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1.
The crystal structure of 12,13-dibromopseurotin has been determined by single crystal X-ray analysis. The crystals belong to space group P21 with a = 16.75, b = 9.63, c = 7.42 Å, β 95.9°, Z = 2. The structure was solved by the heavy atom technique and refined to R = 0.062 with 819 significant reflexions for 299 parameters. 相似文献
2.
(2S,4S)-2-(tert-Butyl)-5-oxo-1,3-dioxolan-4-acetic acid ( 1 ) was dilithiated to the enolate 2 in toluene and THF with lithium diisopropylamide (LiN(i-Pr)2) under various conditions. Deuteration experiments with 2 showed that two different stable forms of the enolate could be produced, depending on whether the deprotonation of 1 had been carried out in toluene or THF. The generated (i-Pr)2NH was coordinated to the enolate and, hence, served as a strong lipophilic solvating agent. LiN(i-Pr)2 could substitute the amine ligands of the two species to a different extent. THF was partially able to displace (i-Pr)2NH that solvated the species produced in toluene, but the coordination of the amine to the one produced in THF was quantitive. Correlations with given explanations are made. 相似文献
3.
From the bulbs of Eucomis punctata L'Hérit. (Liliaceae) and of a hitherto undefined species of Eucomis a new optically active phenolic carboxylic acid, eucomic acid, was isolated. Structure 1 was assigned on the basis of chemical and spectral evidence. The absolute configuration of eucomic acid was determined by its correlation with piscidic acid ((2 R, 3 S)-2-(4′-hydroxybenzyl)-tartaric acid) ( 8 ). Consequently, eucomic acid is (R)-(?)-2-(4′-hydroxybenzyl)-malic acid ( 1 ). For the stereospecific synthesis, methyl cis-p-methoxybenzylidene-succinic acid ( 22 ) was transformed into the γ-lactone 24 which, by catalytic hydrogenolysis, yielded (±)-2-(4′-hydroxybenzyl)-malic acid 1-methyl ester ( 27 ). Resolution with (?)-quinine led to the enantiomeric acids 29 and 30 . The methyl ester of the levorotatory enantiomer 30 was identical with the dimethyl ester 3 of 4′-O-methyl-eucomic acid. 相似文献
4.
Chr. Tamm 《Applied physics. B, Lasers and optics》1993,56(5):295-300
A tunable harmonic output power of 18 W at a wavelength of =370 nm is obtained by resonance-enhanced frequency doubling of an optically-stabilized semiconductor laser. A commercially available AlGaAs laser diode which emits a maximum power of 10 mW at =740 nm is operated in an extended-cavity configuration. Dispersion prisms are used in the extended cavity to obtain longitudinal-mode selection with low loss of optical power. The output is focussed into an optically isolated high-finesse ring resonator which contains a LiIO3 crystal for second-harmonic generation. One potential application of this laser source is the optical excitation and laser cooling of ytterbium in an ion trap. In a related demonstration experiment, the frequency-doubled diode laser is applied to excite the =369.5 nm 2
S
1/2-2
P
1/2 transition of ytterbium ions in a hollow-cathode discharge. 相似文献
5.
The circular dichroism of keto derivatives with trichothecane skeleton and some of their rearrangement products has been measured. The sign (and sometimes even the magnitude) of all COTTON effects can be explained by applying the respective rules for the cyclohexanone, cyclopentanone, enone and ene-ester chromophores. Thus conformations could also be determined in those cases which did not follow unambiguously from conformational analysis. The conformation of the muconic acid moiety of the macrocyclic ring of verrucarin A is the same in dioxane solution as in the crystalline state. 相似文献
6.
1-(2′-Deoxy-5′-O-dimethoxytrityl-′-D -ribofuranosyl)-1 H-benzimidazole 3′-[(p-chlorophenyl)(2-cyanoethyl) phosphate] ( 6 ) has been synthesized from 1-(β-D -ribofuranosyl)-1H-benzimidazole ( 3b ) using regiospecific 2′-deoxygenation. The latter compound was obtained by glycosylation of benzimidazole with the D -ribose derivative 2 leading exclusively of the β-D -anomer. 相似文献
7.
Incorporation of 14C-labelled acetate and amino acids as well as of [1-13C]-, [2-13C]-, and [1,2-13C2] acetate, L -[methyl13C] methionine, [2,3-13C2] succinate, and L -[2,3-13C2] aspartate into spirostaphylotrichin A ( 1 ) by Staphylotrichum coccosporum demonstrates that the building blocks of 1 are 5 units of acetate/malonate, 1 unit of methionine, and a C4-dicarboxylic acid. The latter is most likely aspartate and derived from the citric-acid cycle. Using [2-13C, 2-2H3] acetate as a precursor, the starter unit of the polyketide chain was identified. 相似文献
8.
A new unnatural macrocyclic trichothecene, an analogue of verrucarine A ( 1 ), which was named 3-Isoverrucarin A ((1″-O)(3→4)abeo-verrucarin A; 3 ) was synthesized starting from anguidine ( 5 ). The two key reactions were the removal of the 4β-acetoxy group of anguidine ( 5 ) by a Barton deoxygenation and the final macrolactonization. During the cyclization procedure, two unexpected new macrocyclic by-products, which were named verrucinol ( 19 ) and verrucene ( 20 ), were formed. They represent novel types of macrocyclic trichothecenes, the macrolidic moiety of verrucene ( 20 ) consisting only of the (Z,E)-muconic-acid residue. The formation of the analogous macrolide 26 of verrucene ( 20 ) was not possible, probably because the ring strain is too strong. 相似文献
9.
The antibiotic roridin D (C29H38O9), a companion of roridin A, yields on base catalysed hydrolysis verrucarol ( 3 ) and the hitherto unknown 2, 3-epoxy-2-anhydrororidinic acid ( 4 ) (C14H18O7). Roridin D is a macrocyclic diester to which structure 1 is assigned. In roridin D an epoxy group replaces the hydroxyl group of roridin A. 相似文献
10.
J. Tamm A. Alumaa A. Hallik U. Johanson L. Tamm T. Tamm 《Russian Journal of Electrochemistry》2002,38(2):182-187
The influence of anions ClO4
–, NO3
–, Cl–, SO4
2–, and DDS– (dodecyl sulfate) on the cyclic voltammetric response of polypyrrole-modified electrodes is studied. The change in the film composition is examined by electron probe microanalysis. It is established that essential changes in the shape of voltammograms take place during cycling if the anions are not sufficiently freely mobile in the polymer film and insertion of cations from the solution is necessary to guarantee electroneutrality of the system. Some differences between the mobility of Cl– ions and ClO4
– or NO3
– ions are in good agreement with the results of semi-empirical quantum chemical calculations showing that the interaction of Cl– and Br– ions with pyrrole oligomers is stronger than that of NO3
– or ClO4
– ions. Nevertheless, it is established that the peak current determined from voltammograms increases linearly with the increase of the scan rate with very high correlation coefficient. It means that it is possible to describe the behavior of ClO4
–, NO3
– and Cl– ions in the framework of the model of free ions. The redox behavior of the PPy films doped with anions of low mobility such as SO4
2– and DDS– depends essentially on the nature of cations in the test solution. It is found that the mobility of cations increases in the row Li+ < Na+ < K+ < Cs+. The mobility of DDS– ions in the PPy in ethanolic solution is significantly higher and their electrochemical properties are quite similar to PPy|Cl or NO3
– film in aqueous solution. 相似文献