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21.
The pressure-composition isotherm of the Ho6Fe23D2 system at 0°C was established, revealing the presence of two plateau regions. Using the isotherm, five compositions of the Ho6Fe23Dx system (x = 0, 1.5, 8.2, 12.1, 15.7) were selected for investigation. These were examined by X-ray diffraction and magnetization measurements. The cubic lattice of the host metal is maintained to x = 8.2. A tetragonal structure develops at x = 12.1, but this reverts to cubic symmetry at the highest deuterium concentration studied. The observed structural changes are ascribed to preferential site occupancies by deuterium. Absorption of 15.7 deuterium atoms per formula unit in Ho6Fe23 caused a 10.2% increase of the unit cell volume. Increase in the deuterium content resulted in a striking increase in the Curie temperature Tc and in a linear decrease in compensation temperature Tcomp. The saturation magnetization changed smoothly as the system changed from one structure type to another. There appears to be a significant increase in Fe magnetic moment upon deuterium absorption, which is ascribed to the removal of electrons from the 3d iron band by deuterium. 相似文献
22.
Aqueous solutions of boratei can be titrated amperometrically with standard fi uctose solutions This procedure may be used to determine the boron content of various types of samples after conversion of the boron to the borate form The methode is based upon the observation that the polarographic wave of fructose. in a o I M LiCl, 001 N'LiOH solution is deprcssed by the presence of borate ions Under the prescribed conditions the methode is sensitive to a few hundredths of a milligram of boron The few comnonly occurring intcrferenes can be conveniently removed prior to the titration 相似文献
23.
Wallace WT Wyrwas RB Whetten RL Mitrić R Bonacić-Koutecký V 《Journal of the American Chemical Society》2003,125(27):8408-8414
The discovery that supported gold clusters act as highly efficient catalysts for low-temperature oxidation reactions has led to a great deal of work aimed at understanding the origins of the catalytic activity. Several studies have shown that the presence of trace moisture is required for the catalysts to function. Using near-atmospheric pressure flow reactor techniques, we have studied humidity and temperature effects on the reactivity of gas-phase gold cluster anions with O2. Near room temperature, the humid source produces abundant gold-hydroxy cluster anions, Au(N)OH(-), and these have a reversed O2 adsorption activity: Nonreactive bare gold clusters become active when in the form Au(N)OH(-), while active bare clusters are inactive when -OH is bound. The binding energies for the stable structures obtained from density functional calculations confirm fully these findings. Moreover, the theory provides evidence that electron-transfer induced by the binding of a OH group enhances the reactivity toward molecular oxygen for odd anionic gold clusters and suppresses the reactivity for the even ones. The temperature dependence of O2 addition to Au(3)OH(-) and Au(4)(-) indicates deviations from equilibrium control at temperatures below room temperature. The effects of humidity on gold cluster adsorption activity support the conclusion drawn for the mechanism of O2 adsorption on "dry" gold cluster anions and provides insight into the possible role of water in the enhanced activity of supported gold cluster catalysts. 相似文献
24.
G.G. Wallace 《Trends in analytical chemistry : TRAC》1985,4(6):145-148
Electroanalytical chemistry has been plagued for decades with the problems associated with dissolved oxygen. Dissolved oxygen is electrochemically reduced at potentials less negative than ?0.05 V vs. standard calomel electrode (SCE) and, therefore, interferes with detection of many species when using reductive voltammetry. Historically, electroanalytical chemists have taken the view that dissolved oxygen should be removed from the sample solution in order to overcome the interference problems. However, there are drawbacks associated with this approach, particularly when dealing with flowing solutions. More recently an alternative approach, the development of voltammetric methods which are not so prone to dissolved oxygen interference, has been taken by various workers. 相似文献
25.
J. Shield Wallace Cary J. Morrow 《Journal of polymer science. Part A, Polymer chemistry》1989,27(8):2553-2567
The enantioselective polymerization of bis(2,2,2-trichloroethyl) trans-3,4-epoxyadipate with 1,4-butanediol using the enzyme porcine pancreatic lipase as a catalyst is described. The polymerization was carried out at ambient temperature in anhydrous ethyl ether. End group analysis provided MN = 5,300 daltons, whereas GPC provided Mw = 7,900 daltons for the polymer. The unchanged (+)-enantiomer of the diester was shown to have an enantiomeric purity of > 95% by proton NMR in the presence of the chiral shift reagent Eu(hfc)3. The stereochemical purity of the (?)-polymer was estimated at > 96% by consideration of the amount of the slower reacting enantiomer that could have been incorporated and still attain the observed degree of polymerization (25) when the starting ratio of racemic diester to diol was 2:1. Direct determination of the stereochemical purity of the polymer using Eu(hfc)3 was unsuccessful. Similar studies on polymer having random stereochemical orientations of the epoxide showed that such polymers do not behave as if they are racemic in the presence of the shift reagent. The polymer required for the latter studies was prepared by epoxidation of the product from enzyme catalyzed polymerization of bis(2,2,2-trichloroethyl) trans-3-hexenedioate with 1,4-butanediol. 相似文献
26.
Wallace S. Brey 《Journal of fluorine chemistry》2005,126(3):389-399
Fluorine, hydrogen, and 13C NMR spectral data have been obtained for vinyl alkyl ethers containing fluorines. Some of the molecules are perfluorinated and others include hydrogen, bromine, and chlorine substituents. New generalizations regarding FF spin-spin coupling are developed and used, along with previously recognized correlations, in the confirmation of structures and the assignments of resonances. 13C spectroscopy, especially the analysis of 13C19F coupling, is critical in several of the structure determinations. Chlorine isotope effects on fluorine chemical shifts are observed when the chlorine and fluorine are attached to the same carbon, and are also used in the structure analyses. Long-range couplings between fluorines in the vinyl group and fluorines in the alkyl group are interpreted in terms of molecular geometry which allows certain of the alkyl fluorines to “touch” the fluorines cis and gem to the ether oxygen but not the fluorine trans to the oxygen. Two bond 13C19F coupling across the vinyl double bond is found to vary dramatically with the electronegativity of the vinyl substituents in the ethers, in accordance with previous observations for olefins. 相似文献
27.
Mitsuru Ueda Toshiyuki Suzuki Yoshio Imai Charles U. Pittman Easley Wallace 《Journal of polymer science. Part A, Polymer chemistry》1983,21(10):2997-3008
The kinetics of cyanomethyl methacrylate (CyMA) homopolymerization was investigated in acetonitrile with azobisisobutyronitrile as initiator. The rate of polymerization Rp was expressed by Rp = k[AIBN]0.49[CyMA]1.2 and the overall activation energy was calculated as 72.3 kJ/mol. Kinetic constants for CyMA polymerization were obtained as follows: kp/k = 0.10 L1/2s?1/2; 2fkd = 1.57 × 10?5s?. The relative reactivity ratios of CyMA(M2) copolymerization with styrene (r1 = 0.15, r2 = 0.29) and methyl methacrylate (r1 = 0.43, r2 = 0.75) in acetonitrile were obtained. Applying the Q-e scheme (in styrene copolymerization) led to Q = 1.64 and e = 0.98. The glass transition temperature Tg of poly(CyMA) was observed to be 91°C by thermomechanical analysis. Thermogravimetry of poly(CyMA) showed a 10% weight loss at 265°C in air. 相似文献
28.
The preparation and thermal analysis of metal chelates of benzohydroxarnic acid (BHA) with Al(III), Cd(II), Co(II), Cu(II) (two compounds), Fe(III), La(III), Pb(II), Mn(II), Ni(II), U(VI) and Zn(II) is discussed. The Al(III), La(III), Pb(II) and Mn(II) chelates are new compounds. DTA and TGA curves of the chelates and of BHA are presented, and the heats of decomposition of the chelates are estimated. 相似文献
29.
Wallace T. Ashton Ronald D. Brown Richard L. Tolman 《Journal of heterocyclic chemistry》1978,15(3):489-491
The acid-catalyzed reaction of 6-(N-D-ribityl-3,4-xylidino)uracil ( 1 ) with trimethyl ortho-formate yields a bis(methoxymethylene) derivative ( 2 ), which is readily deprotected to give 5-deazariboflavin ( 3 ). Correspondingly, 5-methyl-5-deazariboflavin ( 6 ) is produced by cyclization of the tetraacetate of 1 with acetyl chloride in the presence of stannic chloride followed by deacetylation. 相似文献
30.
Artificial red cells with crosslinked hemoglobin membranes 总被引:1,自引:0,他引:1
Thomas A. Davis William J. Asher Herbert W. Wallace 《Applied biochemistry and biotechnology》1984,10(1-3):123-132
Artificial cells containing concentrated hemoglobin (Hb) solution were prepared by interfacial polymerization of Hb with glutaraldehyde
(GA) in liquid membrane capsules (LMC). A solution containing 30% of Hb was emulsified in mineral oil as red cell-size microdroplets,
and this emulsion was dispersed in an aqueous phase containing glutaraldehyde to form LMC. The LMC were semipermeable templates
that held the microdroplets of Hb in suspension while GA diffused through the oil to the microdroplet surfaces. The GA crosslinked
Hb at the surface of each microdroplet to form an artificial red-cell membrane encapsulating Hb solution. A water-soluble
surfactant was used to eject the cells from the LMC and suspend them in saline.
Several surfactants were evaluated. Cell size was controlled by agitation speed during preparation of the original emulsion.
Cells of 2.52 = ±1.69 μm were prepared. The encapsulated Hb retained capacity to bind and release O2. The cells had aP
50 of 8.9 torr (1200 Pa) and a capacity of 0.55 cc O2/g of total Hb, indicating that the crosslinked portion of the Hb did not contribute to O2 transport. 相似文献