exhibit qualitatively the same trend down to approximately 100 K regardless of the carrier concentration x, and hence the nature of the electronic ground state. A canonical Fermi-liquid behavior emerges below approximately 100 K only for x approximately 1/3. 相似文献
72.
De Feyter S Abdel-Mottaleb MM Schuurmans N Verkuijl BJ van Esch JH Feringa BL De Schryver FC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(5):1124-1132
The two-dimensional ordering of a number of 2,2'-bipyridine derivatives at the liquid/solid interface has been investigated by scanning tunneling microscopy. By appropriate functionalization of the bipyridine units, their intermolecular distance can be tuned, which has proved to be crucial for complexation with metal ions. The in situ addition of metal salts (Pd(2+), Cu(2+)), leading to the formation of metal-bipyridine complexes, has a dramatic influence on the two-dimensional ordering of the molecules and suggests that these complexes could be used as templates. 相似文献
73.
Hung CH Chang FC Lin CY Rachlewicz K Stepień M Latos-Grazyński L Lee GH Peng SM 《Inorganic chemistry》2004,43(14):4118-4120
Iron and copper complexes of tetraphenyl-m-benziporphyrin (TPmBPH)H have been prepared and structurally characterized. The iron system, (TPmBPH)Fe(II)Br, contains a high-spin Fe(II) center. In the solid state the complex forms dimeric units linked by weak CH.Br hydrogen bonds. The Cu complex contains a tetrameric copper cluster with a Cu(2)Cl(4)(2)(-) unit bridging two [(TPmBPCl)Cu(II)](+) fragments. The formation of (TPmBPCl)H represents an example of copper-catalyzed chlorination on the internal carbon atom of (TPmBPH)H. 相似文献
74.
Electron-rich alkoxy- and chloro-substituted azaspirocyclic cyclohexadienyl Ru(II) complexes have been converted to either azaspiro[4.5]decane derivatives or functionalized tetrahydroisoquinolines by treatment with suitable oxidizing agents. Copper(II) chloride was found to provide demetalated products in high yield relative to the other oxidants examined (FeCl(3), DDQ, CAN, [Cp(2)Fe][PF(6)], phenyliodine diacetate, IBX). In certain instances, the efficiency of oxidative demetalation was enhanced by the inclusion of chloride ion additives in the reaction. Pyridinium dichromate (PDC) was also found to effect the demetalation of a wide range of cyclohexadienyl Ru complexes; however, isolated yields of metal-free products were exceedingly low. The cyclohexadienyl ruthenium complexes used in this study were prepared from (arene)Ru(II) precursors; thus, the isolation of alicyclic cyclohexadienone derivatives upon demetalation constitutes completion of a Ru-mediated dearomatization process. 相似文献
75.
Rigobert S Atalla N Sgard FC 《The Journal of the Acoustical Society of America》2003,114(5):2607-2617
Recently, a mixed pressure displacement [u, P] formulation based on Biot's poroelasticity equations has been presented for porous materials. This model leads to a reduction of the number of degrees of freedom required for the modeling of three-dimensional porous media in comparison to classical displacement-displacement [u, U] formulations. In this paper, an extension of the [u, P] formulation based on hierarchical elements is presented. First, a variant of the weak integral form of the [u, P] formulation is presented and its numerical implementation using hierarchical elements is detailed, together with the application of boundary and loading conditions. Numerical results are presented to show the accuracy and performance of the present approach. In particular, the importance of correctly capturing the coupling effects between the two phases is highlighted. 相似文献
76.
Small-world and scale-free networks are known to be more easily synchronized than regular lattices, which is usually attributed to the smaller network distance between oscillators. Surprisingly, we find that networks with a homogeneous distribution of connectivity are more synchronizable than heterogeneous ones, even though the average network distance is larger. We present numerical computations and analytical estimates on synchronizability of the network in terms of its heterogeneity parameters. Our results suggest that some degree of homogeneity is expected in naturally evolved structures, such as neural networks, where synchronizability is desirable. 相似文献
77.
Motivated by the practical consideration of the measurement of chaotic signals in experiments or the transmission of these signals through a physical medium, we investigate the effect of filtering on chaotic symbolic dynamics. We focus on the linear, time-invariant filters that are used frequently in many applications, and on the two quantities characterizing chaotic symbolic dynamics: topological entropy and bit-error rate. Theoretical consideration suggests that the topological entropy is invariant under filtering. Since computation of this entropy requires that the generating partition for defining the symbolic dynamics be known, in practical situations the computed entropy may change as a filtering parameter is changed. We find, through numerical computations and experiments with a chaotic electronic circuit, that with reasonable care the computed or measured entropy values can be preserved for a wide range of the filtering parameter. 相似文献
78.
Mass spectrometry and non-covalent protein-ligand complexes: confirmation of binding sites and changes in tertiary structure 总被引:2,自引:0,他引:2
Shields SJ Oyeyemi O Lightstone FC Balhorn R 《Journal of the American Society for Mass Spectrometry》2003,14(5):460-470
An experimental approach is described for determining protein-small molecule non-covalent ligand binding sites and protein conformational changes induced by ligand binding. The methodology utilizes time resolved limited proteolysis and the high throughput analysis capability of MALDI TOF MS to determine the binding site in a tetanus toxin C-fragment (51 kDa)-doxorubicin (543 Da) non-covalent complex. Comparing relative ion abundances of peptides released from the time resolved limited proteolysis of tetanus toxin C-fragment (TetC) and the TetC-doxorubicin complex every 10 min from 10 to 120 min of digestion revealed that the binding of doxorubicin induced a significant change in surface topology of TetC. Four of the twenty-nine peptides observed by MALDI MS, including amino acids 351-360, 299-304, 305-311 and 312-316, had a lower abundance in the TetC-doxorubicin complex relative to TetC from 10 to 100 min of digestion. A decrease in ion abundance suggests doxorubicin obstructs the access of the protease to one or both termini of these peptides, identifying doxorubicin binding site(s). Conversely, five peptide ions, including amino acids 335-350, 364-375, 364-376, 281-298, and 316-328, all had a greater abundance in the digest of the complex, indicating an increase in accessibility to these sites. These five peptides flank regions of decreased ion abundance, suggesting that doxorubicin not only binds to the surface, but also induces a conformational change in TetC. 相似文献
79.
Directional synthesis of a dye-linked conducting homopolymer 总被引:2,自引:0,他引:2
We report a new synthesis of a 10,20-diphenyl-5,15-bis(4-cyanophenyl)porphyrin (1) and its reduction to give 10,20-diphenyl-5,15-bis(4-formylphenyl)porphyrin (2). When the conducting polymer poly(2',5'-dioctyl-4,4' '-terphenylenecyanovinylene) was prepared in the presence of 2, we obtained a three-domain structure, compound 3, consisting of two homopolymer blocks (J domains) with the porphyrin dye molecule (P domain) in the middle. The JPJ assembly was subjected to photophysical studies where we showed that the J domain could serve as a light-harvesting antenna for the P domain. 相似文献
80.