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91.
Frontispiece: Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide 下载免费PDF全文
92.
Prof. Dr. Sławomir J. Grabowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14600-14611
Ab initio calculations were performed on complexes of ZH4+ (Z=N, P, As) and their fluoro derivatives, ZFH3+ and ZF4+, with a HCN (or LiCN) molecule acting as the Lewis base through the nitrogen electronegative center. It was found that the complexes are linked by the Z? H???N hydrogen bond or another type of noncovalent interaction in which the tetravalent heavy atom of the cation acts as the Lewis acid center, that is, when the Z???N link exists, which may be classified as the σ‐hole bond. The formation of the latter interaction is usually preferable to the formation of the corresponding hydrogen bond. The Z???N interaction may be also considered as the preliminary stage of the SN2 reaction. This is supported by the observation that for a short Z???N contact, the corresponding complex geometry coincides with the trigonal‐bipyramidal geometry typical for the transition state of the SN2 reaction. The Z???N interaction for some of complexes analyzed here possesses characteristics typical for covalent bonds. Numerous interrelations between geometrical, topological and energetic parameters are discussed. The natural bond orbital method as well as the Quantum Theory of “Atoms in Molecules” is applied to characterize interactions in the analyzed complexes. The experimental evidences of the existence of these interactions, based on the Cambridge Structure Database search, are also presented. In addition, it is justified that mechanisms of the formation of the Z???N interactions are similar to the processes occurring for the other noncovalent links. The formation of Z???N interaction as well as of other interactions may be explained with the use of the σ‐hole concept. 相似文献
93.
A novel flame retardant resin was prepared by modifying benzoxazines with a reactive phosphorus-containing compound, 2-(6-Oxido-6H-dibenzo[c,e][1,2]oxa-phosphorin-6-yl) 1,4-benzenediol (ODOPB). The curing reactions of the benzoxazines containing ODOPB (ODOPB-BOZ) and a type of bifunctional benzoxazine (B-BOZ) were investigated via differential scanning calorimetry. The ODOPB-BOZ precursors exhibited lower curing temperature in comparison with the B-BOZ. Through dynamic mechanical analysis tests, it was found that the glass transition temperature and storage modulus of the cured ODOPB-BOZ were lower than those of the cured B-BOZ. Moreover, the tensile and flexural properties of the cured ODOPB-BOZ were also lower than those of the cured B-BOZ. The TGA tests proved that, owing to the presence of ODOPB, the char yield of the polybenzoxazines were remarkably raised while the decomposition rates at higher temperature were reduced. It was found that the flame retardancy of cured ODOPB-BOZ attained V-0 grade upon the UL-94 tests while that of cured B-BOZ was V-1 grade. SEM images showed that more compact char layers were formed in the cured ODOPB-BOZ after combustion, resulting in the improvement of flame retardance. 相似文献
94.
H. Herzmann 《Isotopes in environmental and health studies》2013,49(2):45-52
Radioaktiv markierte Präparate haben in denletzten Jahren in schnell zunehmendem Maße Eingang in die klinische Medizin gefunden. Sie sind beieiner Reihe von Indikationen schon jetzt außerordentlich wertvolle Hilfsmittel bei der Diagnose, besonders bei der Prüfung von Organfunktionen. 相似文献
95.
Réka Mokrai Jamie Barrett Dr. David C. Apperley Dr. Andrei S. Batsanov Dr. Zoltán Benkő Dr. Dominikus Heift 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(16):4017-4024
To study pnictogen bonding involving bismuth, flexible accordion-like molecular complexes of the composition [P(C6H4-o-CH2SCH3)3BiX3], (X=Cl, Br, I) have been synthesised and characterised. The strength of the weak and mainly electrostatic interaction between the Bi and P centres strongly depends on the character of the halogen substituent on bismuth, which is confirmed by single-crystal X-ray diffraction analyses, DFT and ab initio computations. Significantly, 209Bi–31P through-space coupling (J=2560 Hz) is observed in solid-state 31P NMR spectra, which is so far unprecedented in the literature, delivering direct information on the magnitude of this pnictogen interaction. 相似文献
96.
Monika Cichocka 《光谱学快报》2018,51(2):118-121
The intracellular brain pH in phosphorus magnetic resonance spectroscopy is calculated using the chemical shift between the inorganic phosphate and phosphocreatine with the Henderson–Hasselbalch equations. Researchers use various mathematical formulas that have different parameters and get various results for the same input data as a consequence. Thus, the aim of this article was to determine the mathematical formulas that allow the conversion of the pH values obtained by the most popular analysis methods to each other. To determine the relationships between pH results and the applied mathematical formula, the pH values were calculated using two algorithms for the theoretical chemical shift values. The pH results were compared with each other using the appropriate t-tests. Mathematical formulas were designed to simplify the conversion of pH values obtained by two data analysis methods to each other. The pH values with were obtained this way did not differ significantly from the pH values calculated directly from the given formula. The computed mathematical formulas will make it possible to simplify pH conversions without knowing the chemical shift between inorganic phosphate and phosphocreatine but only basing on the final pH values obtained by one of the formulas. 相似文献
97.
Rolf Appel Nikolaos Siabalis 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):273-274
Abstract Reactions of carbonyl cyclopentadienyl hydrides from molybdenum and tungsten with 1,4-diphosphabuta-1,3-diene yield metalla-diphospha-pentadiene with a metal-phosphorus-double bond. Metalla-diphosphapentadiene mit einer Metall-Phosphor-Doppelbindung werden durch Umsetzung von Carbonylcyclopentadienylhydriden des Molybdäns und Wolframs mit einem 1,4-Diphospha-buta-1,3-dien erhalten. 相似文献
98.
Malek Taher Maghsoodlou Sayyed Mostafa Habibi Khorasani Nourollah Hazeri Mahmoud Nassiri Reza KaKaei Ghasem Marandi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):553-560
Stable crystalline phosphorus ylides were obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine and dialkyl acetylenedicarboxylates, in the presence of strong NH-acids, such as imidazole, 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, benzimidazole, and 5,6-dimethylbezimidazole. These stable ylides exist in solution as a mixture of two geometrical isomers as a result of restricted rotation around the carbon–carbon partial double bond resulting from the conjugation of the ylide moiety with the adjacent carbonyl group. 相似文献
99.
Malek Taher Maghsoodlou Nourollah Hazeri Sayyed Mostafa Habibi Khorasani Aqil Ghulame Shahzadeh Mahmoud Nassiri 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4):913-919
Stable crystalline phosphorus ylides were obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine and dialkyl acetylenedicarboxylates in the presence of strong NH acids, such as indole and 2-methyl indole, 3-methyl indole, and 5-boromo indole. These stable ylides exist in a solution as a mixture of two geometrical isomers as a result of the restricted rotation around the carbon–carbon partial double bond resulting from the conjugation of the ylide moiety with the adjacent carbonyl group. 相似文献
100.