全文获取类型
收费全文 | 3128篇 |
免费 | 156篇 |
国内免费 | 2篇 |
专业分类
化学 | 2316篇 |
晶体学 | 45篇 |
力学 | 85篇 |
数学 | 408篇 |
物理学 | 432篇 |
出版年
2023年 | 26篇 |
2022年 | 23篇 |
2021年 | 38篇 |
2020年 | 54篇 |
2019年 | 54篇 |
2018年 | 58篇 |
2017年 | 55篇 |
2016年 | 114篇 |
2015年 | 82篇 |
2014年 | 94篇 |
2013年 | 216篇 |
2012年 | 264篇 |
2011年 | 272篇 |
2010年 | 148篇 |
2009年 | 130篇 |
2008年 | 226篇 |
2007年 | 218篇 |
2006年 | 170篇 |
2005年 | 169篇 |
2004年 | 155篇 |
2003年 | 111篇 |
2002年 | 109篇 |
2001年 | 76篇 |
2000年 | 85篇 |
1999年 | 52篇 |
1998年 | 42篇 |
1997年 | 23篇 |
1996年 | 33篇 |
1995年 | 17篇 |
1994年 | 23篇 |
1993年 | 15篇 |
1992年 | 18篇 |
1991年 | 14篇 |
1990年 | 9篇 |
1989年 | 12篇 |
1988年 | 12篇 |
1987年 | 6篇 |
1986年 | 9篇 |
1985年 | 11篇 |
1984年 | 9篇 |
1983年 | 8篇 |
1982年 | 4篇 |
1980年 | 4篇 |
1978年 | 1篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1973年 | 4篇 |
1969年 | 1篇 |
1925年 | 1篇 |
排序方式: 共有3286条查询结果,搜索用时 218 毫秒
101.
Fandos R Hernández C Otero A Rodríguez A Ruiz MJ Terreros P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(3):671-677
Titanium complexes with chelating alkoxide ligands [TiCp*(O(2)Bz)(OBzOH)] (1) and [TiCp*(Me)((OCH(2))(2)Py)] (2) were synthesised by reaction of [TiCp*Me(3)] (Cp*=eta(5)-C(5)Me(5)) with 2-hydroxybenzyl alcohol ((HO)(2)Bz) and 2,6-pyridinedimethanol ((HOCH(2))(2)Py), respectively. Complex 1 reacts with [(M(mu-OH)(cod))(2)] (M=Rh, Ir) to yield the early-late heterobimetallic complexes [TiCp*(O(2)Bz)(2)M(cod)] [M=Rh (3), Ir (4)]. Carbon monoxide readily replaces the COD ligand in 3 to give the rhodium dicarbonyl derivative [TiCp*(O(2)Bz)(2)Rh(CO)(2)] (5). Compound 2 reacts with [(M(mu-OH)(cod))(2)] (M=Rh, Ir) with protonolysis of a Tibond;Me bond to give [TiCp*((OCH(2))(2)Py)(mu-O)M(cod)] [M=Rh (6), Ir (7)]. The molecular structures of complexes 3, 5 and 7 were established by single-crystal X-ray diffraction studies. 相似文献
102.
J. Doménech E. Brillas J. A. Garrido R. M. Rodríguez 《Monatshefte für Chemie / Chemical Monthly》1987,118(2):197-202
Viscosities and densities of lithium perchlorate solutions in different ethylene glycol-water compositions have been measured at 25.0 and 35.0 °C. From these data, the correspondingB-coefficients of theJones-Dole equation have been determined. TheB-value depends on the solvent composition and it reaches a maximum in the water-rich region. This behaviour is analysed in terms of ionic solvation and solvent structure.
Viskositäts-B-Koeffizienten für Lösungen von Lithiumperchlorat in Ethylenglykol-Wasser-Mischungen
Zusammenfassung Es wurden die Dichten und Viskositäten für Lösungen von Lithiumperchlorat in verschieden zusammengesetzten Ethylenglykol-Wasser-Mischungen bei 25 °C und 35 °C gemessen. Auf Grund der erhaltenen Daten wurden dieB-Koeffizienten in den entsprechendenJones-Dole-Gleichungen für die relative Viskosität bestimmt. DieB-Werte hängen von der Zusammensetzung des Lösungsmittels ab und erreichen im wasserreichen Konzentrationsgebiet ein Maximum. Dieses Verhalten wird in Hinblick auf die Ionensolvatation und die Struktur des Lösungsmittels analysiert.相似文献
103.
Cabaleiro-Lago EM Rodríguez-Otero J Varela-Varela SM Peña-Gallego A Hermida-Ramón JM 《The Journal of organic chemistry》2005,70(10):3921-3928
[reactions: see text] Electrocyclization reactions of (3Z)-1,3,5-hexatrienone and nitrogen derivatives were studied by performing density functional theory (DFT) calculations together with the 6-31+G* basis set. Reactants, products, and transition states for each reaction were localized and the IRC connecting reactants and products was also obtained. Magnetic properties were evaluated along the reaction path to elucidate the characteristics of the reactions studied. As obtained from the calculations, electrocyclization of (3Z)-1,3,5-hexatrienone is a pericyclic process, as indicated by a variety of indexes, such as Nucleus Independent Chemical Shift (NICS), anisotropy of the magnetic susceptibility, or anisotropy of the current-induced density (ACID). This reaction presents characteristics of pericyclic reactions despite the activation energy lowering relative to the electrocyclization of (4Z)-1,2,4,6-heptatetraene, and the relatively small NICS values observed in the transition state. Magnetic properties indicate that an enhancement of the aromaticity relative to reactants and products occurs revealing the absence of orbital disconnections on the cyclic loop of interacting orbitals. Only two reactions among those studied exhibit pseudopericyclic character due to the in-plane attack of the lone pair on nitrogen. In these cases, the reactions showed no barrier for the electrocyclization process, and no aromaticity enhancement was observed. 相似文献
104.
del Mar Graciani M Rodríguez A Muñoz M Moyá ML 《Journal of colloid and interface science》2001,235(2):260-264
The reaction of dehydrobromination of 2-(p-nitrophenyl)ethyl bromide with hydroxide ions has been studied in aqueous micellar solutions of N-tetradecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate, SB3-14. The kinetic effects of added salts (NaF, NaCl, NaBr, and NaNO(3)) on the reaction rate in SB3-14 aqueous micellar solutions have also been studied. They were rationalized by considering the binding of the anions, which come from the salt, to the sulfobetaine micelles and their competition with the reactive hydroxide ions for the micellar surface. The equilibrium binding constant of the 2-(p-nitrophenyl)ethyl bromide to the sulfobetaine micelles was estimated by recording the changes in the spectra of the organic substrate when the SB3-14 concentration in the micellar medium changed. This value was in agreement with that obtained from fitting of kinetic data. The second-order rate constant in the micellar pseudophase revealed that the reaction is faster in SB3-14 micelles than in water. This acceleration seems independent of the presence of added salts and can be explained by considering that SB3-14 micelles favor reactions in which charge is delocalized in the transition state. Copyright 2001 Academic Press. 相似文献
105.
Canosa P Morales S Rodríguez I Rubí E Cela R Gómez M 《Analytical and bioanalytical chemistry》2005,383(7-8):1119-1126
The degradation of 2-(2,4-dichlorophenoxy)-5-chlorophenol (triclosan) in chlorinated water samples was investigated. Sensitive
determination of the parent compound and its transformation products was achieved by gas chromatography with mass spectrometry
detection after sample concentration, using a solid-phase extraction sorbent and silylation of the target compounds. Experiments
were accomplished using ultrapure water spiked with chlorine and triclosan concentrations in the low mg/l and ng/ml ranges
respectively. Chlorination of the phenolic ring and cleavage of the ether bond were identified as the main triclosan degradation
pathways. Both processes led to the production of two tetra- and a penta-chlorinated hydroxylated diphenyl ether, as well
as 2,4-dichlorophenol. The formation of 2,3,4-trichlorophenol was not detected in any experiment; however, significant amounts
of 2,4,6-trichlorophenol were noticed. All of these five compounds were also identified when triclosan was added to tap-water
samples with free chlorine concentrations below 1 mg/l. Minor amounts of three di-hydroxylated phenols, containing from one
to three atoms of chlorine in their structures, were also identified as unstable triclosan chlorination by-products. The analysis
of several raw wastewater samples showed the co-existence of important concentrations of triclosan and its most stable by-products
(2,4-dichlorophenol and 2,4,6-trichlorophenol), reinforcing the potential occurrence of the described transformations when
products containing triclosan are mixed with chlorinated tap water. 相似文献
106.
Hernández-Borges J Rodríguez-Delgado MA García-Montelongo FJ Cifuentes A 《Electrophoresis》2005,26(20):3799-3813
Chiral separation of enantiomers is one of the most challenging tasks for any analytical technique including CE. Since the first report in 1985 showing the great possibilities of CE for the separation of chiral compounds, the amount of publications concerning this topic has quickly increased. Although chiral electromigration methods have mainly been used for enantioseparation of drugs and pharmaceuticals, they have also been applied to analyze chiral pollutants. This article intends to provide an updated overview, including works published till January 2005, on the principal applications of CE to the chiral analysis of pollutants and their metabolites, with special emphasis on articles published in the last 10 years. The main advantages and drawbacks regarding the use of CE for chiral separation of pollutants are addressed including some discussion on the foreseen trends of electromigration procedures applied to chiral analysis of contaminants. 相似文献
107.
Rodríguez Flores J Berzas Nevado JJ Durán Merás I Rodríguez Gómez MJ 《Journal of separation science》2005,28(7):658-664
A capillary zone electrophoresis (CZE) method using a fused-silica capillary (60.2 cm x 75 microm ID) was investigated for the determination of triamterene (TRI), methotrexate (MTX), and creatinine (CREA) in human urine. The separation was performed using a hydrodynamic injection time of 7 s (0.5 psi), a voltage of 25 kV, a capillary temperature of 30 degrees C, and 40 mM phosphoric acid adjusted to pH 2.25 by addition of triethanolamine as separation electrolyte. Under these conditions, analysis takes about 15 min. A linear response over the 0.5-15.0 mg L(-1) concentration range was found for TRI and MTX, and 0.5-80.0 mg L(-1) for CREA. Dilution of the sample (water:urine, 1:1 for TRI and MTX, and 1:25 for CREA determination) was the only step necessary prior to analysis by electrophoresis. The developed method is easy, rapid, and sensitive and has been applied to determine triamterene,methotrexate, and creatinine in urine samples with satisfactory results. 相似文献
108.
M. T. Fernández-Díaz J. Rodríguez-Carvajal J. L. Martínez G. Fillion F. Fernández R. Saez-Puche 《Zeitschrift für Physik B Condensed Matter》1991,82(2):275-282
Neutron powder diffraction and magnetization measurements have been performed in stoichiometric Pr2NiO4+(0), which at room temperature (RT) is orthorhombic (Bmab). Ni2+ becomes three dimensionally (3D) antiferromagnetically ordered atT
N
325K, with a propagation vectork=[100], and spins oriented along thea axis (parallel to the propagation vector). The magnetic structure belongs to the
7g
(––+)-representation (g
x
mode, Shubnikov groupB
pmab') ofBmab, and a magnetic moment of 1.5
B
is measured at 155K. This compound undergoes two different structural phase transitions. First, going down in temperature, Pr2NiO4 transforms by a first order phase transition from orthorhombic (Bmab) to tetragonal (P42/ncm) atT
c1115K. At high temperature, we can predict a transformation from orthorhombic (Bmab) to tetragonal (I4/mmm) in a continuous way. The extrapolated temperature for this second structural transition isT
c21500±100K. The low temperature structural transformation allows a change in the magnetic structure which forT<T
c1 is better described in the orthorhombic symmetry. Just belowT
c1 the magnetic structure is described by the:
3g
(–+)-representation ofPccn(gxcyfz mode, Shubnikov groupPccn), this magnetic phase begins to disappear going down in temperature and at the same time a new magnetic phase grows. This new magnetic structure is described by the
1g
ofPccn (c
xgyaz mode, Shubnikov groupPccn). Both magnetic structures coexist in a certain temperature range. At 1.5 K thec
xgyaz mode represents the total of the magnetic ordering. To reproduce the observed magnetic intensities we are forced to consider that Pr3+ is polarized below 40 K, with a magnetic structure which is coupled to the Ni sublattices (i.e.
1g
and
3g
). The magnetic moment at low temperature for Pr is about 1.28
B
. 相似文献
109.
The near-UV-vis electronic spectroscopy of [Ru(X)(Me)(CO)(2)(iPr-DAB)] (X = Cl or I; iPr-DAB = N,N'-di-isopropyl-1,4-diaza-1,3-butadiene) is investigated through CASSCF/CASPT2 and TD-DFT calculations on the model complexes [Ru(X)(Me)(CO)(2)(Me-DAB)] (X = Cl or I). Convergence of the calculated transition energies for the low-lying metal-to-ligand charge-transfer (MLCT), X-to-ligand charge-transfer (XLCT, X halide ligand), or sigma-bond-to-ligand charge-transfer (SBLCT) to experimental values is analyzed for both methods. On the basis of these accurate calculations, it is shown that whereas the lowest singlet state can be assigned to a nearly pure XLCT state in [Ru(I)(Me)(CO)(2)(Me-DAB)], its character is mainly MLCT in [Ru(Cl)(Me)(CO)(2)(Me-DAB)]. These results are in agreement with time-resolved emission/IR and resonance Raman experimental data. The experimental UV-vis bands are well reproduced by the CASSCF/CASPT2 calculations. The TD-DFT transition energies to the long-range charge transfer states are dramatically affected by the nature of the functional, with lowering leading to meaningless values in the case of nonhybrid functionals. Both methods reproduce well the red shift of the absorption bands on going from the chloride to the iodide complex as well as the shift of the strongly absorbing higher MLCT transition from the visible to the UV domain of energy. 相似文献
110.
A. Villares S. Rodríguez C. Lafuente F. M. Royo M. C. López 《Journal of solution chemistry》2004,33(9):1119-1133
Experimental viscosities and the corresponding viscosity deviations for the binary mixtures of a cyclic ether (tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, or 2,5-dimethyltetrahydrofuran) with benzene, toluene, fluorobenzene, or chlorobenzene are given at 25°C. The kinematic viscosities and the corresponding densities were measured with an uncertainty of ±10– 4 mm2-s– 1 and ±(5×10– 3) kg-m– 3, respectively. The viscosity data were correlated by the equations of Grunberg–Nissan, McAllister, and Heric. On the other hand, the results have been compared to the predictions, by the method proposed by Asfour. 相似文献