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91.
Dr. Akihiro Ito Kazuhira Hata Kensuke Kawamoto Dr. Yasukazu Hirao Prof. Dr. Kazuyoshi Tanaka Dr. Motoo Shiro Dr. Ko Furukawa Prof. Dr. Tatsuhisa Kato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(35):10866-10878
para‐Phenylene‐bridged spirobi(triarylamine) dimer 2 , in which π conjugation through four redox‐active triarylamine subunits is partially segregated by the unique perpendicular conformation, was prepared and characterized by structural, electrochemical, and spectroscopic methods. Quantum chemical calculations (DFT and CASSCF) predicted that the frontier molecular orbitals of 2 are virtually fourfold degenerate, so that the oxidized states of 2 can give intriguing electronic and magnetic properties. In fact, the continuous‐wave ESR spectroscopy of radical cation 2 .+ showed that the unpaired electron was trapped in the inner two redox‐active dianisylamine subunits, and moreover was fully delocalized over them. Magnetic susceptibility measurements and pulsed ESR spectroscopy of the isolated salts of 2 , which can be prepared by treatment with SbCl5, revealed that the generated tetracation 2 4+ decomposed mainly into a mixture of 1) a decomposed tetra(radical cation) consisting of a tri(radical cation) moiety and a trianisylamine radical cation moiety (≈75 %) and 2) a diamagnetic quinoid dication in a tetraanisyl‐p‐phenylendiamine moiety and two trianisylamine radical cation moieties (≈25 %). Furthermore, the spin‐quartet state of the tri(radical cation) moiety in the decomposed tetra(radical cation) was found to be in the ground state lying 30 cal mol?1 below the competing spin‐doublet state. 相似文献
92.
The mechanism by which the ribosome catalyze peptide bond formation remains controversial. Here we describe the synthesis of dinucleotides that can be used in kinetic isotope effect experiments to assess the transition state of ribosome catalyzed peptide bond formation. These substrates are the isotopically labeled dinucleotide cytidylyl-(3′-5′)-3′-amino-3′-deoxy-3′-l-phenylalanyl-N6,N6-dimethyladenosine (Cm6ANPhe-NH2) and cytidylyl-(3′-5′)-3′-amino-3′-deoxy-3′-(l-2-hydroxy-3-phenylpropionyl)-N6,N6-dimethyladenosine (Cm6ANPhe-OH). These substrates are active in peptide bond formation and can be used to measure kinetic isotope effects in ribosome catalyzed protein synthesis. 相似文献
93.
Synthesis of gold nanoparticles modified with ionic liquid based on the imidazolium cation 总被引:6,自引:0,他引:6
The synthesis and processing of nanoparticles consisting of metallic nanocrystal cores and organic monolayer shells promise interesting technological applications. Here, we report the synthesis of gold nanoparticles modified with ionic liquids based on the imidazolium cation. Aggregation-induced color changes of the gold nanoparticles in an aqueous solution were used as an optical sensor for anions via anion exchange of ionic liquid moiety. We also demonstrated the phase transfer of the gold nanoparticles from aqueous media to ionic liquid. 相似文献
94.
As a novel molecular designing for genuinely organic molecule-based ferrimagnets, we have proposed a strategy of "single-component ferrimagnetics". When a pi-biradical with an S = 1 ground state and a pi-monoradical with S = (1)/(2) are united by sigma-bonds, the pi-conjugation between the biradical and the monoradical moieties should be truncated in the resultant triradical. This gives magnetic degrees of freedom for both S = 1 and (1)/(2) in the single molecule, serving as a building block for organic molecule-based ferrimagnets under favorable conditions (single-component ferrimagnetics). We have designed and synthesized a triradical, 3-(1'-oxyl-3'-oxido-4',4',5',5'-tetramethylimidazolin-2-yl)benzoic acid 2,4-bis(1' '-oxyl-3' '-oxido-4' ',4' ',5' ',5' '-tetramethylimidazolin-2-yl)phenyl ester (4), as a model compound for the novel approach to genuinely organic ferrimagnets. In the triradical 4, a m-phenylene-bis(nitronyl nitroxide) biradical with a triplet (S = 1) ground state is united with a phenyl nitronyl nitroxide monoradical (S = (1)/(2)) by an ester coupler. Solution-phase ESR spectra from 4 exhibited a complex hyperfine splitting due to (14)N and (1)H nuclei. The analysis of the hyperfine structure based on perturbation calculations has revealed that the exchange interaction within the biradical moiety is much larger than those between the biradical and the monoradical moieties and the magnetic degrees of freedom for both S = 1 and (1)/(2) are retained in 4. An X-ray crystal structure analysis showed that the triradical molecules are arranged in a one-dimensional molecular chain in the crystal. The magnetic susceptibility in a crystalline solid state is consistent with the crystal structure. 相似文献
95.
Shigeru Maeda Hideto Fukuyama Emi Yokoyama Takayoshi Kuroiwa Akira Ohki Kensuke Naka 《应用有机金属化学》1997,11(5):393-396
The bioaccumulation and excretion of antimony by the freshwater alga Chlorella vulgaris , which had been isolated from an arsenic-polluted environment, are described. When this alga was cultured in a medium containing 50 μg cm−3 of antimony(III) for 14 days, it was found that Chlorella vulgaris bioaccumulated antimony at concentrations up to 12 000 μg Sb g−1 dry wt after six days' incubation. The antimony concentration in Chlorella vulgaris decreased from 2570 to 1610 μg Sb g−1 dry wt after the cells were transferred to an antimony-free medium. We found that the excreted antimony consists of 40% antimony(V) and 60% antimony(III). This means that the highly toxic antimony(III) was converted to the less toxic antimony (V) by the living organism. Antimony accumulated in living Chlorella vulgaris cells was solvent-fractionated with chloroform/methanol (2:1), and the extract residue was fractionated with 1% sodium dodecyl sulfate (SDS). Gel-filtration chromatography of the solubilized part showed that antimony was combined with proteins whose molecular weight was around 4×104 in the antimony-accumulated living cells. © 1997 by John Wiley & Sons, Ltd. 相似文献
96.
97.
Atsushi Takahara Kensuke Nakamura Keiji Tanaka Tisato Kajiyama 《Macromolecular Symposia》2000,159(1):89-96
During preparation of very thin polymer belnd films from a solution of polymers, the phase‐separated structures which are quite different from that observed for the bulk blend film was observed. From atomic force microscopic(AFM) observation, it is concluded that the surface undulation, which reflects the phase separated morphology of the blend system, is present. In the case of (polystyrene(PS)/poly(methyl methacrylate)(PMMA)) blend system, a large influence of end‐group chemistry on the surface morphology was observed. The phase identification of the (rubbery polymer/glassy polymer) binary blend thin films was successfully achieved by scanning vioscoelasticity microsopy(SVM). 相似文献
98.
Susumu Harada Takeo Taguchi Nobuhito Tabuchi Kensuke Narita Yuji Hanzawa 《Angewandte Chemie (International ed. in English)》1998,37(12):1696-1698
Under mild conditions the acyl group of acylzirconocene chloride 1 formed from an alkene or alkyne and [(C5H5)2ZrHCl] reacts as an “unmasked” acyl anion. The Lewis acid mediated reactions with aldehydes that yield α-ketol products in high yields demonstrate the versatility of this reagent for C–C coupling. 相似文献
99.
Two bacteria exhibiting resistance to toxic arsenic were isolated. These had been contaminated with arsenic in a Chlorella sp. culture medium containing arsenic. The two bacteria were identified as Klebsiella oxytoca and Xanthomonas sp., and grew well in a peptone medium at neutral pH at 30°C, reaching the stationary phase in ca 100h and 70h, respectively. The growth of the bacteria was not affected by arsenic(V) concentrations in the medium as high as 1000mg dm?3. The bacteria bioaccumulated arsenic, a part of the arsenic being methylated. The bioaccumulation exhibited its peak around the turing point from the log phase to the stationary phase. The relative content of methylated arsenic in the excrement was greater than that in the bacterial cells. Adaptation treatment of inorganic arsenic caused an increase in the bioaccumulation of inorganic arsenic by K. oxytoca. Such a situation was not observed in the case of Xanthomonas sp. The bacteria also bioaccumulated methylated arsenic compounds, and demethylation of these species was observed. When the bacteria were killed by ethanol, arsenic was not taken up by the cells. 相似文献
100.
Masazumi Ishiguro Kensuke Harada Keiichi Tanaka Takehiko Tanaka 《Journal of Molecular Spectroscopy》1996,180(2):355-358
Rotational transitions of fluoroacetylene in the ν1(CH stretch) vibrational state have been observed by the laser–microwave double resonance technique using a color center laser as a radiation source in the 3 μm region. The rotational constant and centrifugal distortion constant in the ν1state were determined to be 9684.310(16) MHz and 2.68(62) kHz, respectively, where the uncertainties given in parentheses correspond to 2.5 standard deviations. 相似文献