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171.
172.
Formal meta-specific intramolecular Friedel–Crafts allylic alkylation of phenols was achieved based on spirocyclization–dienone–phenol rearrangement cascades. Systematic screening of acid catalysts revealed that Sc(OTf)3 was a highly effective catalyst for dienone–phenol rearrangement of spiro[4.5]cyclohexadienones. Using 5 mol % of Sc(OTf)3 as the promoter, various spirocyclic substrates were transformed into the corresponding phenol derivatives in good to excellent yield. Furthermore, the one-pot sequential spirocyclization–dienone–phenol rearrangement proceeded using a palladium and scandium multi-catalytic system or a triphenylmethyl cation single-catalyst system, providing the corresponding meta-allylated phenol derivatives in excellent yield. 相似文献
173.
174.
Nishiyama Y Endo Y Nemoto T Utsumi H Yamauchi K Hioka K Asakura T 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2011,208(1):44-48
Substantial resolution and sensitivity enhancements of solid-state (1)H detected (14)N HMQC NMR spectra at very fast MAS rates up to 80 kHz, in a 1mm MAS rotor, are presented. Very fast MAS enhances the (1)H transverse relaxation time and efficiently decouples the (1)H-(14)N interactions, both effects leading to resolution enhancement. The micro-coil contributes to the sensitivity increase via strong (14)N rf fields and high sensitivity per unit volume. (1)H-(14)N HMQC 2D spectra of glycine and glycyl-L-alanine at 70 kHz MAS at 11.7 T are observed in a few minutes with a sample volume of 0.8 μL. 相似文献
175.
Universal Reaction Mechanism of Boronic Acids with Diols in Aqueous Solution: Kinetics and the Basic Concept of a Conditional Formation Constant
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Yuki Furikado Tomomi Nagahata Takuya Okamoto Dr. Tomoaki Sugaya Prof. Dr. Satoshi Iwatsuki Prof. Dr. Masahiko Inamo Prof. Dr. Hideo D. Takagi Prof. Dr. Akira Odani Prof. Dr. Koji Ishihara 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13194-13202
To establish a detailed reaction mechanism for the condensation between a boronic acid, RB(OH)2, and a diol, H2L, in aqueous solution, the acid dissociation constants (${K{{{\rm BL}\hfill \atop {\rm a}\hfill}}}$ ) of boronic acid diol esters (HBLs) were determined based on the well‐established concept of conditional formation constants of metal complexes. The pKa values of HBLs were 2.30, 2.77, and 2.00 for the reaction systems, 2,4‐difluorophenylboronic acid and chromotropic acid, 3‐nitrophenylboronic acid and alizarin red S, and phenylboronic acid and alizarin red S, respectively. A general and precise reaction mechanism of RB(OH)2 with H2L in aqueous solution, which can serve as a universal reaction mechanism for RB(OH)2 and H2L, was proposed on the basis of (a) the relative kinetic reactivities of the RB(OH)2 and its conjugate base, that is, the boronate ion, toward H2L, and (b) the determined pKa values of HBLs. The use of the conditional formation constant, K′, based on the main reaction: RB(OH)2+H2L ${{\mathop \leftrightarrow \limits ^{K{_{1}}}_{}}}$ RB(L)(OH)?+H3O+ instead of the binding constant has been proposed for the general reaction of uncomplexed boronic acid species (B′) with uncomplexed diol species (L′) to form boronic acid diol complex species (esters, BL′) in aqueous solution at pH 5–11: B′+L′ ${{\mathop \leftrightarrow \limits ^{K{^\prime}}_{}}}$ BL′. The proposed reaction mechanism explains perfectly the formation of boronic acid diol ester in aqueous solution. 相似文献
176.
Tomomi Kawasaki Yoshinori Nonaka Ken Matsumura Miyuki Monai Masanori Sakamoto 《合成通讯》2013,43(18):3251-3261
An efficient method for synthesis of 2-methoxy-l,2-dihydro-3H-indol-3-ones using two successive oxidations of indoles is described. 相似文献
177.
Experimental endeavor for addressing the origins of life when viewed from the physical perspective presents a new opportunity of developing physics further for its own sake. A case in point is the issue of intensities. The physics of the origins of life may more readily be approachable by way of the dynamics of intensities or intensive quantities such as temperature and force strengths, compared to the standard dynamics of extensive quantities such as molecule numbers, densities, masses and charges. What is unique to the dynamics of intensities is that it is already contextual in addressing the context under which the intensities in focus are generated and maintained. In particular, because of the contextual nature of temperature grounded upon the material context in which the contextual elements move almost randomly with each other, the occurrence of temperature gradients provides an impetus for transforming the material context. The physical origins of life are just associated with the emergence of the robust material context that can serve as a heat engine. One likely candidate for the material context serving as a heat engine that could emerge in the presence of temperature gradients near hot vents in the primitive ocean on the Earth might have been a citric acid cycle running with no help of enzymes of biological origin. Underlying the emergence of a robust heat engine is the pruning principle of the faster temperature drop going with the greater stored latent heat applied to any reacting molecules crossing the temperature gradients. 相似文献
178.
Hideo Nemoto Hiroshi Kurobe Keiichiro Fukumoto Tetsuji Kametani 《Tetrahedron letters》1984,25(41):4669-4672
Stereocontrolled synthesis of (?)-de-AB-8-oxa-cholest-14-en-9-one (2) as an optically active form was achieved starting from the methylene ketone (7). This work constitutes a formal synthesis of de-AB-cholestan (1). 相似文献
179.
Hirokazu Tsukamoto Takamichi Suzuki Tomomi Uchiyama Yoshinori Kondo 《Tetrahedron letters》2008,49(26):4174-4177
A palladium(0)-tricyclohexylphosphine catalyzes cis-selective alkylative and arylative cyclization of alkyne-containing electron-deficient alkenes with organoboron reagents to provide five- or six-membered rings with exo tri- or tetra-substituted alkenes. The opposite stereoselectivity to that for the alkyne-aldehyde cyclization using the same reagents would result from palladacycle-forming oxidative addition of the substrates to the Pd0 catalyst followed by transmetalation with the boron reagents, protonation, and reductive elimination. The functional group compatibility, availability, stability, and non-toxicity of the reagents, and the fact that no additives are needed make the process more practical than the Ni0-catalyzed cyclization with organozinc reagents. 相似文献
180.
Lipid components from 12 nonpathogenic Mycobacterium species were analysed. A novel cyclic C(35)-terpene, named heptaprenylcycline , was obtained from 3 species, while octahydroheptaprenol , which has 3 Z-double bonds, was obtained from 6 species. The amounts of and in the cultured cells increased after the 4- to 6-d stationary phase. The yield of was considerably greater at a higher temperature of 37 degrees C than at an optimal temperature of 28 degrees C, while that of remained unchanged at all temperatures. A feeding experiment with d-[1-(13)C]glucose revealed that was produced via isopentenyl diphosphate, which is a metabolite of glycolysis and the methylerythritol phosphate pathway. The conversion of octahydroheptaprenyl diphosphate to was successful by using the cell-free extracts of M. chlorophenolicum, demonstrating that is the biosynthetic intermediate of . This is the first example of the biosynthesis of a natural terpene via the cyclisation of a linear C(35)-isoprenoid. The substrate for C(35)-terpene cyclase has Z-type prenyl moieties; however, terpene cyclases usually employ E-type isoprenoids. The gene encoding the terpene cyclase that cyclises prenyl diphosphate containing Z-double bonds as the natural substrate has not yet been detected. Despite a careful search using the FASTA3 program, we could not detect any gene that is homologous to the known diphosphate-triggered type of mono-, sesqui- and diterpene cyclases in the genome of M. vanbaalenii, the DNA sequence of which has recently been elucidated. This suggests that a novel type of terpene cyclase might exist in the nonpathogenic Mycobacterium species. 相似文献