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The interaction of the clathrate Pt6Cl12 · 0.1 EtCl · 5.7H2O with RCN nitriles results in cis-[Pt(PhCH2CN)2Cl2] and in [Pt(RCN)2Cl2] (R = CH2CO2Et, Ph) complexes as a mixture of cis- and trans-isomers which separated and characterized. Cis-[Pt(MeCN)2Cl2] has been synthesized using a well known technique of K2[PtCl4] interaction with acetonitrile in water. Heating cis-[Pt(RCN)2Cl2] (R = Me, CH2Ph, CH2CO2Et) in the solid phase leads to cis-trans isomerization. In case of cis-[Pt(PhCN)2Cl2] thermal conversion results in trans-[Pt(PhCN)2Cl2] but the process of geometrical isomerizations accompained by a considerable decomposition of starting material and/or final products. Boiling of cis-[Pt(PhCH2CN2)Cl2] in mixture of EtNO2? PhCH2CN or cis-[Pt(EtCO2CH2CN)2Cl2] in MeNO2 or EtNO2 solutions results in complete cis-trans conversion. Similarily heating of cis-[Pt(RCN)2Cl2] (R = Me, Ph) in solution produces an equilibrium mixture of cis- and transisomers. 相似文献
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A. V. Turov S. P. Bondarenko A. A. Tkachuk V. P. Khilya 《Russian Journal of Organic Chemistry》2005,41(1):47-53
Various lanthanide shift reagents Ln(fod)3 were found to affect the conformational composition of 2-methoxychalcones. Coordination of Yb(fod)3 occurs mainly at the carbonyl oxygen atom of the substrate, while Eu(fod)3 and shift reagents derived from other lanthanides coordinate substituted chalcones as bidentate ligands, giving rise to a secondary tetrachelate with the corresponding change of conformation of the substrate molecule. The possibility for chelation is determined by steric hindrances in the vicinity of the substrate coordination centers and concurrent coordination of other electron-donor groups present in the substrate molecule.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 51–56.Original Russian Text Copyright © 2005 by Turov, Bondarenko, Tkachuk, Khilya. 相似文献
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The rare-earth intermetallic compounds (RE)12Co5Bi (RE = Y, Gd, Tb, Dy, Ho, Er, Tm) were prepared by arc-melting and annealing at 600 degrees C. These compounds extend the previously known (RE)6M2+xX1-x (M = Co, Ni; X = Ga, In, Sn, Pb) series with the Ho6Co2Ga-type structure to X = Bi. The crystal structure of Ho12Co5Bi was refined by the Rietveld method from powder X-ray diffraction data obtained using synchrotron radiation (Pearson symbol oI36, orthorhombic, space group Immm, Z = 2, a = 9.37598(14) A, b = 9.37871(14) A, c = 9.85465(13) A). Unlike other Ho6Co2Ga-type compounds, the 2a site in Ho12Co5Bi is exclusively occupied by Co atoms. Four-probe electrical resistivity measurements on sintered polycrystalline samples of (RE)12Co5Bi indicated metallic behavior. Magnetic measurements revealed behavior ranging from frequency-dependent maxima in the ac susceptibility for Y12Co5Bi to possible ferrimagnetic ordering for Gd12Co5Bi to antiferromagnetic ordering with metamagnetic transitions for the remaining compounds. As confirmed by band structure calculations using Y12Co5Bi as a model compound, Y-Y and Y-Co interactions are the most important bonding components, but matrix effects are likely responsible for anomalously short Co-Co contacts in the structure. 相似文献
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N. V. Gorbulenko T. M. Tkachuk T. V. Shokol V. V. Semeniuchenko A. V. Turov V. P. Khilya 《Chemistry of Heterocyclic Compounds》2007,43(5):569-575
The interaction has been studied of a series of substituted 3-hetaryl-7-hydroxychromones with amino acids and formaldehyde
(reactants ratio 1: 1: 2 respectively). In the case of glycine and Het = 3-isoxazolyl the product of aminomethylation at position
8 of the chromone was obtained, and with other Het (including Het = 4-phenyl-1,2,4-triazol-3-yl) 2-[6-alkyl-3-hetaryl-4-oxo-9,10-dihydro-4H,8H-chromeno[8,7-e][1,3]-oxazin-9-yl]acetic
acids were formed. With β-alanine and Het = 4-phenyl-1,2,4-triazol-3-yl the corresponding β-substituted propionic acid was
synthesized, but proline did not participate in the reaction, leading to bis(6-ethyl-3-hetaryl-7-hydroxychromon-8-yl)methane.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 683–689, May, 2007. 相似文献
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Garcia Ruano JL Alemparte C Martin Castro AM Adams H Rodriguez Ramos JH 《The Journal of organic chemistry》2000,65(23):7938-7943
The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles. 相似文献
9.
Andriy V. Tkachuk 《Journal of solid state chemistry》2004,177(11):3939-3943
The isostructural ternary transition-metal silicides Zr3Mn4Si6 and Hf3Mn4Si6 can be prepared by direct reaction of the elemental components or by arc-melting. The single-crystal structure of Zr3Mn4Si6 was determined by X-ray diffraction (Pearson symbol tP104, tetragonal, space group P42/mbc, Z=8, , ). Zr3Mn4Si6 is isostructural to Nb3Fe3CrSi6 and contains an essentially ordered arrangement of the transition-metal atoms. Square antiprismatic clusters with Zr and Mn atoms at the corners and Si atoms at the center share opposite faces to form one-dimensional columns extending along the c direction. These columns occupy channels that are outlined by a framework of edge- and face-sharing MnSi6 octahedra. The extensive metal-metal interactions in the structure are complemented by Si-Si bonding in the form of dumbbells, linear chains, and zigzag chains. 相似文献
10.
EI Rodriguez Martinez CI Barriga-Paulino MI Zapata CC Chinchilla AM López-Jiménez CM Gómez 《BMC neuroscience》2012,13(1):104-23
ABSTRACT: BACKGROUND: The peri-adolescent period is a crucial developmental moment of transition from childhood to emergent adulthood. The present report analyses the differences in Power Spectrum (PS) of the Electroencephalogram (EEG) between late childhood (24 children between 8 and 13 years old) and young adulthood (24 young adults between 18 and 23 years old). RESULTS: The narrow band analysis of the Electroencephalogram was computed in the frequency range of 0--20 Hz. The analysis of mean and variance suggested that six frequency ranges presented a different rate of maturation at these ages, namely: low delta, delta-theta, low alpha, high alpha, low beta and high beta. For most of these bands the maturation seems to occur later in anterior sites than posterior sites. Correlational analysis showed a lower pattern of correlation between different frequencies in children than in young adults, suggesting a certain asynchrony in the maturation of different rhythms. The topographical analysis revealed similar topographies of the different rhythms in children and young adults. Principal Component Analysis (PCA) demonstrated the same internal structure for the Electroencephalogram of both age groups. Principal Component Analysis allowed to separate four subcomponents in the alpha range. All these subcomponents peaked at a lower frequency in children than in young adults. CONCLUSIONS: The present approaches complement and solve some of the incertitudes when the classical brain broad rhythm analysis is applied. Children have a higher absolute power than young adults for frequency ranges between 0-20 Hz, the correlation of Power Spectrum (PS) with age and the variance age comparison showed that there are six ranges of frequencies that can distinguish the level of EEG maturation in children and adults. The establishment of maturational order of different frequencies and its possible maturational interdependence would require a complete series including all the different ages. 相似文献