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201.
Takashi Abe Eiji Hayashi Hajime Baba Kazuo Kodaira Shunji Nagase 《Journal of fluorine chemistry》1980,15(5):353-380
Five kinds of 2-alkyl-substituted oxanes like 2-ethyloxane, 2-n-propyloxane, 2-iso-propyloxane, 2-n-butyloxane and 2-n-amyloxane were fluorinated electrochemically to give the corresponding perfluoro(2-alkyloxane)s. The perfluoro(2-alkyloxane)s were obtained in good yields from these starting materials together with isomeric perfluoro(2-alkyloxolane)s, perfluoro(2-alkyl-5-methyloxolane)s and perfluoro(dialkyl ether)s. The purification of the perfluoro(2-alkyloxane)s which contained small amounts of isomeric perfluoro(2-alkyloxolane)s was successfully achieved by recovering the former unreacted after treating these mixture with anhydrous aluminum chloride at 150 /sR 160 °C during /sR 48 hrs in order to convert the latter into the easy-separable perfluoro(2,5,5- trichloro-2-alkyloxolane)s. Small quantities of new perfluoro(5,5-dichloroalkanoyl chloride)s were also among the chlorination products. The spectroscopic data as well as the physical properties of these new fluorination products, and perfluoro(2,5,5-trichloro-2-alkyloxolane)s and perfluoro(5,5-dichloroalkanoyl chloride)s are presented. 相似文献
202.
Takashi Fujita Takao Yoshioka 《Journal of polymer science. Part A, Polymer chemistry》1982,20(6):1639-1647
Copolymerization of N-oxyl biradical with α-chloro-p-xylylene was carried out by varying the feed ratio of α,α′-dichloro-p-xylene which was the precursor of α-chloro-p-xylylene. The structures of the obtained copolymers were determined spectroscopically. The results that the N-oxyl attacked the carbon-bearing chlorine atom of α-chloro-p-xylylene suggest a nucleophilic reactivity of N-oxyl radical. The copolymerization process was also discussed. 相似文献
203.
5-Amino-5-deazaflavin derivatives are newly synthesized by direct coupling of 5-deazaflavins and amines. Some of them revealed potential activity toward tumor cells such as L1210 or KB cells. 相似文献
204.
A theoretical analysis of the current-potential curves for facilitated ion transfer across an oil/water interface is presented for the case where two complex species having an ion-to-ligand ratio of 1:1 and 1:2 are allowed to exist in the oil phase. Cyclic voltammograms are calculated numerically by using a finite difference method assuming that the ion transfer is reversible and the complex formation equilibria are maintained throughout the oil phase. When the ligand concentration in the oil phase is much smaller than the ion concentration in the aqueous phase and the former limits the ion-transfer current, two well separated peaks may develop even under the assumption of equilibrium conditions for the complex formation. The shape of the voltammogram is determined primarily by the ratio of the two reduced stability constants: b1 = K1bcLO and b2 = K1K2(bcOL)2, where K1 and K2 are the stability constants for 1:1 and 1:2 complexes in the oil phase and bcOL the ligand concentration in the bulk of the oil phase. The degree of peak separation thus depends not only on K2/K1 but also on bcOL. A method for estimating the two stability constants from the voltammograms is proposed. 相似文献
205.
The effects of cation symmetry and packing on the mixed-valence state of binuclear ferrocene derivatives are discussed separately by using chiral isomers and racemic modification of 1',1' "-bis(2-phenylbutyl)-1,1' '-biferrocenium pentaiodide. The pentaiodide anion has a polymeric structure and is composed of triiodide anion and iodine molecule units. The (R,S) isomer having an inversion center shows a detrapped-valence state even at 78 K. On the other hand, the (R,R) and the (S,S) isomers having no inversion center show a trapped-valence state at room temperature. The racemic modification, however, consisting of the (R,R) and the (S,S) isomers shows a perfect detrapped-valence state at room temperature. This finding shows that the packing effect overcomes the effect of cation asymmetry. 相似文献
206.
Hiroyuki Hayakawa Hiromichi Tanaka Keiko Sasaki Kazuhiro Haraguchi Takafumi Saitoh Fumi Takai Tadashi Miyasaka 《Journal of heterocyclic chemistry》1989,26(1):189-192
Several 8-substituted cordycepins were prepared via LDA lithiation of 2′,5′-bis-O-(t-butyldimethylsilyl)-cordycepin and successive reactions of its C-8 lithiated species with various types of electrophiles. Wittig reaction of the 8-formyl derivative was also examined. 相似文献
207.
Morishita H Ohashi S Oku T Nakajima Y Kojima S Ryufuku M Nakamura H Ohmiya Y 《Photochemistry and photobiology》2002,75(3):311-315
Two marine dinoflagellates, Lingulodinium polyedrum and Pyrocystis lunula, emit light in a reaction involving the enzymatic oxidation of its tetrapyrrole luciferin by molecular oxygen. The characteristic properties of P. lunula luciferase have not been clarified, whereas L. polyedrum luciferase, which has three active domains, has been characterized. A cloned partial cDNA of the P. lunula luciferase encodes an active fragment corresponding to part of domain 2 and all of domain 3 of L. polyedrum luciferase. The homology of the amino acid sequence between the two luciferases in domain 3 is about 84.3%. A recombinant His-tagged luciferase fragment containing domain 3 (Mr = 46 kDa) catalyzed the light-emitting oxidation of luciferin (lambdamax = 474 nm). This protein was purified by a single affinity-chromatography procedure. The pH-activity profile and the bioluminescence spectrum of the recombinant enzyme having a third domain are almost identical to those of an extract from P. lunula cultured in vitro. The recombinant enzyme is active at pH 8.0, although the recombinant enzyme derived from the second domain of L. polyedrum luciferase is inactive at pH 8.0. Substitution of Glu-201 by histidine in the third domain of P. lunula luciferase showed a decrease of activity above pH 7.0, suggesting that histidine residues could be responsible for pH-sensitivity in dinoflagellate luciferase. 相似文献
208.
We examined the hydrolysis mechanism of salicylic acid-tyrosine (salicyl-tyrosine) and salicylic acid-methionine conjugate (salicyl-methionine) in rabbits by exploring their behavior following intraduodenal and intracecal administration (72 and 36 mumol/kg, respectively: salicylic acid equivalent). A large amount of salicyl-methionine was absorbed following intraduodenal administration of salicyl-methionine, without being metabolized to salicylic acid in the small intestinal mucosa. On the contrary, salicylic acid was detected in the blood following intraduodenal administration of salicyl-tyrosine, suggesting that salicyl-tyrosine was metabolized in the small intestinal mucosa. After oral pretreatment of rabbits with kanamycin sulfate (6 x 400 mg) or tinidazole (6 x 160 mg), the hydrolysis of salicyl-tyrosine and salicyl-methionine following intracecal administration was inhibited significantly, indicating that the intestinal microorganisms were responsible for the biotransformation of these prodrugs. Furthermore, in rabbits orally pretreated with both kanamycin sulfate and tinidazole, a significant inhibition of salicylic acid formation from salicyl-tyrosine and salicyl-methionine following intracecal administration was observed. 相似文献
209.
Fumiyuki Ozawa Takashi Ito Yoshiyuki Nakamura Akio Yamamoto 《Journal of organometallic chemistry》1979,168(3):375-391
New palladium(0) complexes with a variety of coordinated olefins [Pd(olefin)(PMePh2)2] (II) (olefin = styrene, ethyl methacrylate, methyl methacrylate, methyl acrylate, methacrylonitrile, and dimethyl maleate), were prepared by the reactions of [PdEt2(PMePh2)2] (I) with corresponding olefins in toluene. These complexes were characterized by means of elemental analysis, IR and 1H NMR spectroscopy and the chemical reactions. The dissociation of the coordinated olefin from complex II in solution was confirmed by spectroscopic studies of [Pd(mma)(PMePh2)2] (mma = methyl methacrylate). From the variable temperature NMR study, kinetic parameters for the dissociation process were determined as Ea = 7 kcal/mol, and ΔS3 (293 K) = -30 cal/deg · mol. Some new hydrido complexes, [Pd(H)ClL2] (IV) (L = PMePh2, PEtPh2 and PEt2Ph), were prepared by the reactions of [Pd(olefin)L2] with dry HCl. 相似文献
210.
Layer-by-layer assembled multilayer films of titanate nanotubes, Ag- or Au-loaded nanotubes, and nanotubes/nanosheets with polycations 总被引:1,自引:0,他引:1
Aqueous suspensions of hydrothermally synthesized titanate nanotubes and poly(diallyldimethylammonium chloride) (PDDA) have been employed to fabricate multilayer films on various substrates in a layer-by-layer fashion. Atomic force microscopy displays the dense coverage of the substrate surface by the nanotubes. UV-vis absorption spectroscopy confirms the consecutive growth of PDDA/nanotube layer pairs. Single crystalline Ag and Au nanoparticles with narrow size distribution spatially correlating with the nanotubes have been obtained by treating the nanotubes with AgNO(3) or HAuCl(4) aqueous solution followed by chemical reduction. The noble metal nanoparticles show a strong surface plasmon absorption band. A multilayer film construction of the noble-metal-loaded nanotubes has also been achieved. This process has been further extended to the heteroassembly of nanotubes/nanosheets in different layer sequences. 相似文献