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61.
Guang Shao Akihiro Orita Prof. Dr. Koji Nishijima Kanako Ishimaru Makoto Takezaki Prof. Dr. Kan Wakamatsu Prof. Dr. Rolf Gleiter Prof. Dr. Junzo Otera Prof. Dr. 《化学:亚洲杂志》2007,2(4):489-498
A variety of arylethynylsilanes (Ar‐C?C? C6H4? C?C)nSiMe4?n were prepared successfully by reaction of the corresponding chlorosilanes Me4?nSiCln with Ar? C?C? C6H4? C?CM (M=Li, MgBr), which was prepared by treatment of ethynyl(diarylethyne)s Ar? C?C? C6H4? C?CH with BuLi or MeMgBr. The ethynyl(diarylethyne)s were readily prepared in good yields by the double‐elimination method: addition of lithium hexamethyldisilazide to a mixture of ArCH2SO2Ph, TMS? C?C? C6H4? CHO, and ClP(O)(OEt)2, followed by desilylation. In the tetrakis(arylethynyl)silanes (Ar? C?C? C6H4? C?C)4Si thus prepared, through‐space conjugation of four triple bonds on the silicon atom emerges as a result of participation of the silicon orbitals in the acetylenic π orbitals. This participation enhances the emissive quantum yields of arylethynylsilanes with an increase in the number of arylethynyl moieties on silicon: quantum yields of emission (ΦF) of 0.72 for (MeOC6H4? C?C? C6H4? C?C)4Si, 0.53 for (MeOC6H4? C?C? C6H4? C?C)2SiMe2, and 0.47 for MeO‐C6H4? C?C? C6H4? C?CSiMe3 were obtained. Although this enhancement effect was also observed in the phenylethynylarylsilane (MeOC6H4? C?C? C6H4)2SiMe2, the bis(arylethynyl)disilane (MeOC6H4? C?C? C6H4? C?C‐SiMe2)2 exhibited non‐enhanced emission. 相似文献
62.
Kenji Hamase Yurika Miyoshi Kyoko Ueno Hai Han Junzo Hirano Akiko Morikawa Masashi Mita Tsuneaki Kaneko Wolfgang Lindner Kiyoshi Zaitsu 《Journal of chromatography. A》2010,1217(7):1056-1062
A validated two-dimensional HPLC system combining a microbore-monolithic ODS column and a narrowbore-enantioselective column has been established for a sensitive and simultaneous analysis of hydrophilic amino acid enantiomers (His, Asn, Ser, Gln, Arg, Asp, allo-Thr, Glu and Thr) and the non-chiral amino acid, Gly, in biological samples. To accomplish this goal, the amino acids were first tagged with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F) to the respective fluorescent NBD derivatives which were separated in the first dimension by a micro-reversed-phase column. The automatically collected fractions of the target peaks were then transferred to the second dimension consisting of a Pirkle type enantioselective column generating separation factors higher than 1.13 for all the enantiomeric target analytes. The system was validated using standard amino acids and a rat plasma sample, and analytically satisfactory calibration and precision results were obtained. The present 2D-HPLC system enables the fully automated determination of hydrophilic amino acid enantiomers in mammalian samples. The d-isomers of all the investigated 9 amino acids were found in rat urine but at various enantiomeric ratios. 相似文献
63.
Masahiro Kikuchi Mohammad S. Hussain Norio Morishita Mitsuko Ukai Yasuhiko Kobayashi Yuhei Shimoyama 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2010,75(1):310-313
An electron spin resonance (ESR) spectroscopic study of radicals induced in irradiated fresh mangoes was performed. Mangoes in the fresh state were irradiated with γ-rays, lyophilized and then crushed into a powder. The ESR spectrum of the powder showed a strong main peak at g = 2.004 and a pair of peaks centered at the main peak. The main peak was detected from both flesh and skin specimens. This peak height gradually decreased during storage following irradiation. On the other hand, the side peaks showed a well-defined dose–response relationship even at 9 days post-irradiation. The side peaks therefore provide a useful means to define the irradiation of fresh mangoes. 相似文献
64.
Fluoroalkyl end‐capped cooligomers containing diphenylacetylene segments [RF‐(DPMA)x‐(Co‐M)y‐RF] were prepared by reaction of fluoroalkanoyl peroxide with 4‐(phenylethynyl)phenyl methacrylate (DPMA) and radical polymerizable comonomers such as N,N‐dimethylacrylamide (DMAA) and acryloylmorpholine (ACMO) under very mild conditions. Fluorinated cooligomers containing diphenylacetylene segments thus obtained exhibited a good solubility in a variety of organic solvents. These fluorinated cooligomers were also applied to the surface modification of traditional organic polymers such as poly(methyl methacrylate) (PMMA) to exhibit not only a good surface active property imparted by fluorine but also a fluorescent characteristic related to diphenylacetylene segments on their surface. In addition, these fluorinated cooligomers could form the nanometer size‐controlled fluorinated molecular aggregates in chloroform. Interestingly, some benzenes and biphenyl (BP) derivatives could interact with these fluorinated oligomeric aggregates as guest molecules, and in particular 2‐chloro‐5‐nitrobenzotrifluoride (CNB) was most effective for enhancing the fluorescent intensity of these guest molecules. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
65.
Organotin perfluorooctanesulfonates as air-stable Lewis acid catalysts: synthesis, characterization, and catalysis 总被引:1,自引:0,他引:1
An de L Peng Z Orita A Kurita A Man-e S Ohkubo K Li X Fukuzumi S Otera J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(6):1642-1647
The reactions of 1,3-dichloro-1,1,3,3-tetrabutyldistannoxane and dialkyltin dihalides with silver perfluorooctanesulfonate provided the corresponding sulfonates as hydrates. The number of water molecules (n) of hydration was dependent on the conditions. The distannoxane derivative was identified as n from 0.5 to 6, while in the hydrated mononuclear species and DMSO complexes n varied widely from 4 to 13. 119Sn NMR spectroscopy and conductivity measurements indicated the ionic dissociation of these compounds in solution. These compounds exhibited unusually high solubility in polar organic solvents. The ionic dissociation together with facile hydration probably causes the unusual solubility. The Lewis acidity of these compounds was found to be high among organotin derivatives on the basis of ESR spectra of superoxide/metal-ion complexes. In contrast to well-known organotin triflates, these compounds suffered no hydrolysis upon storage in open air. The high catalytic activity of the distannoxane 1 was exemplified for various carbon-carbon bond-forming reactions, such as Mukaiyama-aldol as well as -Michael reactions and allylation of aldehydes. 相似文献
66.
Several types of organic reactions were accelerated by immediate evaporation of solvents because of remarkable enhancement of molecule-to-molecule contacts between reactants. 相似文献
67.
Shimoyama Y Ukai M Nakamura H 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,63(4):888-890
We revealed free radicals in wheat flour before and after gamma-ray irradiation and their thermal behavior during heat-treatment using electron spin resonance (ESR) spectroscopy. The ESR spectrum of wheat flour before irradiation consists of a sextet centered at g = 2.0 and a singlet signal at the same g-value position. The first one is attributable to a signal with hyperfine (hf) interactions of Mn2+ ion (hf constant: 7.4 mT). The second is originated from carbon-centered radical. Upon gamma-ray irradiation, however, a new signal with two triplet lines at the low and high field ends was detected in wheat flour on top of the Mn2+ sextet lines. We analyzed the triplet ESR lines as powder spectra (rhombic g-tensor symmetry) with nitrogen (14N) hyperfine interactions. This indicates that a new organic radical was induced in the conjugated protein portion of wheat flour by the gamma-ray irradiation. Intensity of the organic free radical at g = 2.0 detected in irradiated wheat flour increased monotonically by the thermal treatment. The analysis of the time-dependent evolution and decay process based on the theory of transient phenomena as well as the nonlinear least-squares numerical method provided a unique time constant for the radical evolution and decay in wheat flour during the heat-treatment. 相似文献
68.
Ukai M Nakamura H Shimoyama Y 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,63(4):879-882
We found various free radicals in a commercially available pepper in Japan before and after irradiation using electron spin resonance (ESR) spectroscopy. The typical ESR spectrum of the pepper consists of a sextet centered at g = 2.0, a singlet at the same g-value and a singlet at g = 4.0. Upon gamma ray irradiation, a new pair of signals appeared in the pepper. The progressive saturation behavior (PSB) at various microwave power levels indicated quite different relaxation behaviors of those radicals. Namely, the peak intensity of the organic free radical component decreases in a monotonic fashion, whereas the Mn2+ and Fe3+ ESR signals substantially keep constant. This reflects the evidence of three independent radicals in the pepper before irradiation. The PSB of the pair peaks as induced by irradiation possessed quite different PSB from that of the free radical located at g = 2.0. We proposed a new protocol for the ESR detection of irradiated foods by the PSB method at different microwave power levels. This would call for a major modification of the CEN protocol in European Union. 相似文献
69.
A new type of fluorous distannoxanes, [XRf2SnOSnRf2Y]2 (Rf = C6F13C2H4; X, Y = C6F13SO3 (2) and (C6F13SO2)2N, Cl (3)) was prepared successfully as hydrates from the reaction of [ClRf2SnOSnRf2Cl]2 with C6F13SO3Ag and (C6F13SO2)2NAg, respectively. Despite their high fluorine content (59.85 and 59.27% F), these distannoxanes were completely insoluble in fluorocarbons as well as hydrocarbons and halo alkanes. In contrast to this, fluorous distannoxanes 2 and 3 were soluble in polar organic solvents, such as EtOAc, acetone, and THF. When 2 and 3 were added to a two-phase mixture of fluorocarbon and EtOAc, the mixture turned miscible in proportion to the amount of 2 and 3 added, and finally, the mixture turned to a homogeneous solution. 相似文献
70.
Jing-Kun Fang De-Lie An Kan Wakamatsu Tetsuo Iwanaga Shin-ichi Akita Akihiro Orita Junzo Otera 《Tetrahedron》2010,66(29):5479-5485
To gain insight into substituent electronic effect on charge-transfer excitation of acetylenic π-systems, phenylene-(poly)ethynylenes substituted by Ph2N or Ph2N/cyano groups were synthesized by combination of Sonogashira coupling and double elimination protocol of β-substituted sulfones. These substituted phenyleneethynylenes showed large molar absorption coefficients ?, and emitted strong fluorescence upon UV light irradiation. Phenylene-(poly)ethynylenes, which involve butadiyne or hexatriyne motifs, emitted fluorescence in remarkably lower fluorescence quantum yields ΦF as their polyethynylene motifs -(CC)n- expanded. The drastic decrease of fluorescence quantum yields ΦF were explained in terms of increasing nonradiative reaction rate constants knr, which had been determined by the corresponding fluorescence quantum yields ΦF and lifetime values τ. The emission underwent a large bathochromic shift in polar solvents because the charge-separated excited state is more stabilized than the ground state. Comparison of slope values ρ in Lippert/Mataga plot for the Ph2N and Ph2N/cyano-substituted phenylene-(poly)ethynylenes revealed that the latter underwent large change of dipole moments upon photo-excitation although highly expanded acetylenic π-systems with cyano group did little. 相似文献