取代效应对脂滴检测NAPBr染料分子的双光子吸收和激发态性质影响的理论探究

双光子荧光染料分子在生物医学成像中具有广阔的应用前景,但取代效应对分子结构以及光物理性质影响的探求相对匮乏. 本文设计并研究了一系列脂滴检测染料分子,分析了分子的光学性质以及无辐射跃迁等. 通过分子内弱相互作用和电子- 空穴布居分析,阐述了其内在机理. 结果表明,所研究的分子均具有优良的光物理性能、高效荧光量子产量、大的斯托克斯位移以及显著的双光子吸收截面等. 本工作合理地解释了实验现象并阐述了取代效应对脂滴检测NAPBr染料分子的双光子吸收和激发态性质的影响,这为设计新型的高效有机分子提供了理论指导.     

二乙烯三胺吸收CO2分子机理的半经验量子化学研究

以半经验分子轨道的AMl方法计算出分子热力学参数,研究了二乙烯三胺吸收二氧化碳过程的热力学.二乙烯三胺吸收二氧化碳包括两个过程:靠分子间作用力的物理吸收和形成甲酸胺的化学吸收.在两个过程中,一个二乙烯三胺吸收两个二氧化碳分子在热力学上最为有利;氨基甲酸分子中羟基氢离子的电离,在质子受体(如水分子)存在下更为有力,与实验结果相一致.     

1，4-二甲氧基-2，5-二乙烯基苯系列衍生物的双光子吸收截面

在HF水平上，利用解析响应函数方法，研究了1，4_二甲氧基_2，5_二乙烯基苯系列衍生物 分子的单光子和双光子吸收特性. 实验测量了反，反_2，5_双(4′_N,N_二丁胺基苯乙烯)_1 ，4_二甲氧基苯分子的单光子和双光子荧光谱. 研究结果表明该系列分子具有较强的双光子 吸收特性. 在低能量范围内，对于D_π-A型分子，分子的单光子吸收强度和双光子吸收截面 最大值都发生在分子的第一激发态. 对于D_π_D型分子，单光子吸收强度最大值出现在分子 的第一激发态，而最大双光子吸收值则对应于分子的第二激发态. 分子的单和双光子吸收强 度和分子官能团的电性有关. 对于由该类π中心部分构成的分子，其对称型不一定比不对称型更有利于提高双光子吸收截面. 分子基态与电荷转移态的电荷转移过程定性地解释了双光 子聚合反应的聚合机理. 关键词： 双光子吸收 响应函数方法 非线性光学     

酒精的光学特性及浓度检测

通过对酒精透射光谱和吸收光谱的研究发现,其特征吸收峰随浓度不同发生漂移,从分子结构能级角度对其做了定性解释;根据部分稳定的特征吸收峰处不同波长点的吸光度,利用最小二乘法建立了多元线性回归模型,运用此模型实现了根据特征吸收峰波长的位置、强度、形状来预测酒精浓度,测定数据与样品浓度之间在一定范围呈良好的线性关系.     

以二乙烯硫/砜基为中心的新型电荷转移分子双光子吸收特性

理论研究分子结构与双光子吸收性质之间的关系对于指导实验者设计与合成功能分子材料具有重要意义. 在杂化密度泛函水平上, 利用响应函数方法, 计算了一类以二乙烯硫/砜基为中心的新型电荷转移分子的双光子吸收截面, 并在相同计算水平上, 与联苯乙烯类强双光子吸收分子做了比较; 以新型电荷转移分子为基础, 利用异构效应, 设计出了可以增强双光子吸收强度的分子结构. 研究表明, 在可应用波长范围内, 该系列分子表现出较强的双光子吸收响应, 与相似共轭长度的强双光子吸收分子具有相同量级的双光子吸收截面; 二乙烯硫/砜基在分子中心作为吸电子基团可以形成有效的电荷转移分子; 改变咔唑基的连接方式可以有效提高双光子吸收截面. 该研究为实验合成新型双光子吸收分子材料提供了理论依据.     

反-4,4''-双(N,N-二丁胺基)二苯乙烯分子双光子吸收性质研究

对于实验室合成的反-4,4'-双(N,N-二丁胺基)二苯乙烯分子,实验测量了该分子的单光子和双光子荧光谱,然后从理论上研究了其单光子和双光子吸收特性.研究结果表明,在低能量范围内,分子的单光子吸收主要发生在分子的第一激发态,而分子的双光子吸收主要发生在分子的第二和第四激发态上.该分子在相应系列衍生物中具有最大的双光子吸收截面.分子的相关能对分子的激发态能量影响较大.我们给出了分子基态与电荷转移态的电荷转移过程,并从理论上定性解释了双光子聚合反应的聚合机理.     

基于分子内电荷转移的多枝状荧光探针光学性质与响应机理分析

本文采用含时密度泛函理论研究了用于检测生物硫醇的荧光探针分子的光学性质.通过计算探针分子Mol.1、Mol.2和Mol.3与半胱氨酸和同型半胱氨酸反应前后的单光子吸收和发射性质,研究了碳碳三键和苯环结构对荧光探针性质的影响.随着给电子体三苯胺结构的逐渐完善和碳碳三键的加入,探针分子的振子强度逐渐增大,展现出了更好的荧光探针性质.同时,研究了不同侧枝数目对探针分子性质的影响,结果表明,相较于单枝分子Z1和三枝分子Mol.3,两个侧枝的探针分子Z2振子强度更大,检测效果更佳.增加了碳碳三键和苯环后的单枝新型探针分子Mol.4,相较于具有三枝结构的探针分子Mol.3,具有良好的探针性质,且结构更为简单.     

(E,E)-1,4-双{2''-[5''-(B,B-二甲基苯硼)-2-噻吩基]乙烯基}-苯分子双光子吸收特性的理论研究

在密度泛函水平上,利用响应函数方法,研究了分子的单光子和双光子吸收特性.计算出了该分子在低能量范围内的最大双光子吸收截面为6.47×10-47cm4s/photon,与实验符合的较好.研究结果表明该分子具有较强的双光子吸收特性,是较好的双光子吸收材料.     

(E,E)-1,4-双{2''-[5''-(B,B-二甲基苯硼)-2-噻吩基]乙烯基}-苯分子双光子吸收特性的理论研究

在密度泛函水平上,利用响应函数方法,研究了分子的单光子和双光子吸收特性.计算出了该分子在低能量范围内的最大双光子吸收截面为6.47×10-47 cm4 s/photon,与实验符合的较好.研究结果表明该分子具有较强的双光子吸收特性,是较好的双光子吸收材料.     

阿比特龙的红外光谱与前线轨道

采用密度泛函理论的B3LYP混合泛函和6-311G(d,p)基组,通过几何结构优化得到了阿比特龙分子的稳定构型.计算了阿比特龙分子的红外吸收光谱,并与文献数据进行比较,将2971.01、1588.31、1536.13、1450.40、1112.13和1074.44 cm~(-1)等处吸收峰指认为特征吸收峰.在优化计算的基础上,结合Multiwfn软件分析了阿比特龙分子的前线轨道成分,得出阿比特龙分子的亲核能力明显强于其亲电能力,C55、O54原子在95αHOMO中占据的权重分别为61.79%和17.05%,C=O-H部位是其亲核反应的活性中心.研究结果对阿比特龙分子的检测、活性应用等方面具有一定的理论指导意义.     

A spectroscopic database for water vapor adapted to spectral properties at high temperature, and moderate resolution

The prediction of infrared spectral radiance from high temperature media such as combustion gases requires spectroscopic data for triatomic molecules like water vapor and carbone dioxyde. At temperature above 2000 K, water vapor spectrum is composed of hundreds of thousands lines making practical computations uneasy. We have set up a spectroscopic database for water vapor, based on three existing lines compilations. This database is well suited to computation of remote sensing spectra where hot gases emission is seen through atmospheric paths. The database enables efficient computation of water vapor spectra between 600 and 6600 cm⁻¹ at moderate spectral resolution (5 cm⁻¹). It has been used to compute parameters of a statistical narrow band model which are used in practical applications.     

Recombination radiation from landau states in impactionized GaAs

Recombination radiation from Landau states in impact ionized high-purity GaAs has been observed. The narrow band (～ 3 cm^?1) emission has been magnetically tuned from 80–120 cm^?1, and used to observe rotational transitions in water vapor.     

Dielectrophoretic assembly of ZnO nanowires

The synthesis of zinc oxide （ZnO） nanowires is achieved by vapor phase transportation （VPT） method. The designed quartz tube, whose both ends are narrow and the middle is wider, is used to control the growth of ZnO nanowires. Dielectrophoresis （DEP） method is employed to align and manipulate ZnO nanowires which are ultrasonic dispersed and suspended in ethanol solution. Under the dielectrophoretic force, the nanowires are trapped on the pre-patterned electrodes, and further aligned along the electric field and bridge the electrode gap. The dependence of the alignment yield on the applied voltage and frequency is investigated.     

QEPAS detector for rapid spectral measurements

A quartz enhanced photoacoustic spectroscopy sensor designed for fast response was used in combination with a pulsed external cavity quantum cascade laser to rapidly acquire gas absorption data over the 1196–1281 cm⁻¹ spectral range. The system was used to measure concentrations of water vapor, pentafluoroethane (freon-125), acetone, and ethanol both individually and in combined mixtures. The precision achieved for freon-125 concentration in a single 1.1 s long spectral scan is 13 ppbv.     

Radiation sintering of magnesia: Pore structure studies

Co⁶⁰ γ-ray irradiation of a nonequilibrium surface of magnesium oxide produced tremendous effects on both the extent of the surface area, and on the pore structure. In all cases investigated incompletely decomposed crystals showed appreciable lowering of surface area which indicated activated sintering of the material. The pores present are mainly wide, but with a very narrow distribution of their sizes. Their most probable hydraulic radius is about 10 Å. Upon irradiation sintering is accompanied by widening of pores, and a second group of pores showed its appearance in the pore size distribution curves. These effects seem to be associated with the presence of traces of the volatile component of the parent material, and in particular with the presence of traces of water vapor. Irradiation of the completely decomposed material produced no changes in surface area or pore structure.

The role played by water vapor in accelerating the sintering of magnesia is discussed and possible explanations are given for the effects of irradiation. Dual effects of water vapor might lead to the sintering acceleration of magnesia; chemisorption of OH groups which create cation vacancy on the surface leading to activated surface diffusion, and oxygen bridging between two adjacent/or opposite OH groups particularly in narrow pores, leading to their blocking.     

Strain-induced anodization of SiGe/Si multiple layers to form high density SiGe/Si heterogeneous nanorods

SiGe/Si heterogeneous nanostructures are prepared by electrochemical anodization of SiGe/Si multiple layers grown by ultra-high vacuum chemical vapor deposition. Nanorods with densities up to ～2×10¹¹ cm^?2 have been observed with a relatively uniform distribution confirmed by scanning electron microscope images of both top and cross-sectional views. The samples show visible photoluminescence with multiple peaks and narrow widths which is related to the interference effect. Finally, a model is proposed to explain the role of strain during the anodization of SiGe/Si multiple layers.     

Fabrication of a graphene field effect transistor array on microchannels for ethanol sensing

A new approach to the fabrication of back-gated graphene FET (field effect transistor) arrays on microchannels was investigated. Narrow walls fabricated on a substrate with SU-8 (a negative photoresist), with top metal electrodes were pressed onto another silicon/SiO₂ substrate with predeposited graphene pieces such that the electrodes came into contact with graphene pieces and formed the source and drain contact. The SU-8 narrow walls with the top metal layer were fabricated by the conventional lift-off process. The graphene pieces were reduced chemically from graphite oxide. The I_DS changed immediately by more than 17% when the device was exposed to an ethanol atmosphere. The current recovered very well after the ethanol gas was pumped out. The SU-8 microchannels served as gas flow passages that helped the ethanol vapor reach the sensitive region of the device: the graphene channel. This work provides a convenient way of constructing back-gated graphene FETs for sensing applications. This method could potentially be scaled up for mass production.     

Ion-beam formation of electrocatalysts for fuel cells with polymer membrane electrolyte

Active layers of electrocatalysts are prepared by the ion-beam assisted deposition (IBAD) of platinum onto carbon-based AVCarb® Carbon Fiber Paper P50 and Toray Carbon Fiber Paper TGP-H-060 T supports and Nafion® N 115 polymer membrane electrolyte in the mode where the deposited metal ions are used as ions assisting the deposition process. Metal deposition and mixing of the deposited layer with the substrate under an accelerating voltage of 10 kV by the same metal ions are carried out from a neutral fraction of metal vapor and the ionized plasma of a pulsed vacuum-arc discharge, respectively. The composition and microstructure of the surface layers obtained are studied by Rutherford backscattering spectrometry (RBS), scanning electron microscopy (SEM), electron-probe microanalysis (EPMA), and X-ray fluorescence (XRF) analysis. The platinum concentration in the layers is (0.5–1.5) × 10¹⁶ at/cm². The prepared electrocatalysts exhibit activity in the process of the electrochemical oxidation of methanol and ethanol, which form the basis for the principle of operation of low temperature fuel cells (direct methanol fuel cells (DMFC) and direct ethanol fuel cells (DEFC)).     

Structures of nanowires with Zn-ZnO:CuO junctions for detecting ethanol vapors

The synthesis of ZnO-ZnO:CuO structures in the form of overlapping layers of nanowires of pure and copper oxide-doped zinc oxide is described. These structures are tested as ethanol vapor sensors. The following two-stage method is used to form ZnO:CuO nanowires. At the first stage, ZnO nanowires are formed by chemical deposition from a solution. At the second stage, arrays of ZnO nanowires are coated with a copper-containing layer. The CuO content on the surface of ZnO nanowires is changed by varying the number of immersions in a Cu(NO₃)₂ solution. The formed structures are studied by scanning electron microscopy, X-ray diffraction, and energy dispersive X-ray analysis. The interaction of the grown sensor structures with ethanol vapors is analyzed by measuring the potential difference between the layers of pure zinc oxide and copper oxide-modified zinc oxide in the temperature range 190–300°C. The response of the sensor is investigated at various ethanol vapor concentrations and detection temperatures.     

Intensities and widths of H2O lines between 1800 and 2100 cm-1

A non-linear, least-squares program was used to obtain the line intensities and widths of 91 air-broadened lines in the ν₂ rotation-vibration band of water vapor in the region from 1800 to 2100 cm^-1. The values obtained for the line intensities are, on the average, about 7% stronger than the Air Force Cambridge Research Laboratories (AFCRL) Atmospheric Absorption Line Parameters Compilation. The experimental values for the half widths of the H₂O lines are, on the average, 4% higher than the calculated AFCRL values. The measurements have confirmed the narrow widths of some high J transition lines measured by tunable diode laser spectroscopy.