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41.
Stable polyacrylamide (polyAA)–montmorillonite adducts were prepared by two distinct processes: (1) free radical copolymerization of AA with alkaline clay previously treated with 2-(N-methyl-N,N-diethyl ammonium iodide)ethylacrylate (QD1) and (2) direct interactions of alkaline montmorillonite with various preformed copolymers of AA with QD1. The structure of the adducts as determined by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and X-ray diffraction was shown to consist of AA macromolecules inserted between lamellar layers whose spacing was larger than in the polymer-free clay. The polymer was strongly attached to the inorganic surfaces, probably due to cooperative formation of electrostatic bonding. The thermal stability of the organic polymers in the resulting complexes was substantially enhanced while the mobility of macromolecules decreased. 相似文献
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Kyung‐Youl Baek Masami Kamigaito Mitsuo Sawamoto 《Journal of polymer science. Part A, Polymer chemistry》2002,40(12):1937-1944
A series of functionalized 2‐bromoisobutyrates and 2‐chloro‐2‐phenylacetates led to α‐end‐functionalized poly(methyl methacrylate)s in Ru(II)‐catalyzed living radical polymerization; the terminal functions included amine, hydroxyl, and amide. These initiators were effective in the presence of additives such as Al(Oi‐Pr)3 and n‐Bu3N. The chlorophenylacetate initiators especially coupled with the amine additive gave polymers with well‐controlled molecular weights (Mw/Mn = 1.2–1.3) and high end functionality (Fn ~ 1.0). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1937–1944, 2002 相似文献
44.
Fokin AA Tkachenko BA Gunchenko PA Gusev DV Schreiner PR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(23):7091-7101
The structures, strain energies, and enthalpies of formation of diamantane 1, triamantane 2, isomeric tetramantanes 3-5, T(d)-pentamantane 6, and D(3d)-hexamantane 7, and the structures of their respective radicals, cations, as well as radical cations, were computed at the B3LYP/6-31G* level of theory. For the most symmetrical hydrocarbons, the relative strain (per carbon atom) decreases from the lower to the higher diamondoids. The relative stabilities of isomeric diamondoidyl radicals vary only within small limits, while the stabilities of the diamondoidyl cations increase with cage size and depend strongly on the geometric position of the charge. Positive charge located close to the geometrical center of the molecule is stabilized by 2-5 kcal mol(-1). In contrast, diamondoid radical cations preferentially form highly delocalized structures with elongated peripheral C-H bonds. The effective spin/charge delocalization lowers the ionization potentials of diamondoids significantly (down to 176.9 kcal mol(-1) for 7). The reactivity of 1 was extensively studied experimentally. Whereas reactions with carbon-centered radicals (Hal)(3)C(*) (Hal=halogen) lead to mixtures of all possible tertiary and secondary halodiamantanes, uncharged electrophiles (dimethyldioxirane, m-chloroperbenzoic acid, and CrO(2)Cl(2)) give much higher tertiary versus secondary selectivities. Medial bridgehead substitution dominates in the reactions with strong electrophiles (Br(2), 100 % HNO(3)), whereas with strong single-electron transfer (SET) acceptors (photoexcited 1,2,4,5-tetracyanobenzene) apical C(4)-H bridgehead substitution is preferred. For diamondoids that form well-defined radical cations (such as 1 and 4-7), exceptionally high selectivities are expected upon oxidation with outer-sphere SET reagents. 相似文献
45.
We report a convenient method for quantitative non-covalent functionalization of single-walled carbon nanotubes (SWNT) with phthalocyanine (Pc) compounds, in which a surface coverage of 49% was achieved. The effect of several process parameters on the functionalization process was elucidated. Firstly, as-produced SWNT gave the largest extent of functionalization compared with purified SWNT and as-produced multi-walled carbon nanotubes (MWNT). Secondly, the extent of functionalization was sensitive to the specific molecular structures of the Pc compounds. Finally, in terms of solvent selection, dimethylformamide (DMF) was found to give the largest extent of functionalization, which is then followed by chloroform (CHCl3) and 1,2-dichlorobenzene (ODCB). The method reported in this paper provides new insights on the interactions between Pc molecules and carbon nanotubes and paves the way for rational control of the degree of functionalization, which is an important step from the perspective of carbon nanotube applications.
Electronic supplementary material Supplementary material for this article is avilable at and is accessible for authorised users. 相似文献
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Rina Chun Saegun Kim Sang Hoon Han Ashok Kumar Pandey Neeraj Kumar Mishra In Su Kim 《Tetrahedron letters》2018,59(43):3848-3852
The site-selective C–H nitration reaction of 7-azaindoles with t-butyl nitrite under palladium catalysis is described. This protocol provides an efficient method for the construction of ortho-nitrated N-aryl-7-azaindoles with excellent site-selectivity and functional group compatibility. The formed 7-azaindole derivatives can be readily transformed into 7-azaindoles containing an aniline functional group under palladium-catalyzed hydrogenation conditions. 相似文献
48.
Dr. Tsubasa Nakashima Haruka Fujimori Dr. Kohsuke Ohmatsu Prof. Takashi Ooi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(36):9253-9256
Intermediary radical cations, generated through single-electron oxidation of enol silyl ethers by excited Ir-based photocatalysts, can be exploited as Brønsted acids for the activation of heteroarylcyanides. This strategy enables the direct allylic C−H heteroarylation of enol silyl ethers under visible-light irradiation. 相似文献
49.
The synthesis and copolymerization of 4-hydroxybenzylglycolide: experimental and theoretical aspects
《Mendeleev Communications》2021,31(5):701-703
Based on tyrosine, 4-hydroxybenzylglycolide was synthesized. Its study in ring-opening copolymerization with lactides in view of the ability of the phenolic hydroxy group to initiate polymerization was performed experimentally and with DFT modeling. 相似文献
50.
Dr. Manuel Vázquez Sulleiro Ramiro Quirós-Ovies Mariano Vera-Hidalgo Dr. I. Jénnifer Gómez Dr. Víctor Sebastián Prof. Jesús Santamaría Prof. Emilio M. Pérez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(9):2993-2996
The combination of 2D materials opens a wide range of possibilities to create new-generation structures with multiple applications. Covalently cross-linked approaches are a ground-breaking strategy for the formation of homo or heterostructures made by design. However, the covalent assembly of transition metal dichalcogenides flakes is relatively underexplored. Here, a simple covalent cross-linking method to build 2H-MoS2–MoS2 homostructures is described, using commercially available bismaleimides. These assemblies are mainly connected vertically, basal plane to basal plane, creating specific molecular sized spaces between MoS2 sheets. Therefore, this straightforward approach gives access to the controlled connection of sulfide-based 2D materials. 相似文献