全文获取类型
收费全文 | 1107篇 |
免费 | 36篇 |
国内免费 | 6篇 |
专业分类
化学 | 899篇 |
晶体学 | 6篇 |
力学 | 16篇 |
数学 | 101篇 |
物理学 | 127篇 |
出版年
2023年 | 5篇 |
2022年 | 19篇 |
2021年 | 32篇 |
2020年 | 32篇 |
2019年 | 16篇 |
2018年 | 21篇 |
2017年 | 16篇 |
2016年 | 33篇 |
2015年 | 23篇 |
2014年 | 31篇 |
2013年 | 53篇 |
2012年 | 74篇 |
2011年 | 109篇 |
2010年 | 47篇 |
2009年 | 34篇 |
2008年 | 85篇 |
2007年 | 62篇 |
2006年 | 77篇 |
2005年 | 85篇 |
2004年 | 59篇 |
2003年 | 47篇 |
2002年 | 50篇 |
2001年 | 13篇 |
2000年 | 10篇 |
1999年 | 8篇 |
1998年 | 8篇 |
1997年 | 16篇 |
1996年 | 17篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1993年 | 8篇 |
1992年 | 6篇 |
1991年 | 2篇 |
1989年 | 3篇 |
1987年 | 4篇 |
1985年 | 5篇 |
1984年 | 2篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有1149条查询结果,搜索用时 15 毫秒
201.
202.
Guilherme G. Bessegato Michelle F. Brugnera Maria Valnice Boldrin Zanoni 《Current Opinion in Electrochemistry》2019
Color is an important element of the final product of many industries, including the textile, leather, food, cosmetic, pharmaceutical, plastic, and fuel-marking industries. Dyes are complex organic substances with chromophore and auxochromic groups, which can be electrochemically oxidized and/or reduced; this constitutes the basis of their electroanalytical determination. Despite some controversies, dyes pose risks to living organisms, especially after biotransformation, as the metabolites can be more toxic, mutagenic, or carcinogenic than the original dyes. The present work provides a brief overview of the recent progress in electrochemical sensors used for dye detection in diversified matrices. Sensors developed over the recent years are characterized by high sensitivity and selectivity, besides being economically advantageous once they allow the use of little or no clean-up samples in portable and miniaturized systems. 相似文献
203.
A variety of theoretical methods have been used to study the gas-phase acidity of benzene and its eleven fluorine-substituted derivatives: fluorobenzene, three isomers of difluorobenezene, three isomers of trifluorobenzene, three isomers of tetrafluorobenzene and 1,2,3,4,5-pentafluorobenzene. The high-level ab initio methods, G3//B3-LYP and CBS-QB3, are shown to reproduce experimental data to within an average of 1.9 and 1.4 kcal mol−1, respectively. Of the lower-cost methods studied, M05-2X and MP2 showed the best overall performance with mean absolute deviations of just 1.2 and 1.1 kcal mol−1, respectively. The effect of substitution and position on the acidity of the protons in the various compounds are studied and the structure-reactivity trends in these heterolytic C-H bond dissociation energies (BDEs) are compared with the corresponding homolytic C-H BDEs for the same species. 相似文献
204.
Solid-state 95Mo NMR spectroscopy is shown to be an efficient and effective tool for analyzing the diamagnetic octacyanomolybdate(IV) anions, Mo(CN)(8)4-, of approximate dodecahedral, D(2d), and square antiprismatic, D(4d), symmetry. The sensitivity of the Mo magnetic shielding (sigma) and electric field gradient (EFG) tensors to small changes in the local structure of these anions allows the approximate D(2d) and D(4d) Mo(CN)(8)4- anions to be readily distinguished. The use of high applied magnetic fields, 11.75, 17.63 and 21.1 T, amplifies the overall sensitivity of the NMR experiment and enables more accurate characterization of the Mo sigma and EFG tensors. Although the magnitudes of the Mo sigma and EFG interactions are comparable for the D(2d) and D(4d) Mo(CN)(8)4- anions, the relative values and orientations of the principal components of the Mo sigma and EFG tensors give rise to 95Mo NMR line shapes that are significantly different at the fields utilized here. Quantum chemical calculations of the Mo sigma and EFG tensors, using zeroth-order regular approximation density functional theory (ZORA DFT) and restricted Hartree-Fock (RHF) methods, have also been carried out and are in good agreement with experiment. The most significant and surprising result from the DFT and RHF calculations is a significant EFG at Mo for an isolated Mo(CN)(8)4- anion possessing an ideal square antiprismatic structure; this is contrary to the point-charge approximation, PCA, which predicts a zero EFG at Mo for this structure. 相似文献
205.
Carlson JC Jena SS Flenniken M Chou TF Siegel RA Wagner CR 《Journal of the American Chemical Society》2006,128(23):7630-7638
The exploitation of biological macromolecules, such as nucleic acids, for the fabrication of advanced materials is a promising area of research. Although a greater variety of structural and functional uses can be envisioned for protein-based materials, systematic approaches for their construction have yet to emerge. Consistent with theoretical models of polymer macrocyclization, we have demonstrated that, in the presence of dimeric methotrexate (bisMTX), wild-type Escherichia coli dihydrofolate reductase (DHFR) molecules tethered together by a flexible peptide linker (ecDHFR(2)) are capable of spontaneously forming highly stable cyclic structures with diameters ranging from 8 to 20 nm. The nanoring size is dependent on the length and composition of the peptide linker, on the affinity and conformational state of the dimerizer, and on induced protein-protein interactions. Delineation of these and other rules for the control of protein oligomer assembly by chemical induction provides an avenue to the future design of protein-based materials and nanostructures. 相似文献
206.
The following novel solvatochromic probes were synthesized: 2,6-dibromo-4-[(E)-2-(1-alkylpyridinium-4-yl)ethenyl] phenolate, where the alkyl groups are methyl, n-butyl, n-hexyl, and n-octyl, respectively. Solvatochromism of three of these probes (C(1), C(4), and C(8)) was studied in 36 protic and aprotic solvents. A modified linear solvation energy relationship has been applied to the data obtained at 25 degrees C. Correlation of (empirical) polarities with other solvent properties showed more dependence on lipophilicity than on basicity. A similar conclusion has been reached for a series of other solvatochromic indicators. Exceptions are those that carry acidic hydrogens, being biased toward solvent basicity. Thermosolvatochromism has been studied in mixtures of water with methanol, 1-propanol, acetonitrile, and DMSO. Thermosolvatochromic data have been treated according to a model that explicitly considers the presence in bulk solution of three "species": water, organic component, and solvent-water hydrogen-bonded aggregate. Solvation by the latter is favored over solvation by either of the two precursor solvents (aqueous DMSO is an exception). Temperature increase resulted in desolvation of the probes, due to concomitant decrease of the structures of the component solvents. The above-mentioned modified solvation equation has been successfully applied to solvatochromism in aqueous methanol and aqueous 1-propanol. 相似文献
207.
High-level ab initio calculations demonstrate that alkoxy-thiocarbonyl radicals (ROC*=S) undergo beta-scission significantly faster than alkoxycarbonyl radicals (ROC*=O) despite having similar exothermicities. The relatively low reactivity of the ROC*=O radicals is reduced further by electron-donating R groups and arises from the large polarization of the C*-O bonds of the reactant radicals. The results suggest that the generation of alkyl radicals from ROC*=S should be particularly efficient when the R group bears radical-stabilizing and/or electron-accepting groups, such as CN. 相似文献
208.
D. Michelle Motley Judith A. Walmsley Julio Zukerman-Schpector Edward R. T. Tiekink 《Journal of chemical crystallography》2009,39(5):364-367
Abstract The gold(III) atom in [Au(NH2CH2CH2NH2)Cl2]NO3 is chelated by the ethylenediamine (en) ligand and the approximately square planar geometry is completed by two chloride
atoms. Weak Au···O and Au···Cl contacts are noted above and below the square plane leading to a tetragonally distorted octahedron
for the gold(III) center. Extensive charge-assisted hydrogen bonding of the type N–H···O leads to the formation of a 2-D array
and layers are consolidated into a 3-D network via C–H···O and C–H···Cl contacts. The compound crystallizes in the orthorhombic
space group Pbca with a = 10.3380(11) ?, b = 8.2105(7) ?, c = 19.625(2) ?, and Z = 8.
Index Abstract Square planar complex cations form additional Au···O and Au···Cl interactions to form a tetragonally distorted octahedron
for gold. The ionic components are connected into a 2-D array via charge-assisted N–H···O hydrogen bonding interactions.
相似文献
209.
Surface defects are commonly believed to be fundamentally important to gas-sensor performance. We examine the effect of gas coverage and ethanol orientation on its adsorption on the stoichiometric and oxygen deficient (101(-)0) nanowire surface. Our density functional theory calculations show that ethanol adsorbs in multiple stable configurations at coverages between 1/4 and 1 ML, highlighting the ability of ZnO to detect ethanol. Ethanol prefers to bind to a surface Zn via the adsorbate oxygen atom and, if a surface oxygen atom is in close proximity, the molecule is further stabilized by formation of a hydrogen bond between the hydrogen of the hydroxyl group and the surface oxygen. Two primary adsorption configurations were identified and have different binding strengths that could be distinguished experimentally by the magnitude of their OH stretching frequency. Our findings show that ethanol adsorbed on the oxygen deficient ZnO(101(-)0) surface has a reduced binding strength. This is due to either the lack of a hydrogen bond (due to a deficiency in surface oxygen) or to surface reconstruction that occurs on the defect surface that weakens the hydrogen bond interaction. This reduced binding on the oxygen deficient surface is in contrast to the defect enhanced gas-sensor interaction for other gases. Despite this difference, ethanol still acts as a reducing gas, donating electrons to the surface and decreasing the band gap. We show that multiple adsorbed ethanol molecules prefer to be orientated parallel to each other to facilitate the hydrogen bonding to the defect-free surface for enhanced interaction. 相似文献
210.
Saltarelli M Luz PP Matos MG de Faria EH Ciuffi KJ Calefi PS Rocha LA Nassar EJ 《Journal of fluorescence》2012,22(3):899-906
YVO(4):Eu(3+) phosphors have been prepared by the hydrolytic sol-gel methodology, with and without alkaline catalyst. The solid powder was obtained by reaction between yttrium III chloride and vanadium alkoxides; the europium III chloride was used as structural probe. The powder was treated at 100, 400, 600, or 800 °C for 4 h. The samples were characterized by X-ray diffraction, thermal analysis, and photoluminescence. The XRD patterns revealed YVO(4) crystalline phase formation for the sample prepared without the catalyst and heat-treated at 600 °C and for the sample prepared in the presence of ammonium as catalyst and heat-treated at 100 °C. The average nanosized crystallites were estimated by the Scherrer equation. The sample which was produced via alkaline catalysis underwent weight loss in two stages, at 100 and 400 °C, whereas the sample obtained without catalyst presented four stages of weight loss, at 150, 250, 400, and 650 °C. The excitation spectra of the samples treated at different temperatures displayed the charge transfer band (CTB) at 320 nm. PL data of all the samples revealed the characteristic transition bands arising from the (5)D(0) → (5)F(J) (J = 0, 1, 2, 3, and 4) manifolds under maximum excitation at 320, 394, and 466 nm in all cases. The (5)D(0) → (7)F(2) transition often dominates the emission spectra, indicating that the Eu(3+) ion occupies a site without inversion center. The long lifetime suggests that the matrix can be applied as phosphors. In conclusion, the sol-gel methodology is a very efficient approach for the production of phosphors at low temperature. 相似文献