全文获取类型
收费全文 | 1097篇 |
免费 | 38篇 |
国内免费 | 9篇 |
专业分类
化学 | 722篇 |
晶体学 | 30篇 |
力学 | 21篇 |
数学 | 160篇 |
物理学 | 211篇 |
出版年
2023年 | 5篇 |
2022年 | 41篇 |
2021年 | 52篇 |
2020年 | 24篇 |
2019年 | 26篇 |
2018年 | 31篇 |
2017年 | 33篇 |
2016年 | 47篇 |
2015年 | 23篇 |
2014年 | 54篇 |
2013年 | 63篇 |
2012年 | 80篇 |
2011年 | 81篇 |
2010年 | 56篇 |
2009年 | 46篇 |
2008年 | 60篇 |
2007年 | 60篇 |
2006年 | 54篇 |
2005年 | 55篇 |
2004年 | 51篇 |
2003年 | 34篇 |
2002年 | 20篇 |
2001年 | 14篇 |
2000年 | 11篇 |
1999年 | 10篇 |
1998年 | 5篇 |
1997年 | 7篇 |
1996年 | 5篇 |
1995年 | 8篇 |
1994年 | 6篇 |
1993年 | 8篇 |
1992年 | 5篇 |
1991年 | 8篇 |
1990年 | 11篇 |
1989年 | 1篇 |
1988年 | 6篇 |
1987年 | 1篇 |
1986年 | 6篇 |
1985年 | 4篇 |
1984年 | 11篇 |
1983年 | 6篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1973年 | 2篇 |
排序方式: 共有1144条查询结果,搜索用时 15 毫秒
31.
The structure of bis(dimethylammonium) pentachloroantimonate(III), [(CH3)2NH2]2[SbCl5], BDP, was studied at 15 K and ambient pressure by single-crystal X-ray diffraction as well as at ambient temperature and high pressures up to 4.87(5) GPa by Raman spectroscopy. BDP crystallizes in the orthorhombic Pnma space group with a=8.4069(4), b=11.7973(7), c=14.8496(7) Å, and Z=4; R1=0.0381, wR2=0.0764. The structure consists of distorted [SbCl6]3− octahedra forming zig-zag [{SbCl5}n]2n− chains that are cross-linked by dimethylammonium [(CH3)2NH2]+ cations. The organic and inorganic substructures are bound together by the N-H…Cl hydrogen bonds. The distortions of [SbCl6]3− units increase, partly due to the influence of the hydrogen bonds which became stronger, with decreasing temperature. The preliminary room temperature, high-pressure X-ray diffraction experiments suggest that BDP undergoes a first-order phase transition below ca. 0.44(5) GPa that destroys single-crystal samples. The transition is accompanied by changes in the intensities and positions of the Raman lines below 400 cm−1. 相似文献
32.
Maciej Bujak Jacek Zaleski Victor Prezhdo Boris Uspenskiy 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(2):o76-o77
The title molecule, C11H12O3, is almost planar, with an average deviation of the C and O atoms from the least‐squares plane of 0.146 (4) Å. The geometry about the C=C bond is trans. The phenyl ring and –COOCH3 group are twisted with respect to the double bond by 9.3 (3) and 5.6 (5)°, respectively. The endocyclic angle at the junction of the propenoate group and the phenyl ring is decreased from 120° by 2.6 (2)°, whereas two neighbouring angles around the ring are increased by 2.3 (2) and 0.9 (2)°. This is probably associated with the charge‐transfer interaction of the phenyl ring and –COOCH3 group through the C=C double bond. The molecules are joined together through C—H?O hydrogen bonds between the methoxy and ester groups to form characteristic zigzag chains extended along the c axis. 相似文献
33.
Dabkowska I Rak J Gutowski M Nilles JM Stokes ST Bowen KH 《The Journal of chemical physics》2004,120(13):6064-6071
The photoelectron spectrum of the uracil-alanine anionic complex (UA)(-) has been recorded with 2.540 eV photons. This spectrum reveals a broad feature with a maximum between 1.6 and 2.1 eV. The vertical electron detachment energy is too large to be attributed to an (UA)(-) anionic complex in which an intact uracil anion is solvated by alanine, or vice versa. The neutral and anionic complexes of uracil and alanine were studied at the B3LYP and second-order M?ller-Plesset level of theory with 6-31++G(*) (*) basis sets. The neutral complexes form cyclic hydrogen bonds and the three most stable neutral complexes are bound by 0.72, 0.61, and 0.57 eV. The electron hole in complexes of uracil with alanine is localized on uracil, but the formation of a complex with alanine strongly modulates the vertical ionization energy of uracil. The theoretical results indicate that the excess electron in (UA)(-) occupies a pi(*) orbital localized on uracil. The excess electron attachment to the complex can induce a barrier-free proton transfer (BFPT) from the carboxylic group of alanine to the O8 atom of uracil. As a result, the four most stable structures of the uracil-alanine anionic complex can be characterized as a neutral radical of hydrogenated uracil solvated by a deprotonated alanine. Our current results for the anionic complex of uracil with alanine are similar to our previous results for the anion of uracil with glycine, and together they indicate that the BFPT process is not very sensitive to the nature of the amino acid's hydrophobic residual group. The BFPT to the O8 atom of uracil may be relevant to the damage suffered by nucleic acid bases due to exposure to low energy electrons. 相似文献
34.
Bożena Tutaj Anna Kasprzyk Jan Czapkiewicz 《Journal of inclusion phenomena and macrocyclic chemistry》2003,47(3-4):133-136
A survey of the literature reveals that the spectroscopic displacement method, in which phenolphthalein is used as a competitive chromophore to determine binding constants of β-cyclodextrin with surfactants was successful in the case of homologous hydrocarbon and fluorocarbon anionic surfactants. We show here that this method can be applied also for homologous alkyltrimethylammonium bromides (with alkyl varying from octyl- to hexadecyl) under the condition that the concentration of the cationic surfactant is distinctly lower than the value of itscritical micelle concentration. 相似文献
35.
A.?González-PérezEmail author J.?Czapkiewicz J.?M.?Ruso J.?R.?Rodríguez 《Colloid and polymer science》2004,282(10):1169-1173
The specific conductivity of dodecyldimethylbenzylammonium bromide (C12BBr) in aqueous solutions, in the temperature range of 15 to 40 °C, has been measured as a function of molality. The two breaks which were found on the conductivity against molality plots were attributed to the critical micelle concentration, cmc, and second critical micelle concentration, 2nd cmc, respectively. The ratio of the slopes, S, of the three linear fragments on the plots, S2/S1 and S3/S1, was attributed to the degree of ionization of the micelles at cmc and 2nd cmc respectively. It was shown that the values of the 2nd cmc estimated above 27 °C are only apparent due to thermal disintegration of the micelles. In the temperature range of 15 to 27 °C, the values of the 2nd cmc increase gradually and the plot of the 2nd cmc against temperature is concave. The ratio of 2nd cmc/cmc for C12BBr at 25 °C amounts to 15 and appears to be high compared to the literature values for other surfactants. For comparative purposes the cmc and 2nd cmc values were also estimated conductometrically for decyldimethylbenzylammonium bromide (C10BBr) at 25 °C. The 2nd cmc value for this surfactant is higher compared to the value for the C12 homologue by a factor of 2.6.The standard Gibbs free energies of micellization at cmc and at the 2nd cmc were estimated from the experimental data for both surfactants at 25 °C. 相似文献
36.
A fast and simple method for the oxidative iodination of some activated arenes and heteroarenes, either under microwave irradiation or by conventional heating, is reported, using diiodine and ortho-periodic acid as the oxidant. The reactions were carried out in hot 95% ethanol under a reflux condenser. For the microwave assisted reactions, the reaction times were always notably shortened, but the yields were nearly the same as those afforded by the conventional method. 相似文献
37.
The binding constants, K′, for the reaction between some alkyldimethylbenzylammonium bromide homologues (alkyl = methyl, ethyl, propyl, butyl, hexyl,
decyl, and dodecyl, respectively) and β-cyclodextrin in water at 25.0 ± 0.1 ∘C have been determined, by applying the spectral displacement technique with phenolphthalein as the displacing anion. It has
been shown that the ln K′ values increase linearly with the number of carbon atoms in the alkyl chain for the salts whose alkyl chain has at least
four carbon atoms. The ln K′ values estimated for the parent compound benzyltrimetylammonium bromide and its two nearest homologues are distinctly lower
than might be expected by extrapolation of the linear relation found for the higher homologues. Assuming that it is the organic
cation that undergoes association with β-cyclodextrin, then one may suppose that a change occurs in the mode of inclusion of the cation upon passing to higher homologues.
In the case of the lighter homologues, it is the phenylene group that undergoes inclusion. This model of inclusion is confirmed
by analysis of rotating-frame overhauser effect spectroscopy (ROESY) spectra. 相似文献
38.
The reversed-phase high-performance liquid Chromatographic (RP-HPLC) behaviour of the binary chelates of V(V) and V(IV) with 4-(2-pyridylazo) resorcinol (PAR) and ternary chelates of vanadium with PAR and auxiliary ligands: hydrogen peroxide, hydroxylamine, tartrate and citrate were studied using a C18 column. The complex double-peak chromatograms of V(IV)/V(V)-PAR systems were studied and the origin of each peak was proved. Vanadium in ternary systems with PAR and hydrogen peroxide was found exclusively in V(V)-H2O2-PAR complex (single peak on the chromatogram) despite its initial oxidation state. The double role of hydroxylamine (complex agent and reductor) in vanadium systems with PAR was confirmed: in the V(V) system three species were identified (V(V)-PAR, V(V)-NH2OH-PAR and V(IV)-PAR), but in the V(IV) system only two: V(IV)-PAR and V(V)-NH2OH-PAR. Citrate and tartrate giving single peak were found as auxiliary ligands in ternary V(V) systems of analytical importance. Due to its masking potential towards iron (III) ions, citrate was chosen as the most suitable third component of a ternary vanadium system with PAR, to form the basis of an RP-HPLC method for direct determination of V in steel. 相似文献
39.
Lapinski L Nowak MJ Kwiatkowski JS Leszczynski J 《Photochemistry and photobiology》2003,77(3):243-252
N2-hydroxyisocytosine and 1-methyl-N2-hydroxyisocytosine were studied using a matrix isolation technique combined with infrared absorption spectroscopy. For N2-hydroxyisocytosine isolated in an Ar matrix (at 10 K), two imino-oxo isomers, one with the hydroxyimino =N-OH group directed toward the N1-H group (the form called further anti) and the second with the =N-OH group directed toward N3-H (syn), were observed in the ratio 1.4:1. The syn isomer is converted totally to the anti form after UV (lambda > 295 nm) irradiation of the matrix. A small amount of the N(3)H-hydroxy-amino tautomer of N2-hydroxyisocytosine was also detected in the matrix. This form did not react photochemically. For 1-methyl-N2-hydroxyisocytosine, only the syn form of the imino-oxo tautomer was observed after deposition of the matrix. UV (lambda > 295 nm) irradiation induced a photoreaction converting this isomer into the anti form. After 15% of the starting material had been converted into the product, a photostationary state was achieved, and no further progress of the reaction was observed. Subsequent UV irradiation (lambda > 335 nm) caused a back reaction, leading to a disappearance of the anti form and to the recovery of the initial syn isomer. All isomers were identified by comparing their experimental IR spectra with the spectra theoretically calculated at the DFT(B3LYP)/6-31G(d,p) level, where DFT is the density functional theory. Good agreement between the observed and predicted patterns of the spectral lines allowed for reliable identification. The experimental IR spectra were interpreted and discussed. The relative energies of the 12 isomers of N2-hydroxyisocytosine were calculated at the MP2/6-31G(d,p) and MP4//MP2/6-31G(d,p) levels. For six isomers of 1-methyl-N2-hydroxyisocytosine, the calculations were carried out at the MP2/6-31G(d,p) level. The anti form of the imino-oxo tautomer of N-hydroxyisocytosine and the syn form of the imino-oxo tautomer of 1-methyl-N2-hydroxyisocytosine were predicted to be the most stable. 相似文献
40.
Maciej PisklakFranciszek Herold Romana Anulewicz-OstrowskaIwona Wawer 《Journal of Molecular Structure》2002,605(1):85-92
13C cross-polarisation magic angle spinning NMR data have been reported for four derivatives of 4-aryl-octahydro-pyrido[1,2-c]pyrimidine-1,3-dione and the X-ray diffraction data for two (with 2′-Me and 2′-OMe). The crystal structures show the presence of centrosymmetric cyclic dimers with intermolecular C1O?H-N or C3O?H-N hydrogen bonds, the configuration at the chiral centres (C4 and C4a) was determined as RR (SS). The twisting of aromatic ring at C4 with respect to the pyrido[1,2-c]pyrimidine skeleton is about 68-109°. 相似文献