Possible spectroscopic manifestation of the angular group induced bond alteration (AGIBA) effect in toluene

The most obvious consequence of the concept of aromaticity is the common confidence that in aromatic compounds, bond lengths do not alternate and are between typical to the single and double ones. However, in 1994, performing crystal structure investigations of substituted pyridines and their salts, Krygowski and co‐workers have discovered a very surprising angular group induced bond alteration (AGIBA) effect: It appears that some angular substituents, like methoxy or nitrozo groups, can induce bond alternation in aromatic rings. Crystal studies do not allow one to operate with liquids that are more common in organic chemistry. This paper presents the first possible evidence of spectroscopic manifestations of the AGIBA effect. Raman spectra of the liquid toluene are analyzed. It is found that instead of being single, the line corresponding to the ring breathing vibrations is clearly split by 1.0–1.4 cm^?1, thus indicating the presence of two (cis‐ and trans‐) AGIBA isomers. The energy difference between these isomers estimated in temperature dependent Raman studies is found equal to 6.68 kJ mol^?1. The low‐wavenumber line therefore corresponds to the cis‐AGIBA isomer and the high‐wavenumber line to the trans‐AGIBA isomer stabilized by the AGIBA effect. Copyright © 2007 John Wiley & Sons, Ltd.     

On‐line Determination of Particle Size Distributions in Flowing Dispersions

Emulsions are of great importance to industry. They are involved in many engineering operations, including chemical reactions, extraction, emulsification and suspension polymerization, etc. However, an important problem for these processes is how to control the size distribution of the dispersed phase. Indeed, off‐line analysis of the emulsion may generate uncertainties due to sampling and dilution of the product, which are likely to change the dispersion state and physico‐chemical properties. In this work, an on‐line optical method is proposed to characterize dispersed media in real flowing conditions. This method is based on the time‐analysis of back‐scattered light fluctuations. The present paper deals with the development of this method and its application to dispersions of alumina in water. The results obtained with the on‐line optical method are compared with those acquired by classical laser light scattering and microscopy.     

类型γ射线能谱指纹的识别机理

放射源的辐射指纹能起到标识和鉴别放射性物体的作用.在涉及核弹头不可逆销毁过程的深度核裁军核查中,核弹头的辐射指纹对标识和鉴别裁减下来的核弹头将起到关键作用.预先研究辐射指纹的有关技术,如识别机理的研究,将有助于深度核裁军的核弹头核查技术发展.以实验室放射源为研究对象,探索了类型γ射线能谱指纹的同一性识别机理.类型γ射线指纹识别机理的研究,就是要找出一种合适的方法,以较高的置信度,描述两个正在进行比较的γ射线指纹是否为同一放射源的指纹.采用了谱形比较法,并用谱相似度概念来描述两个指纹的相似程度.在谱形比较思想的指导下,编制了放射源类型指纹识别软件,并通过放射源同一性的识别实验验证了软件的有效性,同时研究了谱相似度随统计涨落和测量条件,如时间、源强和本底等因素的变化情况.研究结果表明:1)用相似度概念来描述两个指纹的相似程度,回答两个待比较的γ射线能谱是否代表同一类型放射源,是切实可行的;2)该识别机理只具备识别放射源类型的能力,而对同一类型、差异甚微的放射源个体还不能识别 关键词： γ射线能谱指纹 辐射指纹 识别机理 核查技术     

Families of Line-Graphs and Their Quantization

Any directed graph G with N vertices and J edges has an associated line-graph L(G) where the J edges form the vertices of L(G). We show that the non-zero eigenvalues of the adjacency matrices are the same for all graphs of such a family L ⁿ (G). We give necessary and sufficient conditions for a line-graph to be quantisable and demonstrate that the spectra of associated quantum propagators follow the predictions of random matrices under very general conditions. Line-graphs may therefore serve as models to study the semiclassical limit (of large matrix size) of a quantum dynamics on graphs with fixed classical behaviour.     

Fluorescence line narrowed spectra of Zn and metal-free cytochrome c

Fluorescence line narrowing (FLN) spectroscopy was used to study the role of the polypeptide chain in influencing the spectrum of Zn-substituted cytochrome c (Zn cyt c) and metal-free cyt c (porphyrin cyt c). For both derivatives the spectra show characteristics of relaxed fluorescence from an inhomogeneously broadened sample. Zero phonon lines and phonon wings can be clearly distinguished, and vibrational frequencies of the ground and excited states were identified. The inhomogeneous distribution width for porphyrin cyt c is slightly wider than that of Zn cyt c and a second population of molecules was apparent in the porphyrin cyt c. The phonon coupling was greater for Zn cyt c than for porphyrin cyt c, which may be due to the extra coupling to the polypeptide chain by metal ligation.This work has been done in partial fulfillment of the requirements for the Doctor of Philosophy degree.     

用光学多通道分析仪系统作高分辨光谱测量的技术

通常的光多通道分析仪(OMA)存在着同时谱宽与分辨率的矛盾.本文所述方法,在不减小谱宽的前提下,可将该分析仪光谱分辨率提高1～2量级,使之可适用于高分辨率谱研究.     

用于曲面精密检测的新型光纤三角传感器研究

基于光纤传感技术和三角测量方法，提出了一种用于曲面检测的新型光纤三角传感器。根据所设计的轮辐式接收光纤结构，可以在测量曲面与传感头间位移时，首先获取被测点处微面元的倾斜信息，以便对传感器测量值进行实时误差修正，从而解决了被测表面倾斜对坐标测量带来的影响。该传感器还能有效地消除环境光干扰、光源波动、表面反射率变化等对测量带来的影响。建立了传感器测量的数学模型。理论分析和初步的实验结果证明了系统的有效性和实用性。该传感器系统不稳定性好于0.3%，横向分辨率好于8μm，高度分辨率好于0.1μm。     

含铒碲酸盐玻璃的上转换荧光性质研究

在室温下,用804nm波长的半导体激光器作激发源,在TeO_2-PbO基掺铒碲酸盐玻璃中实现了中心波长分别为525nm,550nm和660nm的上转换发射.荧光强度与激发功率呈非线性关系.估测了PbO含量对上转换荧光相对强度的影响.     

Pauli-Fierz Hamiltonians defined as quadratic forms

We study Pauli-Fierz Hamiltonians-self-adjoint operators describing a small quantum system interacting with a bosonic field. Using quadratic form techniques, we extend the results of Dereziński-Gérard and Gérard about the self-adjointness, the location of the essential spectrum and the existence of a ground state to a large class of Pauli-Fierz Hamiltonians.     

一种新的$1/f$过程小波模型

给出了一种新的二进小波1/f过程模型,从理论上证明了一类谱指数为H的近似1/f过程可通过一簇平稳随机过程产生.由于所提方法利用了1/f过程小波系数的相关性,因而有效地减少了合成1/f过程的谱误差.数值实验结果表明,新模型很好地改进了已有模型.