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31.
The π-π stacking interactions between maleimide's and nitrone's aromatic rings during the 1,3-dipolar cycloaddition were assumed to control the exo-endo selectivity of the reaction. The exo-endo ratios change during the reactions until they reach a constant value, which depends on the substituent. Electron-withdrawing groups favour the exo adduct while electron-donating groups favour the endo adduct. The nitrone ZnBr2 complexes react much more slowly than the free nitrone and the cycloaddition is exo selective in all cases independent of the substituents on the maleimide's aromatic ring. Thermal retrocycloaddition of the cycloadducts produce the corresponding nitrones. The ring opening in the presence of secondary amines did not induce imine formation. endo Adducts were shown for the first time to be the stable paramagnetic compounds. 相似文献
32.
Y. Goto K. Nakashima K. Mitsuishi M. Takafuji S. Sakaki H. Ihara 《Chromatographia》2002,56(1-2):19-23
Summary Poly(octadecyl acrylate) exists in a crystalline state at room temperature. This crystalline state was formed even after being
grafted onto silica through the terminal group of the polymer. When this polymer-grafted silica (Sil-ODAn) was used as a reversed phase liquid chromatography packing material, better selectivity for diastereomerized phenylethylamines
derivatized by (S)-(−)-(2,3-naphthalenedicarboximidyl)propionyl fluoride was observed at room temperature than was observed
for simple octadecylated silica (ODS). On the other hand, increasing temperature reduced the selectivity to be close to that
of ODS. Additional experiments showed the better selectivity derived from Sil-ODAn was due to both the highly-oriented structure of the polymer and the carbonyl-π interaction with the diastereomer. A theoretical
investigation of this carbonyl-π interaction is also described briefly. 相似文献
33.
Serially coupled capillary columns supercritical fluid chromatography with midpoint pressure control
Two capillary columns of different polarities were coupled in series by means of a coupling restrictor. The pressure of the first column and the midpoint pressure (between the coupling restrictor and the second column) were controlled independently of each other using two pumps. The selectivity of this separation system was highly dependent on the pressure difference and could be continuously changed between those of two columns. The pressure difference could be changed even in course of separation for fine tuning of the selectivity. Several examples were shown to demonstrate the utility of this method. 相似文献
34.
Structural tuning of coordination polymers by 4-connecting metal node and secondary building process
Due to variation in ligand's conformation, metal node's connecting geometry, and secondary building process by anions, bat-like, dumbell-like, diamondoid, or pillar-layer topologies are achieved. 相似文献
35.
36.
Qiong Dai Rosa Lebrn-Aguilar Elena Fernndez-Snchez Jos Antonio García-Domínguez Jesus Eduado Quintanilla-Lpez 《Journal of separation science》1993,16(12):721-724
Four poly(methyl 3,3,3-trifluoropropyl siloxanes) with trifluoro-propyl group content (group substitution) between 8 and 35 percent have been synthesized and characterized as stationary phases for gas chromatography in borosilicate glass capillary columns. Results are compared with those from two commercial stationary phases–a polydimethylsiloxane and a poly(methyl 3,3,3-trifluoropropyl siloxane) with a fifty percent trifluoropropyl group content (group substitution). Retention index values, McReynolds constants, polarity (as defined by McReynolds) and retention polarity (as defined by Takács) increase regularly with the trifluoropropyl group content of the stationary phase. The temperature coefficient of the retention indices of the McReynolds probes, and that of the polarities, have been determined at temperatures between 60 and 180 °C. Specific retention volumes do not follow the linear dependence on trifluoropropyl group content observed for retention indices or polarities. Substances with electron-donor groups show maximum retention for a trifluoropropyl group content of ca 30%, whereas the retention of hydrocarbons, halogenated compounds, and alcohols decreases as the degree of trifluoropropyl group substitution increases from 0 to 50%. It is felt that a polysiloxane with a trifluoropropyl group content of ca 30 to 35% would be the best choice for the separation of ketones, nitro compounds or amines. 相似文献
37.
The 25% niobium substituted crystalline titanosilicate with the composition Na1.5Nb0.5Ti1.5O3SiO4·2H2O (Nb-TS) was synthesized under hydrothermal conditions. Its selectivity for radioactive 137Cs and 89Sr was compared with the TS, Na2Ti2O3SiO4·2H2O, having sitinakite topology. The Nb-TS shows significantly higher uptake value for 137Cs but lower for 89Sr than the TS. To investigate the origin of selectivity, the ion exchanged Cs+ and Sr2+ forms with the composition, CsxNaHyNb0.5Ti1.5O3SiO4·zH2O (x=0.1, 0.2 and 0.3, x+y=0.5 and z=1-2) and Sr0.2Na0.6H0.5Nb0.5Ti1.5O3SiO4·H2O, respectively, were structurally characterized from the X-ray powder diffraction data using the Rietveld refinement technique. Simultaneously the kinetics of 137Cs and 89Sr uptake was investigated for the NbV free and doped samples. While the Cs+ and Sr2+ exchanged form of Nb-TS and the Cs+ exchanged form of TS retain the symmetry of the parent compound, the Sr2+ exchanged form of TS undergoes a symmetry change. The differences in the uptake of Cs+ and Sr2+ result from the different coordination environments of cesium and strontium in the eight-ring channel, that result from various hydration sites in the tunnel. The origin of selectivity appears to arise from the higher coordination number of cesium or strontium. Other effects due to NbV substitution are reflected in the increase of both, the a- and c-dimensions and thus the unit cell volume, and the population of water vs. Na+ in the channel to charge-balance the Nb5+↔Ti4+ substitution. 相似文献
38.
Polar groups in the skeletons of conjugated microporous polymers (CMPs) play an important role in determining their porosity and gas sorption performance. Understanding the effect of the polar group on the properties of CMPs is essential for further advances in this field. To address this fundamental issue, we used benzene, the simplest aromatic system, as a monomer for the construction of two novel CMPs with multi-carboxylic acid groups in their skeletons (CMP-COOH@1 and CMP-COOH@2). We then explored the profound effect the amount of free carboxylic acid in each polymer had on their porosity, isosteric heat, gas adsorption, and gas selectivity. CMP-COOH@1 and CMP-COOH@2 showed Brunauer-Emmett-Teller (BET) surface areas of 835 and 765 m2·g-1, respectively, displaying high potential for carbon dioxide storage applications. CMP-COOH@1 and CMP-COOH@2 exhibited CO2 capture capabilities of 2.17 and 2.63 mmol·g-1 (at 273 K and 1.05 × 105 Pa), respectively, which were higher than those of their counterpart polymers, CMP-1 and CMP-2, which showed CO2 capture capabilities of 1.66 and 2.28 mmol·g-1, respectively. Our results revealed that increasing the number of carboxylic acid groups in polymers could improve their adsorption capacity and selectivity. 相似文献
39.
40.
Morpholine amides are cheap and safe alternative to Weinreb amides as acylating agents of organometallic species. Herein, the in-situ lithiation/borylation of 18 ortho- meta- and para-substituted morpholine benzamides has been investigated. 10 of the 18 substrates provided the desired boronic esters as the major isomer (>90% regioselectivity) in crude isolated yields ranging from 68 to 93%. The synthetic usability of such building blocks was subsequently illustrated via the synthesis of a kinase inhibitor. 相似文献