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The shaped pulses were shown to be phase-sensitive at intensities too low to access different higher electronic states, and so these pulses apparently steer the isomerization through constructive and destructive interference effects, a mechanism supported by observed signatures of vibrational coherence.
脉冲形状被证明是在太低以至于不能进入不同的较高电子态的强度上对相位变化灵敏的,因此这些脉冲机制通过构成和破坏干扰反应操纵着异构化作用,这种机制由观测到的相干信号支持。
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The shaped pulses were shown to be phase-sensitive atintensities too low to access different higher electronic states,and so these pulses apparently steer the isomerization throughconstructive and destructive interference effects, a mechanismsupported by observed signatures of vibrational coherence.
变过形的脉冲在低强度下显得很敏感,这种强度很小,因此很难进入更高的电子状态。于是,很明显地,这些脉冲能给通过破坏性和建设性的干扰效应来操控异构化作用。观测到的振动一致信号更支持了这样一种机制。
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Several transient compounds were synthesized by the homo- and heterogeneous reactions of reactive halogen compounds, In-situ ultraviolet photoelectron spectroscopy and photoionization mass spectroscopy as well as theoretical calculations were used to study their molecular structures, stability and molecular orbital properties, their electronic structures and geometric structures were obtained for the first time; Simultaneously, the electronic structure and thermal dissociation of acetyl peroxynitrate and trifluoroacetyl peroxynitrate which have great importance in the atmospheric chemistry were studied; The substituent effects of series of halopyridines and halothiophenes were studied by the ultraviolet photoelectron spectroscopy method for the first time. The atmospheric chemical reaction between peroxyacetyl radicals with IO radicals as well as the dissociation of the most stable isomer of CH3COIO3 were calculated by density functional theory, it was found that the CH3COOIO2 isomer may be act as a new reservoir of inorganic iodine in the stratosphere.
通过活性卤素的系列均相与非均相化学反应合成了几种瞬态物种,采用原位紫外光电子能谱和光电离质谱结合量子化学理论计算对化合物的分子结构、稳定性以及分子轨道特性进行了研究,首次获得了这些物种的电子结构和几何结构的信息;同时研究了大气中有重要作用的乙酰过氧硝酸酯和三氟乙酰过氧硝酸酯的电子结构性质及热解过程;采用紫外光电子能谱手段首次研究了系列卤代吡啶和噻吩的取代基效应;通过量子化学理论计算研究了乙酰基过氧自由基与IO自由基的大气化学反应及其最稳定异构体CH3COOIO2的解离,发现该物种可能是无机碘化合物在平流层中的储库物种。
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RESULT: 1.Ouabain act on lens sodium-pump,under the LM,lens anterior capsular membrane discontinuous,epithelium cells clustered,occluding zonule seperated,lens fiber layers fractured.Under the EM,cells totally hollowed,mitochondria swelling,myelin figure appeared.RT-PCR examine the expression condition of αsubunit of sodium pump on mRNA level,α1、α2 and α3-isoform are all decreased.2.Digoxin act on lens sodium-pump,under the LM,lens cell oedema,linkage distructed,extensive exfoliation.Under the EM,plasma appeared little half-transparant hollow region,mitochondria swelling and ridge disappeared. RT-PCR examine,α1、α2 and α3-isoform are all decreased.3.Amphotericin B act on lens sodium-pump,under the LM,lens epithelium cells linked tightly,arranged in-line,lens fiber layers arranged tightly and regularily.Under the EM,abbundant cellular organes,exuberant cells function indicated. RT-PCR examine the expression condition of αsubunit of sodium pump on mRNA level,α1 and α3-isoform are increased significantly,demonstrated isoform-specific action.4D-thyroxine act on lens sodium-pump,under the LM,lens plasmalemma integrated,cells arranged tightly and regularily.Under the EM,nucleus fission appeared,desmosome half-desmosome and tensile microfilaments linked the cells. RT-PCR examine,α2 and α3-isoform are increased, also demonstrated isoform-specific action.5.Vitamin E act on lens sodium-pump,under the LM,lens anterior capsular membrane continuous and smooth,epithelium cells tightly linked,lens fiber layers appearede hollow region occasionally.Under the EM,lateral membrane high density belt appeared,abundant nucleolus. RT-PCR examine,onlyα1-isoform are increased, demonstrated significantly isoform-specific action.6.DMSO act on lens sodium-pump,under the LM,lens anterior capsular membrane slightly thicker,cells linkage partly distructed.Under the EM,plasmalemma denaturation,mitochondria swelling.RT-PCR examine,α1、α2 and α3-isoform are all altered slightly and haven't significant meanning.
结果:1、哇巴因作用于晶状体钠泵后,光镜下晶状体前囊膜断裂、上皮细胞聚积、闭合连接分离、纤维板层裂隙,电镜下全层细胞空泡化、线粒体肿胀出现髓样结构,RT-PCR法检测晶状体钠泵α亚单位α1、α2及α3三种重整异构体在mRNA水平的表达均减弱。2、地高辛作用于晶状体钠泵后,光镜下晶状体细胞水肿、细胞连接破坏、广泛剥离,电镜下胞质见少许半透明空化区、线粒体肿胀嵴消失,RT-PCR法检测晶状体钠泵α亚单位α1、α2及α3三种重整异构体在mRNA水平的表达均减弱。3、两性霉素B作用于晶状体钠泵后,光镜下晶状体上皮细胞紧密连接、线状排列、纤维板层紧密规整,电镜下细胞器丰富、细胞功能旺盛,RT-PCR法检测α1及α3表达显著增强、具有一定的重整异构作用特异性。4、D甲状腺素作用于晶状体钠泵后,光镜下晶状体质膜完整、细胞排列紧密规整,电镜下胞核见分裂像、细胞间有桥粒、半桥粒及张力微丝,RT-PCR法检测α2及α3表达均增强、亦有一定的重整异构作用特异性。5、维生素E作用于晶状体钠泵后,光镜下晶状体前囊膜连续光滑、上皮细胞紧密连接、纤维板层偶见空化,电镜下囊侧膜内有高电子密度带、细胞核仁丰富,RT-PCR法检测仅有α1的表达显著增强、具有极强的重整异构作用特异性。6、二甲基亚砜作用于晶状体钠泵后,光镜下晶状体前囊膜轻度增厚、细胞连接部分破坏,电镜下质膜变性、线粒体肿胀,RT-PCR法检测晶状体钠泵α亚单位α1、α2及α3三种重整异构体在mRNA水平的表达无显著改变。
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Photoinduced Electron Transfer [2+2] Cycloaddition Reactions ofBenzannelated Isoquinolin-1-ones with Electron Deficient Alkenes Photoinduced [2+2] cycloaddition reactions of 11H-benzoxazolo[3,2-b]isoquinolin-11-one 8 and 11H-benzothiazolo[3,2-b]isoquinolin-11-one 13 with electron deficient alkenessuch as acrylonitrile, methyl acrylate, dimethyl fumarate and dimethyl maleate afforded a group of polycyclic isoquinoline derivatives bearing cyclobutane moieties ingood to excellent yields and resulted in the Schenck isomerization of the alkenes.
3苯并增环异喹啉-1-酮与缺电子烯烃的光诱导电子转移[2+2]环加成反应 11H-苯并恶唑[3,2-b]异喹啉-11-酮8和11H-苯并噻唑[3,2-b]异喹啉-11-酮13与缺电子烯烃如丙烯腈,丙烯酸甲酯,富马酸二甲酯及马来酸二甲酯的光诱导[2+2]环加成反应以高产率给出一系列含有环丁烷结构单元的多环异喹啉衍生物并导致烯烃的Schenck异构化作用。