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101.
W. Heinemann 《Fresenius' Journal of Analytical Chemistry》1969,280(2):127-132
Zusammenfassung Die Bedingungen für die atomabsorptions-spektroskopische Bestimmung von Edelmetallen werden über die Minimierung der Variationskoeffizienten der Meßwerte optimiert. Die optimalen Meßbedingungen für die Bestimmung der Elemente Ag, Au, Ir, Pd, Pt, Rh und Ru werden gegeben.
Optimizing of measuring conditions for the determination of noble metals by atomic absorption spectrometry
The parameters for the determination of noble metals by atomic absorption technique are optimized by minimizing of the coeffizients of variation. The optimal conditions for the determination of the elements Ag, Au, Ir, Pd, Pt, Rh and Ru are given.相似文献
102.
The kinetics of the unusually fast reaction of cis- and trans-[Ru(terpy)(NH3)2Cl]2+ (with respect to NH3; terpy=2,2':6',2"-terpyridine) with NO was studied in acidic aqueous solution. The multistep reaction pathway observed for both isomers includes a rapid and reversible formation of an intermediate Ru(III)-NO complex in the first reaction step, for which the rate and activation parameters are in good agreement with an associative substitution behavior of the Ru(III) center (cis isomer, k1=618 +/- 2 M(-1) s(-1), DeltaH(++) = 38 +/- 3 kJ mol(-1), DeltaS(++) = -63 +/- 8 J K(-1) mol(-1), DeltaV(++) = -17.5 +/- 0.8 cm3 mol(-1); k -1 = 0.097 +/- 0.001 s(-1), DeltaH(++) = 27 +/- 8 kJ mol(-1), DeltaS(++) = -173 +/- 28 J K(-1) mol(-1), DeltaV(++) = -17.6 +/- 0.5 cm3 mol(-1); trans isomer, k1 = 1637 +/- 11 M(-1) s(-1), DeltaH(++) = 34 +/- 3 kJ mol(-1), DeltaS(++) = -69 +/-11 J K(-1) mol(-1), DeltaV(++) = -20 +/- 2 cm3 mol(-1); k(-1)=0.47 +/- 0.08 s(-1), DeltaH(++)=39 +/- 5 kJ mol(-1), DeltaS(++) = -121 +/-18 J K(-1) mol(-1), DeltaV(++) = -18.5 +/- 0.4 cm3 mol(-1) at 25 degrees C). The subsequent electron transfer step to form Ru(II)-NO+ occurs spontaneously for the trans isomer, followed by a slow nitrosyl to nitrite conversion, whereas for the cis isomer the reduction of the Ru(III) center is induced by the coordination of an additional NO molecule (cis isomer, k2=51.3 +/- 0.3 M(-1) s(-1), DeltaH(++) = 46 +/- 2 kJ mol(-1), DeltaS(++) = -69 +/- 5 J K(-1) mol(-1), DeltaV(++) = -22.6 +/- 0.2 cm3 mol(-1) at 45 degrees C). The final reaction step involves a slow aquation process for both isomers, which is interpreted in terms of a dissociative substitution mechanism (cis isomer, DeltaV(++) = +23.5 +/- 1.2 cm3 mol(-1); trans isomer, DeltaV(++) = +20.9 +/- 0.4 cm3 mol(-1) at 55 degrees C) that produces two different reaction products, viz. [Ru(terpy)(NH3)(H2O)NO]3+ (product of the cis isomer) and trans-[Ru(terpy)(NH3)2(H2O)]2+. The pi-acceptor properties of the tridentate N-donor chelate (terpy) predominantly control the overall reaction pattern. 相似文献
103.
Sellmann D Geipel F Heinemann FW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(23):4279-4284
The azide and amide complexes (NBu4)[Ni(N3)('S3')] (2) and (NBu4)[Ni[N(SiMe3)2]('S3')] (4) were found to react with CO, CO2, and SO2 under very mild conditions at temperatures down to -50 degrees C. Depending on the N oxidation state of the nitrogen ligands, addition or partial to complete desoxygenation of the oxides takes place. The reaction between 2 and CO gives (NBU4)[Ni(NCO)('S3')] (3). The reactions between 4 and CO, CO2, and SO2 afford selectively the cyano, isocyanato, and sulfinylimido complexes (NBu4)[Ni(X)('S3')] with X = CN- (5), NCO- (3), and NSO- (6). The silyl groups act as oxygen acceptors. Mechanisms are suggested which have in common the formation of reactive five-coordinate (NBu4)[Ni(L)(L')('S3')] intermediates. In these reactions, highly activated L and L' react with each other. The complexes were characterized by standard methods, and (NBu4)[Ni(CN)('S3')] (5) was also analyzed by X-ray crystallography. 相似文献
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105.
Multiphase polymer systems with special phase structures and properties can be achieved by the proper design of the polymer constitution and the appropriate sample treatment. Multiblock copolymers consisting of molecularly uniform polyurethane segments of various molecularly engineered structures and connected by highly flexible polyether segments have been synthesized. The segregation of the hard segments and the size, shape and perfection of the hard domains can be controlled by the hard segment's architecture in that either extended chain crystallization or chain folding occurs. The same superstructure and properties as of the above multiblock copolymers can be mimicked by specially designed graft copolymers with polyether backbone and polyurethane branches, again uniform and molecularly engineered. This study has shown that the morphology and superstructure of macromolecular systems can be precisely controlled by the molecularly designed chain architecture and the sample history, and is correlated with special material properties. 相似文献
106.
本文叙述了高架点源非连续排放的废空气烟羽的γ剂量估算方法,并给出了部分估计算结果,讨论了该方法的应用前景。 A method of evaluating the γ-submersion dose from the waste air-plume emitted by elevated point sources is presented in this paper. Results of the calculation are given in figures.Application of the method is discussed. 相似文献
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