全文获取类型
收费全文 | 123篇 |
免费 | 5篇 |
国内免费 | 1篇 |
专业分类
化学 | 65篇 |
力学 | 4篇 |
数学 | 36篇 |
物理学 | 24篇 |
出版年
2023年 | 2篇 |
2022年 | 2篇 |
2021年 | 2篇 |
2020年 | 2篇 |
2019年 | 1篇 |
2018年 | 3篇 |
2017年 | 2篇 |
2016年 | 7篇 |
2015年 | 2篇 |
2014年 | 2篇 |
2013年 | 9篇 |
2012年 | 4篇 |
2011年 | 3篇 |
2010年 | 10篇 |
2009年 | 4篇 |
2008年 | 7篇 |
2007年 | 3篇 |
2006年 | 10篇 |
2005年 | 4篇 |
2004年 | 8篇 |
2003年 | 4篇 |
2002年 | 4篇 |
2001年 | 2篇 |
2000年 | 5篇 |
1999年 | 2篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1992年 | 2篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1966年 | 1篇 |
1965年 | 2篇 |
1963年 | 1篇 |
1962年 | 1篇 |
排序方式: 共有129条查询结果,搜索用时 234 毫秒
1.
We have developed bond additivity correction (BAC) procedures for the G3-based quantum chemistry methods, G3B3 and G3MP2B3. We denote these procedures as BAC-G3B3 and BAC-G3MP2B3. We apply the procedures to compounds containing atoms from the first three rows of the periodic table including H, B, C, N, O, F, Al, Si, P, S, and Cl atoms. The BAC procedure applies atomic, molecular, and pairwise bond corrections to theoretical heats of formation of molecules. The BAC-G3B3 and BAC-G3MP2B3 procedures require parameters for each atom type but not for each bond type. These parameters have been obtained by minimizing the error between the BAC-G3B3 and BAC-G3MP2B3 predictions and the experimental heats of formation for a 155 molecule reference set, containing open and closed shell molecules representing various functional groups, multireference configurations, isomers, and degrees of saturation. As compared to former BAC-MP4, BAC-G2, and BAC-hybrid methods, BAC-G3B3 provides better agreement with experiment for a wider range of chemical moieties, including highly oxidized species involving SOx s, NOx s, POx s, and halogens. The BAC-G3B3 and BAC-G3MP2B3 procedures are applied to an extended test suite involving 273 compounds. We assess the overall quality of BAC-G3B3 with experiments and other theoretical approaches. For the reference set, the average error for the BAC-G3B3 results is 0.44 kcal/mol as compared to 0.82 kcal/mol for the raw G3B3. For the extended test set, the average error for the BAC-G3B3 results is 0.91 kcal/mol as compared to 1.38 kcal/mol for the raw G3B3. As compared to the other BAC procedures, the improved predictive capability of BAC-G3B3 and BAC-G3MP2B3 procedures is, to a large extent, due to the improved quality of G3-based methods resulting in much smaller BAC correction terms. 相似文献
2.
A highly sensitive and selective spectrofluorimetric method for the determination of 0.05-2.00 mug germanium is described. Germanium is treated with chromotropic acid at pH 2.5 and the resultant anionic complex is extracted as an ion pair with rhodamine into toluene. Addition of butanol to the organic extract releases the fluorescent dye and facilitates its measurement at 570 nm after exciting at 540 nm. The method provides a detection limit of 0.003 mug ml(-1) and is virtually free from interference from extraneous ions. The relative standard deviaiton is 2.9% for ten determinations of 1.0 mug germanium. The method has been applied to the determination of germanium in various ores, minerals and rock samples. 相似文献
3.
Reaction of aminosilanetriol RSi(OH)(3) (1) (R = (2,6-i-Pr(2)C(6)H(3))N(SiMe(3))) with diethyl zinc at room temperature in 1:1 stoichiometric ratio affords [(THF)Zn(O(2)(OH)SiR)](4) (2) (R = (2,6-i-Pr(2)C(6)H(3))N(SiMe(3))) in good yield. The single-crystal X-ray diffraction studies reveal that 2 is monoclinic, P2(1), with a = 17.117(3) A, b = 16.692(5) A, c = 17.399(4) A, alpha = gamma = 90 degrees, beta = 91.45(7) degrees, and Z = 2. The molecular structure of 2 contains two puckered eight-membered Zn(2)Si(2)O(4) rings, which are connected by the Zn-O bonds and form two planar four-membered Zn(2)O(2) rings. Compound 2 contains an unreacted hydroxyl group on each silicon atom, and hence, we carried out the reactions of 2 with dimethylzinc and methyllithium to form [Zn(4)(THF)(4)(MeZn)(4)(O(3)SiR)(4)] (3) (R = (2,6-i-Pr(2)C(6)H(3))N(SiMe(3))) and [(L)ZnLi(O(3)SiR)](4) (4) (L = 1,4-(Me(2)N)(2)C(6)H(4), R = (2,6-i-Pr(2)C(6)H(3))N(SiMe(3))), respectively. This suggested that 2 could be an intermediate product formed during the synthesis of 3 and 4. 相似文献
4.
Summary Compounds of composition TiCl4–n(OPh)n · 2L (L = monodentate ligand, n = 1–4) have been prepared by the reaction of the parent titanium phenoxides (1 mol) with the ligand (2 mols) and characterized by elemental analysis, molar conductance, molecular weight and i.r. spectral studies. 相似文献
5.
In this paper, the transport of Cu(II) in the presence of lipophilic Cu(II) organic complexes through permeation liquid membranes (PLMs) have been investigated. In natural waters, small organic compounds, which form liposoluble neutral complexes with Cu(II), are potentially toxic and bioavailable. Hence, to understand the role of liposoluble Cu(II) complexes in natural waters, four organic ligands: phthalic acid, bipyridyl, pyrocatechol and hydroxyquinoline, which form uncharged or lipophilic Cu(II) complexes, were tested. The results showed that the transport of lipophilic Cu(II) complexes through PLM depends on the lipophilicity of the complex. Applications of PLMs in natural waters are presented. 相似文献
6.
Senoy Thomas D. Sakthikumar Yasuhiko Yoshida M. R. Anantharaman 《Journal of nanoparticle research》2008,10(1):203-206
Sol–gel glasses with Fe3O4 nanoparticles having particle sizes laying in the range 10–20 nm were encapsulated in the porous network of silica resulting
in nanocomposites having both optical and magnetic properties. Spectroscopic and photoluminescence studies indicated that
Fe3O4 nanocrystals are embedded in the silica matrix with no strong Si–O–Fe bonding. The composites exhibited a blue luminescence.
The optical absorption edge of the composites red shifted with increasing concentration of Fe3O4 in the silica matrix. There is no obvious shift in the position of the luminescence peak with the concentration of Fe3O4 except that the intensity of the peak is decreased. The unique combinations of magnetic and optical properties are appealing
for magneto–optical applications. 相似文献
7.
We study fluctuations in the force at the boundary of a 2D granular flow. The forces are mainly impulsive at all flow rates. The probability distribution of impulses decays exponentially at large impulses, as do the forces in a static granular medium. At small impulses, the distribution evolves continuously with flow rate with no indication of the transition from collisional flow to intermittently jamming flows. However, the distribution of the time interval between collisions tends to a power law, P(tau) - tau(-3/2), showing a clear dynamical signature of the approach to jamming. 相似文献
8.
The rate constants of O2(1Δg) with aliphatic alcohols, terpenes, unsaturated hydrocarbons, chlorinated hydrocarbons, oxygen, and diamines have been studied in thepresence of NO2. The rate constants for oxygen, 1,2-ethane diamine, and 1,2-propane diamine are (9.9 ± 0.4) × 102, (8.7 ± 0.7) × 104, and (1.4 ± 0.3) × 104 1/mol/s, respectively. The rate constants for all other compounds are less than the oxygen rate constant. 相似文献
9.
A. Stephen K. Hashmi Prof. Dr. Christian Lothschütz Dipl.‐Chem. Martin Ackermann Dipl.‐Chem. René Doepp Dipl.‐Chem. Sankaran Anantharaman Benjamin Marchetti Dipl.‐Chem. Helmut Bertagnolli Prof. Dr. Frank Rominger Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(27):8012-8019
Gold complexes were prepared and investigated as catalysts for the oxidative esterification of aldehydes. Stabilisation by pyridine ligands gave good conversions and the in situ extended X‐ray absorption fine structure (EXAFS) study of the reactions indicated that the reaction mixtures contained only mononuclear gold species. Thus, this is the first proof for a homogeneous gold‐catalysed oxidation reaction; the presence of nanoparticles could be excluded experimentally. 相似文献
10.
R. Murugavel G. Anantharaman D. Krishnamurthy M. Sathiyendiran M. G. Walawalkar 《Journal of Chemical Sciences》2000,112(3):273-290
This article describes the recent results obtained in our laboratory on the interaction of polyfunctional ligands with divalent
alkaline earth metal ions and a few divalent transition metal ions. Treatment of MC12·nH2O (M = Mg, Ca, Sr or Ba) with 2-amino benzoic acid leads to the formation of complexes [Mg(2-aba)2] (1), [Ca(2-aba)2(OH2)3]∞ (2), [Sr(2-aba)2(OH2)2
2·H2O)]∞ (3), [Ba(2-aba)2(OH2)]∞ (4), respectively. While the calcium ions in2 are hepta-coordinated, the strontium and barium ions in3 and4 reveal a coordination number of nine apart from additional metal-metal interactions. Apart from the carboxylate functionality,
the amino group also binds to the metal centres in the case of strontium and barium complexes3 and4. Complexes [Mg(H2O)6(4-aba)2·2H2O] (5), [Ca(4-aba)2(H2O)2] (6) prepared from 4-aminobenzoic acid reveal more open or layered structures. Interaction of 2-mercaptobenzoic acid with MCl2·6H2O (M = Mg, Ca), however, leads to the oxidation of the thiol group resulting in the disulphide 2,2′ -dithiobis(benzoic acid).
New metal-organic framework based hydrogen-bonded porous solids [M(btec) (OH2)4
n·n(C4H12N2)·4nH2O] (btec = 1,2,4,5-benzene tetracarboxylate) (M = Co9; Ni10; Zn11) have been synthesized from 1,2,4,5-benzene tetracarboxylic acid in the presence of piperazine. These compounds are made up
of extensively hydrogen-bonded alternating layers of anionic M-btec co-ordination polymer and piperazinium cations. Compounds2- 11 described herein form polymeric networks in the solid-state with the aid of different coordinating capabilities of the carboxylate
anions hydrogen bonding interactions. 相似文献