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11.
Zusammenfassung Komplexometrische Methoden zur Bestimmung von Zink in Gegenwart von Palladium(II) wurden ausgearbeitet. Dabei wird Palladium(II) mit Kaliumcyanid getarnt und der Zinkgehalt entweder bei pH 5,8 oder nach Demaskierung mit Chloralhydrat bei pH 10 mit ÄDTA gegen Methylthymolblau titriert. Diese Zinkbestimmung läßt sich auch in Anwesenheit einer Mischung von Palladium(II), Kupfer(II), Nickel und Kobalt(II) durchführen.
Summary Complexometric methods have been developed for determining zinc in the presence of palladium(II). In these procedures, Pa(II) is masked with potassium cyanide and the zinc content is titrated either at pH 5.8 or after demasking with chloralhydrate is titrated with EDTA at pH 10 in the presence of methylthymol blue. This zinc determination may also be conducted in the presence of a mixture of palladium(II), copper(II), nickel(II),and cobalt(II).相似文献
12.
Riedl Z Kövér P Soós T Hajós G Egyed O Fábián L Messmer A 《The Journal of organic chemistry》2003,68(14):5652-5659
2-Arylsulfanyl and 2-benzylsulfanylpyridinium N-arylimides (2) easily prepared from 3-aryltetrazolopyridinium salts (1) with aryl and benzylthiolates, respectively, reacted with various dipolarophiles yielding cycloadducts that underwent transformation to give tetrahydropyrrolo[3,2-b]pyridines (5, 6, and 8) in good yields. A similar rearrangement (formation of 15) was also observed in the case of parent derivatives being unsubstituted in position 2 (12). The abscence of any significant solvent effect, comparison of the sulfur and non-sulfur analogues, as well as the stereoselective nature of the observed ring transformation seem to support a sigmatropic mechanism. Structure elucidation of the products has been carried out by single-crystal X-ray diffraction and (1)H NMR experiments. 相似文献
13.
Conformations of 2-methoxytetrahydropyran as a model for the six-membered ring in aldopyranosides have been calculated by the PCILO method using the algorithm of the conjugated gradient to optimize the geometry. The calculated geometry of the fourteen basic forms of 2-methoxytetrahydropyran was found to be in agreement with the available data obtained by X-ray diffraction of pyranosides. The results indicate differences in the geometry of 2-methoxytetrahydropyran resulting from the change of the axial vs. equatorial position of the methoxyl group. These changes are particularly meaningful in the values of bond angles and they are in agreement with the anomeric and exoanomeric effects. The experimentally found differences in the energies of an axial (4
C
1) and equatorial (1
C
4) conformer, G = 2.9–3.7 kJ/mol, and the dipole moment, = 1.20 ± 0.05 D (1D = 3.33 10–30mAs) agree well with the calculated values E = 3.18 kJ/mol and <> = 1.18 D which, in turn, suggest that the axial conformer is preferred over the equatorial one by a ratio a:e = 78:22. 相似文献
14.
The possibility of coulometric titrations of cysteine, 2-thio-uracil, 6-mercaptopurine, and 6-thioguanine with iodine and bromine in methanol and with bromine in acetic acid has been investigated. Conditions have been found for the direct titration of the test substances with iodine in methanol based on their 1-electron oxidation to the corresponding disulphides and for their direct and indirect determination with bromine in acetic acid based on their 6-electron oxidation to the corresponding sulphonic acids.On leave from Department of Analytical Chemistry, Charles University, Prague, Czechoslovakia 相似文献
15.
Kótai László Horváth Tibor Szentmihályi Klára Keszler Ágnes 《Transition Metal Chemistry》2000,25(3):293-294
We have investigated the effect of temperature on the postulated quasi-intramolecular acid-base reactions in aqueous solutions of Cu(NH3)4(MnO4)2 and Ag(NH3)2ClO4. Pure ammonium permanganate and perchlorate were obtained above 5 C and at room temperature, respectively, due to quasi-intramolecular acid-base reactions. 相似文献
16.
Gyula Záray Tibor Kántor Gerhard Wolff Zdravka Zadgorska Hubertus Nickel 《Mikrochimica acta》1992,107(3-6):345-358
The analytical capability of high-temperature halogenation with carbon tetrachloride vapour in a graphite furnace was investigated for silicon carbide powder with known chemical composition and particle size. Intensity vs heating time curves were determined for analytical lines of Al, B, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Ti, V and Si constituents, volatilized with and without the presence of CCl4 vapour in the furnace atmosphere. Igniting 10 mg SiC at 2100 °C for 60 s in chlorinating atmosphere, the evaporated fraction of most of the constituents was higher than 90% (for Al about 50%). The line intensity vs sample mass (4–26 mg) relationships were linear for all impurities studied, while the intensity of silicon line showed a relatively small change with the sample mass. BEC (background equivalent concentration) values for this solid sampling technique (10 mg loaded sample) were 2–20 fold lower than those calculated for the conventional solution sample introduction method. 相似文献
17.
We studied the reactions of some N-methylpyrrole derivatives with isopropenyl acetate and different acetic anhydrides. We have found that the reaction with isopropenyl acetate afforded 5-acetylpyrrole derivatives while with acetic anhydrides acetylation occurred on the α-carbon atom of the side-chain of pyrrole-2-acetic acid derivatives. 相似文献
18.
For everyt>1 and positiven we construct explicit examples of graphsG with |V (G)|=n, |E(G)|c
t
·n
2–1/t
which do not contain a complete bipartite graghK
t,t
!+1 This establishes the exact order of magnitude of the Turán numbers ex (n, K
t,s
) for any fixedt and allst!+1, improving over the previous probabilistic lower bounds for such pairs (t, s). The construction relies on elementary facts from commutative algebra.Research supported in part by NSF Grants DMS-8707320 and DMS-9102866.Research supported in part by Hungarian National Foundation for Scientific Research Grant 相似文献
19.
Pham TN Hinchley SL Rankin DW Liptaj T Uhrín D 《Journal of the American Chemical Society》2004,126(40):13100-13110
We have developed methodology for the determination of solution structures of small molecules from residual dipolar coupling constants measured in dilute liquid crystals. The power of the new technique is demonstrated by the determination of the structure of methyl beta-d-xylopyranoside (I) in solution. An oriented sample of I was prepared using a mixture of C(12)E(5) and hexanol in D(2)O. Thirty residual dipolar coupling constants, ranging from -6.44 to 4.99 Hz, were measured using intensity-based J-modulated NMR techniques. These include 15 D(HH), 4 (1)D(CH), and 11 (n)D(CH) coupling constants. The accuracy of the dipolar coupling constants is estimated to be < +/- 0.02 Hz. New constant-time HMBC NMR experiments were developed for the measurement of (n)D(CH) coupling constants, the use of which was crucial for the successful structure determination of I, as they allowed us to increase the number of fitted parameters. The structure of I was refined using a model in which the directly bonded interatom distances were fixed at their ab initio values, while 16 geometrical and 5 order parameters were optimized. These included 2 CCC and 6 CCH angles, and 2 CCCC and 6 CCCH dihedral angles. Vibrationally averaged dipolar coupling constants were used during the refinement. The refined solution structure of I is very similar to that obtained by ab initio calculations, with 11 bond and dihedral angles differing by 0.8 degrees or less and the remaining 5 parameters differing by up to 3.3 degrees . Comparison with the neutron diffraction structure showed larger differences attributable to crystal packing effects. Reducing the degree of order by using dilute liquid crystalline media in combination with precise measurement of small residual dipolar coupling constants, as shown here, is a way of overcoming the limitation of strongly orienting liquid crystals associated with the complexity of (1)H NMR spectra for molecules with more than 12 protons. 相似文献
20.
István Szilágyi Krisztina Imrik Dariusz Sarzisky Sándor Dóbé Tibor Bérces 《Reaction Kinetics and Catalysis Letters》2002,77(2):341-345
The title reactions have been studied at room temperature by applying the discharge flow method coupled with laser induced fluorescence detection of methoxy radicals and resonance fluorescence detection of bromine atoms. The following rate constants were determined: CH3O + Br Õ products (1) k
1 (298 K) = (3.4 ± 0.4 (1)) × 1013 cm3 mol-1 s-1, CH3O + Br2 Õ products (2) k
2 (298 K) £ 5 × 108 cm3 mol-1 s-1. 相似文献