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121.
Ring cleavage α to the oxygen function leads to [C3H5O]+ and [C4H7O]+ ions in the mass spectra of 4-arylcyclohexanols and their methyl ethers, respectively. Cleavage α to the aryl group gives rise to [C3H7O]+ (from the alcohols), [C4H9O]+ (from the ethers) and [ArC3H4]+ (from both) ions. The competition between the two ring cleavages explains the effect of the substituents of the aryl groups on the relative abundances of the resulting ions. 相似文献
122.
检验分子晶体非线性光学极化率的可加性,对于确认有向气体模型(Oriented-Gas Model) 具有重要的科学意义,对探索新型实用的分子非线性光学材料也有实际的意义。本文对尿素晶体中分子簇非线性光学极化率的可加性做了详尽的理论研究。首次做到了尿素分子最近邻排布团簇的非线性光学极化率的从头算,从而扩展了前人的工作。研究结果有效地确认了有向气体模型。同时,我们还提出了壳层结构模型 (Shell-Structure Model),用以解决有向气体模型中的缺陷,可实现更为有效可靠地计算晶体宏观非线性光学系数。 相似文献
123.
Could the New Absorption Cross Section of J/ψ Change the Aspect of Nuclear Absorption Mechanism
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The enlarged new absorption cross sections of J/ψ by π and ρ were put into the hadron and string cascade model, JPCIAE, and the J/ψ suppression factors in P-A, O-U, S-U and Pb-Pb minimum bias collisions at 200A GeV/c were calculated with nuclear absorption mechanism only. The results seem to indicate that, with new enlarged cross section it is still hard to change the aspect that nuclear absorption mechanism itself could not easily account for the J/ψ anomalous suppression in Pb-Pb collisions. 相似文献
124.
Qian Rong LI* Ting Hu ZHANG Robert S.WARD Structure Research Laboratory University of Science Technology of China Hefei Chemistry Department University of Wales Swansea Singleton Park Swansea SA PP UK 《中国化学快报》2001,(12)
Introduction 2, 3-Dichloro-5, 6-dicyanobenzoquinone (DDQ) can react with lignans of the mono- arylidene-butyrolactone1, aryltetralin2, dibenzylbutane3 and aryltetralin-butyrolactone4,5 series. We have studied the reactions of this reagent with podophyllotoxin 1, which is a well-known natural product on account of its long history of use in folk medicine and the biological activity of its many derivatives6. In particular, derivatives of 4-demethyl epipodophyllotoxin are used in cancer chemo… 相似文献
125.
S A Asher A Ianoul G Mix M N Boyden A Karnoup M Diem R Schweitzer-Stenner 《Journal of the American Chemical Society》2001,123(47):11775-11781
UV resonance Raman studies of peptide and protein secondary structure demonstrate an extraordinary sensitivity of the amide III (Am III) vibration and the C(alpha)H bending vibration to the amide backbone conformation. We demonstrate that this sensitivity results from a Ramachandran dihedral psi angle dependent coupling of the amide N-H motion to (C)C(alpha)H motion, which results in a psi dependent mixing of the Am III and the (C)C(alpha)H bending motions. The vibrations are intimately mixed at psi approximately 120 degrees, which is associated with both the beta-sheet conformation and random coil conformations. In contrast, these motions are essentially unmixed for the alpha-helix conformation where psi approximately -60 degrees. Theoretical calculations demonstrate a sinusoidal dependence of this mixing on the psi angle and a linear dependence on the distance separating the N-H and (C)C(alpha)H hydrogens. Our results explain the Am III frequency dependence on conformation as well as the resonance Raman enhancement mechanism for the (C)C(alpha)H bending UV Raman band. These results may in the future help us extract amide psi angles from measured UV resonance Raman spectra. 相似文献
126.
Photochemical incorporation of silver quantum dots in monodisperse silica colloids for photonic crystal applications. 总被引:1,自引:0,他引:1
We developed a novel method to fabricate nanocomposite monodisperse SiO2 spheres (approximately 100 nm) containing homogeneously dispersed Ag quantum dots (approximately 2 to 5 nm). The inclusion morphology is controlled through the timing of the photochemical reduction of silver ions during hydrolysis of tetraethoxysilane in a microemulsion. Depending on the timing, Ag quantum dots can be directed to different annuli within the SiO2 spheres, as well as onto the SiO2 sphere surfaces. The embedded Ag quantum dots show a plasmon resonance absorption band at 438 nm. These Ag@SiO2 particles have significant surface charge and readily self-assemble into crystalline colloidal array (CCA) photonic crystals which Bragg-diffract light in the visible region. The magnitude of the plasmon resonance absorption depends on the CCA Bragg diffraction condition. The negative dielectric constant of the silver nanoparticles may be decreasing the silica-silver nanodot composite refractive index below that of the water medium. We may be observing an analogue of the Borrmann effect previously observed in X-ray scattering, where the incident and diffracted electric field standing wave becomes localized in regions of small CCA crystal absorption. 相似文献
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Kimble KW Walker JP Finegold DN Asher SA 《Analytical and bioanalytical chemistry》2006,385(4):678-685
We have developed an ammonia-sensitive material by coupling the Berthelot reaction to our polymerized crystalline colloidal array (PCCA) technology. The material consists of a periodic array of highly charged colloidal particles (110 nm diameter) embedded in a poly(hydroxyethyl acrylate) hydrogel. The particles have a lattice spacing such that they Bragg-diffract visible light. In the Berthelot reaction, ammonia, hypochlorite, and phenol react to produce the dye molecule indophenol blue in an aqueous solution. We use this reaction in our sensor by covalently attaching 3-aminophenol to the hydrogel backbone, which forms cross-links through the Berthelot mechanism. Ammonia reacts with hypochlorite, forming monochloramine, which then reacts with a pendant aminophenol to form a benzoquinone chlorimine. The benzoquinone chlorimine reacts with another pendant aminophenol to form a cross-link. The creation of new cross-links causes the hydrogel to shrink, which reduces the lattice spacing of the embedded colloidal array. This volume change results in a blue-shift in the diffracted light proportional to the concentration of NH3 in the sample. We demonstrate that the NH3 photonic crystal sensing material is capable of quantitative determination of concentrations in the physiological range (50–350 μmol NH3 L−1) in human blood serum. 相似文献