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121.
Henri Brunner Manfred Muschiol Ivan Bernal George M. Reisner 《Journal of organometallic chemistry》1980,198(2):169-178
C7H7Mo(CO)(PN★)I (I) (PN★ (S)(+)-(C6H5)2PN(CH3)CH(CH3)(C6H5)) is prepared in 90% yield by reaction of C7H7Mo(CO)2I and PN★. The two diastereo-isomers Ia and Ib differing only in the Mo-configuration exhibit chemical shift differences of their C7H7 and CH3 signals. Ia and Ib can be separated by fractional crystallization. In solution Ia epimerizes with respect to the Mo configuration. The half lives in benzene for the equilibration Ia ? Ib are 5.5, 30, and 104 min at 60, 50, and 40°C, respectively. Phosphine exchange experiments show that the epimerization proceeds via PN★ dissociation.An X-ray structure analysis was carried out on a single crystal of Ia. The absolute configuration at Mo was determined to be (R). 相似文献
122.
Organophosphorus compounds have been applied in two ways in chemical synthesis. They can either be used as a reagent in a step of the synthesis (for example, in the Wittig reaction) or they can be incorporated directly into the target molecule. This second application, in particular, has expanded greatly in the last few years with the preparation of low-coordination phosphorus compounds. These include the phosphaalkynes, which are of great interest to organic and inorganic chemists. Phosphaalkynes have been employed in the synthesis of heterocyclic compounds, phosphaarenes and their valence isomers, and polycyclic compounds. Further applications have been the use of phosphaalkynes as new ligand systems in complex chemistry and their cyclooligomerization with organometallic reagents. While the chemical properties of phosphaalkynes have little in common with those of nitriles, they are in many ways very similar to those of the isoelectronic acetylenes. 相似文献
123.
Trimethylsilyl Cyanide — A Reagent for Umpolung, VI. Anionic 1,4-O→C-Silyl Group Rearrangement The adducts 6 from substituted acroleins 5a – f and trimethylsilyl cyanide form the anions 6 A on deprotonation at −78°C, which are silylated by trimethylsilyl chloride to 7 or (and) 8 in positions 3 or (and) 1. On warming up to room temperature, 6a A and 6b A undergo smoothly 1,4-O→C-silyl group rearrangements to form 13a A and 13b A which can be trapped by silylation. 6c – d A decompose on warming up. Triethylsilyl instead of trimethylsilyl groups decelerate the rearrangement appreciably. Structure and configuration of the different products are determined. 相似文献
124.
Hoebbel Dagobert Nacken Manfred Schmidt Helmut 《Journal of Sol-Gel Science and Technology》1998,13(1-3):37-43
Heterometal materials based on glycidoxypropyltrialkoxysilane and titaniumalkoxide are used for optical applications and require a high homogeneity on the molecular level. The presence of heterometal titanosiloxanes, their distribution and hydrolytic stability should influence the homogeneity of these materials. 29Si and 17O NMR spectroscopy has been used to investigate sols with molar ratios Si : Ti = 1 and H2O : OR (H) = 0.5 – 2.0 and their gels after heat treatment at 130°C. The presence of Si—O—Ti bonds in sols with a low water content (H < 0.2) and in the corresponding gels was identified by the high-field shift of the 29Si NMR signals of T1 and T2 units of up to 2–3 ppm compared to corresponding signals of homo-condensed Si—O—Si bonds. The existence of Si—O—Ti bonds in the sols is supported by 17O NMR spectra which show a characteristic signal around 340 ppm. A cleavage of the Si—O—Ti bonds occurs with increasing water/OR ratio in the sols. The cleavage of the heterometal bonds and the building up of homo-condensed species leads to a separation into areas with predominantly Ti—O—Ti and Si—O—Si bonds resulting in a decreased molecular homogeneity of the materials. 相似文献
125.
Metallcarbonyl-Synthesen,XIV. Neuartige Vanadium-, Niob- und Tantal-Komplexe mit Wasserstoff-Brücken
Wolfgang A. Herrmann Helmut Biersack Barbara Balbach Peter Wülknitz Manfred L. Ziegler 《欧洲无机化学杂志》1984,117(1):79-94
Syntheses of Metal Carbonyls, XIV. Novel Vanadium, Niobium, and Tantalum Complexes Having Hydrido Bridges The novel homo- and heterodinuclear organometallic μ-hydrido compounds 3a – c of vanadium, niobium, and tantalum have been synthesized by light-induced reactions of the hydridoniobium complex (η5-C5H5)2NbH3 ( 1 ) with the half-sandwich complexes (η5-C5H5)M(CO)4 ( 2a : M = V; 2b : M = Nb; 2c : M = Ta). These compounds have the general composition LxM – H – Nb(CO)(η5-C5H5)2. The formation of the M – H – Nb moieties is a dark-reaction preceded by two photoreactions that are independent from each other elimination of CO from 2a – c and elimination of H2 from 1 , with the extruded carbon monoxide being transfered to the (η5-C5H5)2NbH fragment; subsequent fixation of the species (η5-C5H5)2Nb(CO)H thus generated to the photogragments (η5-C5H5)M(CO)3 results in donor stabilization of these latter groups. The structural architecture of the derivatives 3a und b was established by X-Ray diffraction. The hydrogen bridges are to be considered as three-center two-electron functions that are responsible for a serious lengthening of the otherwise by at least 40 pm shorter metal-to-metal distances amounting to 371.3 pm in 3a and 373.3 pm in 3b (mean values). 相似文献
126.
Klaus Weissermel Hanns-Jerg Kleiner Manfred Finke Utz-Hellmuth Felcht 《Angewandte Chemie (International ed. in English)》1981,20(3):223-233
Besides phosphorus trichloride and phosphane, dichloro(methyl)phosphane is gaining importance as a starting material for the synthesis of organophosphorus compounds. It provides ready access to phosphonic, phosphinic and phosphonous acid derivatives, as well as their secondary products. The synthetic and application potential of organophosphorus compounds—based on industrially produced dichloro(methyl)phosphane—is illustrated by means of numerous examples. 相似文献
127.
The protected 2-formyl-L-arabinal 2 reacted with thiourea and cyanamide in the presence of sodium hydride to afford via ring transformations the 5-[1R,2S-1,2- bis(benzyloxy)-3-hydroxypropyl]-1,2-dihydropyrimidines 3 and 4, respectively. Similarly, treatment of 2 with 3-amino-2H-1,2,4-triazole yielded 6-[1R,2S-1,2- bis(benzyloxy)-3-hydroxypropyl][1,2,4]-triazolo[1,5-a]pyrimidine (5). 相似文献
128.
Manuel Tzouros Laurent Bigler Stefan Bienz Manfred Hesse Akira Inada Hiroko Murata Yuka Inatomi Tsutomu Nakanishi Dedy Darnaedi 《Helvetica chimica acta》2004,87(6):1411-1425
The investigation of the MeOH extract of the leaves of Chisocheton weinlandii Harms (Meliaceae) revealed two new open‐chain spermidine alkaloids, chisitine 1 ( 1 ) and chisitine 2 ( 2 ). Their structures were elucidated by NMR spectroscopy, tandem‐mass spectrometry, and independant syntheses (Scheme 3). Detailed MS/MS fragmentation pathways are discussed for both compounds based on H/D exchange and 18O‐labeling experiments (Schemes 1 and 2). 相似文献
129.
Peter ?ernoch Petr Štěpánek Miroslav Šlouf Manfred Stamm 《European Polymer Journal》2007,43(4):1144-1153
A systematic study of formation of surface patterns in block copolymer thin layers after their exposure to solvent vapors was performed. The studied effect involves layers of thickness approximately equal to the ordering size of polymers - about 45 nm. Experiments were performed on three styrene - methacrylate derivative block copolymers, synthesized by living anionic polymerization: poly(4-octylstyrene)-block-poly(butyl methacrylate), poly(4-fluorostyrene)-block-poly(butyl methacrylate) and poly(p-octylstyrene)-block-poly(methyl methacrylate). The polymers were exposed to vapors of chloroform, 1,4-dioxane, hexane, acetone and tetrahydrofuran. 相似文献
130.
Lambert C Nöll G Zabel M Hampel F Schmälzlin E Bräuchle C Meerholz K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(17):4232-4239
Two highly substituted azulene derivatives were synthesised by Pd-mediated dimerisation from the corresponding tolan species. One azulene derivative (2) has donor functionalities (dianisylaminophenyl and dianisylamino) in the 1-, 2-, 3- and 6-positions, while the other (1) has donors (dianisylaminophenyl) in the 2- and 6-positions and acceptors (nitrophenyl) in the 1- and 3-positions. Each azulene derivative shows strong bond length alternation in the solid state, determined by X-ray crystal analysis, and an intense CT band around 450-500 nm in its UV/Vis spectrum. The first-order hyperpolarisability of 1 and of 2 was measured by hyper-Rayleigh scattering and is about that of disperse red DR1. Both azulene derivatives show multiple oxidation processes. The intramolecular adiabatic ET behaviour of the mixed valence radical cations of 1 and of 2 was investigated by UV/Vis/NIR spectroelectrochemistry. The intervalence-CT band of 1(+) could be analysed by the Generalised Mulliken-Hush theory, which yields an electronic coupling V=1140 cm(-1) for the optically induced adiabatic hole transfer. 相似文献