Solvatochromism and solvatofluorochromism of the intramolecular charge transfer band of 4-dimethylaminochalcone in the electronic spectra of its solutions

The solvatochromic and solvatofluorochromic dependences pertaining to the intense intramolecular charge transfer electronic band of the 4-dimethylaminochalcone molecule, widely used as an efficient spectralluminescent probe in various medical and biological studies, are systematically and quantitatively investigated. The data obtained are interpreted based on the new variant of the semiempirical theory of the influence of the dielectric properties of individual solvents on the shift in the optical spectra of molecules occurring as a result of the gas-solution phase transition that was proposed previously by one of the authors of this study. It is shown that the main contribution (at least 70–80%) to the absolute solvation shift in the absorption and fluorescence spectra of the 4-dimethylaminochalcone molecule is made by universal dipole-dipole interactions of orientation, induction, dispersion, and inductive-resonance nature, as well as by repulsive forces.     

4-苯乙炔基-4′-二甲氨基查尔酮的合成与溶剂极性敏感的发光特性

以4-溴-4′-二甲氨基查尔酮和苯乙炔为原料,通过Sonogashira钯催化偶联反应合成了4-苯乙炔基-4′-二甲氨基查尔酮,并通过红外光谱和核磁共振氢谱对其结构进行了表征。进一步研究了4-苯乙炔基-4′-二甲氨基查尔酮在不同极性的溶剂中的紫外可见吸收光谱和荧光光谱,结果表明该化合物具有极性敏感的发光特性。     

Study of the complexation and solvation of polar molecules in binary solvents by differential spectroscopy

A method of application of differential absorption spectroscopy for determining the absorption spectra of primary 1: 1 solvated complexes between polar molecules of an organic dye and the active component of a binary solvent whose neutral component is a nonpolar liquid is proposed. The method was tested on diluted solutions of 4-dimethylaminochalcone (4-DMC) (which is one of the most efficient spectral-luminescent probes used in present-day medical and biological investigations) in mixtures of n-hexane with acetone at extremely small concentrations of the polar component. It is shown that the experimentally found absolute shift of the long-wavelength absorption band of 4-DMC is in satisfactory quantitative agreement with the analogous value obtained independently on the basis of the theory describing the joint effect of nonlinear (complexation) and linear (solvation) dipole-dipole interactions on the spectral band positions.     

Application of the method of selective fluorescence excitation to investigation of complexation and solvation processes of polar organic dye molecules in binary solvents

It is proposed to use the method of selective fluorescence excitation to find absorption spectra (fluorescence excitation spectra) of 1 : 1 primary solvated complexes between polar molecules of an organic dye and the active component of a binary solvent, whose neutral component is a nonpolar or low-polarity liquid. The technique was tested with diluted solutions of 4-dimethylaminochalcone (4-DMC) in mixtures of ethylbenzene with dimethyl formamide at extremely low contents of the latter. It is shown that the experimental absolute shift of the long-wavelength vibronic absorption band of three-component DMC solutions is in a good quantitative agreement with the analogous shift obtained independently based on the semi-empirical theory describing the joint effect of nonlinear (complexation) and linear (solvation) dipole-dipole interactions on the shift of spectral bands.     

Fluorescent probe 4-dimethylaminochalcone: Solvatochromism according to the data of semiempirical and quantum-chemical calculations

The solvatochromic regularities observed in solutions of 4-dimethylaminochalcone (DMCh) are investigated in terms of two independent theoretical approaches, i.e., semiempirical and quantum-chemical, and the results of these investigations are directly compared with each other for the first time. It has been shown that the values of the absolute solvation shift of the long-wavelength DMCh electronic absorption band determined by different methods are in a good quantitative agreement both with each other and with experimental data. This fact can be considered as a substantial additional justification of the conclusion on the predominantly nonspecific origin of intermolecular forces determining the mechanisms by which the DMCh fluorescent probe functions in biological systems.     

Nature of the influence of a solvent on the fluorescence quantum yield of solutions of the fluorescent probe 4-dimethylaminochalcone

The fluorescence quantum yields of solutions of 4-dimethylaminochalcone (DMC) in a series of individual solvents of different chemical nature have been measured using a technique based on studying the kinetics of fluorescence decay. A new quantitative regularity, namely, the dependence of the fluorescence quantum yield on the absolute solvation shift in the fluorescence spectrum due to the gas-solution phase transition, has been revealed. The opinion has been advanced and justified that the revealed regularity has a fundamental character, which is determined by the dominant contribution from the universal intermolecular interactions to the formation of the properties of the solvated DMC molecule in the excited electronic state.     

Estimation of the number of polar molecules in a solvate shell of a fluorescent probe 4-dimethylaminochalcone

The fluorescence decay kinetics has been studied in different parts of the emission spectrum of diluted solutions of a membrane fluorescent probe, 4-dimethylaminochalcone, in a binary n-heptane + acetone solvent with the volume fractions of polar and nonpolar components of the latter varying in a wide range. It has been shown that the fluorescence of these solutions has a significantly heterogeneous character, which is indicative of the presence of several types of solvate complexes with controllable ratios of components (1: 1, 1: 2, 1: 3, etc.) in the studied systems. Based on a quantitative analysis of the mentioned kinetic dependences, a model has been proposed in which these data can serve as a source of information about statistical features of the structure of solvate shells of polar dye molecules in an excited electronic state. This information can in turn be used to obtain new biophysical data.     

不同Yb掺杂浓度的ZnO的电子结构与光学特性

本文基于密度泛函理论(DFT)框架下的第一性原理计算方法,研究了不同Yb浓度掺杂ZnO体系的电子结构和光学性质.计算得到的结果证明,Yb掺杂ZnO后会造成电子结构和光学性质的明显改变.增加掺杂浓度使能带带隙逐渐变窄,其费米能级向上移动到导带,表现出n型半导体的特性;在Yb-4f态导带附近的带隙中产生了新的缺陷,同时观察到更好的吸收系数和折射率.因此,Yb掺杂ZnO对其电子性质和光学结构有很大的影响,为进一步深入了解掺杂ZnO性质的影响提供理论基础.     

The effects of indium segregation on the valence band structure and optical gain of GaInAs/GaAs quantum wells

The effects of indium segregation on the valence band structures and the optical gain in GaInAs/GaAs quantum wells are theoretically investigated using 4×4 Luttinger–Kohn Hamiltonian matrix. The method for the band structure calculation is based on the finite difference method, then the optical gain is calculated using the density matrix approach. For segregation coefficient R less than 0.7, indium segregation has little influence on optical gain, but for segregation coefficient R more than 0.7, it has a significant influence on optical gain, the gain spectra can be blue-shifted with the increase of segregation coefficient R, and the peak gains are decreased as segregation coefficient R increases, which is mainly due to the reduction of the carrier population inversion.     

Spectrophotometric investigations of protonated forms of heterocyclic compounds

2,4,6-trimethylpyridine, quinoline, 2-methylquinoline, 4-chlorine-2-methylquinoline, and acridine aromatic heterocycles, as well as protonated forms thereof, are studied by electronic absorption spectroscopy in solution. The influence of protonation on the electronic absorption spectra of heterocycles consists in a long-wavelength shift of the absorption spectrum in comparison with the absorption of initial molecules. The spectra of the protonated forms of all compounds exhibit a relative increase in the intensity of the long-wavelength absorption band compared to the short-wavelength band and a smearing of the vibrational structure in the long-wavelength band.     

Lamb waves in two-dimensional phononic crystal plate with anisotropic inclusions

An analysis is given to the band structure of the two-dimensional phononic crystal plate constituted of a square array of elastic anisotropic, circular Pb cylinders embedded in elastic isotropic epoxy. The numerical results show that the band gap can be tuned by rotating the anisotropic material orientation. It is found that the influence of anisotropy on band gap of Lamb wave is clearly different from that on the band gap of bulk waves. The thickness of the system under study is a sensitive parameter to affect the influence of anisotropic materials on the normalized gap width.     

Tuning transport coefficients of monolayer MoSi_2N_4 with biaxial strain

Experimentally synthesized MoSi_2N_4(Science 369 670(2020)) is a piezoelectric semiconductor. Here, we systematically study the large biaxial(isotropic) strain effects(0.90–1.10) on electronic structures and transport coefficients of monolayer MoSi_2N_4 by density functional theory(DFT). With a/a0 from 0.90 to 1.10, the energy band gap firstly increases, and then decreases, which is due to transformation of conduction band minimum(CBM). Calculated results show that the MoSi_2N_4 monolayer is mechanically stable in the considered strain range. It is found that the spin-orbital coupling(SOC) effects on Seebeck coefficient depend on the strain. In unstrained MoSi_2N_4, the SOC has neglected influence on Seebeck coefficient. However, the SOC can produce important influence on Seebeck coefficient, when the strain is applied,for example, 0.96 strain. The compressive strain can change relative position and numbers of conduction band extrema(CBE), and then the strength of conduction bands convergence can be enhanced, to the benefit of n-type ZT_e. Only about0.96 strain can effectively improve n-type ZT_e. Our works imply that strain can effectively tune the electronic structures and transport coefficients of monolayer MoSi_2N_4, and can motivate farther experimental exploration.     

Lipid Bilayer Interactions of Amyloidogenic N-Terminal Fragment of Apolipoprotein A-I Probed by Förster Resonance Energy Transfer and Molecular Dynamics Simulations

The effects of one of the amyloidogenic mutations of apolipoprotein A-I (apoA-I), G26R, on the thermal stability, structural dynamics and lipid-associating properties of the 1–83 N-terminal fragment of apoA-I (A83) have been investigated using the Förster resonance energy transfer (FRET) and molecular dynamics (MD) simulation. The measurements of FRET between the tryptophan residues of the single Trp variants of A83 as donors and the membrane-incorporated fluorescent probe 4-dimethylaminochalcone as an acceptor provided evidence for a less depth of A83/G26R penetration into phosphatidylcholine (PC) bilayer compared to WT counterpart. The unfolding MD simulations showed that G26R mutation destabilizes the overall structure of A83, with individual alpha-helices differing in their thermal stability. The MD simulations performed at physiological temperature revealed that A83 and A83/G26R differ in their conformational behavior in an aqueous solution, PC and PC/Cholesterol bilayers. These findings may prove of importance for deeper understanding of the key determinants of apoA-I amyloidogenesis.     

Nonlinear bandgap properties in a nonlocal piezoelectric phononic crystal nanobeam

Applying nonlocal elasticity theory, von Kármán type nonlinear strain-displacement relation and plane wave expansion (PWE) method to Euler-Bernoulli beam, the calculation method of band structure of a nonlinear nonlocal piezoelectric phononic crystal (PC) nanobeam is proposed and formulized. In order to investigate the properties of wave propagating in the nanobeam in detail, band gaps of first four orders are picked, and the corresponding influence rules of electro-mechanical coupling fields, nonlocal effect and geometric parameters on band gaps are studied. During the researches, external electrical voltage and axial force are chosen as the influencing parameters related to electro-mechanical coupling fields. Scale coefficient is chosen as the influencing parameter corresponding to nonlocal effect. Length ratio between materials PZT-4 and epoxy and height-width ratio are chosen as the influencing parameters of geometric parameters. Moreover, all the influence rules are compared to those in linear nanobeam. The results are expected to be of help for the design of micro and nano devices based on piezoelectric periodic nanobeam.     

二维6H-SiC光学特性的应变调控

为了减小6H-SiC的带隙、提高对可见光的吸收效率和载流子迁移速率,采用第一性原理研究了应变对6H-SiC的能带结构、光学吸收系数、载流子迁移率以及光催化特性的影响。结果表明：应变能够降低6H-SiC的导带底,但对价带顶没有影响,导致带隙减小。随着应变的增加,吸收曲线向低能级方向移动,即发生红移,有利于可见光的吸收。施加应变后空穴的载流子迁移率提高,有利于载流子移动,且空穴的载流子迁移率是电子的2.5倍,有利于空穴和电子的分离。综合应变对带隙大小、带边位置的影响可知,应变在±2%、±4%时对可见光的吸收以及光催化制氢最有效。综上所述,应变能够对6H-SiC的光学吸收和光催化特性有很好的调控作用。     

原电池法室温制备Ba_(1-x)Ca_xMoO_4固溶体薄膜

在含Ca_~(2+)和Ba~(2+)的碱性溶液中,通过原电池法在室温条件下制备了Ba_(1-x)Ca_xMoO_4多晶固溶体薄膜。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和荧光分析(FA)对所制备的薄膜进行了分析表征,研究了Ba摩尔分数对薄膜的晶相结构、表面形貌和发光性能的影响。结果表明,原电池法制备的Ba_(1-x)Ca_xMoO_4薄膜致密、均匀、结晶完好,为四方相结构。随着初始溶液中Ba含量的增加,所得Ba_(1-x)Ca_xMoO_4固溶体薄膜的形貌逐渐从CaMoO_4微晶的球形转变为BaMoO_4微晶的四方锥形。在290nm紫外光的激发下,制备的薄膜均在350nm和495nm附近呈现两个宽的发射带,其中495nm的蓝光发射明显强于350nm的紫光发射。初始溶液中的Ba/Ca的量比对所制备的Ba_(1-x)Ca_xMoO_4固溶体薄膜的发射光谱的形状和发射波长影响甚微,但对其发射强度有明显影响。     

Band gap structure of disordered chiral photonic crystals

Based on the non-symmetric transmission-line method, the band gap structure of disordered chiral photonic crystals (CPC) has been investigated. The influence of the chiral parameters, the disorder, the periods and the refractive index on the band gap structure has been discussed. It is found that the photonic band gap (PBG) in CPC is more obvious than that in the conventional photonic crystals, and the PBG can be increased by increasing the periods or the contrast of the refractive index of the two media. It is also found that the existence of disorder will influence the band edge of the PBG, and such influence will increase with the increment of periods or the contrast of the refractive index of the two media.     

三元1维含缺陷层光子晶体带隙结构

利用传输矩阵法研究了含缺陷三元1维光子晶体的带隙结构,并通过数值模拟分析了光子晶体缺陷层厚度的变化对带隙结构产生的影响。结果表明:含缺陷对称分布的三元1维光子晶体,缺陷层厚度对禁带的带宽影响不大;在较宽的禁带中存在一个很窄的透射峰,该透射峰随着缺陷厚度的增加而红移。在一定的范围内,给出了该透射峰波长随缺陷厚度变化的非线性函数关系,在此基础上对禁带中该透射峰的半峰全宽做了计算,给出了半峰全宽随缺陷厚度变化的关系图。     

超元胞方法研究平移群对称性对声子带隙的影响

采用基于超元胞的平面波展开法，计算了由水银(水)正四棱柱体按正方格子排列于水(水银)基体中所组成的两种声子晶体的能带结构.通过改变两相邻的柱体底面边长之比来改变声子晶体的平移群对称性.结果发现，改变相邻柱体的底面边长之比，具有很好的调节声学带隙的作用.研究表明，声子晶体的平移群对称性对于其带隙的形成具有重要影响,同时还表明,超元胞方法也是研究声子晶体平移群对称性影响声子带隙形成的一种有效方法. 关键词： 声子晶体 带隙 对称性     

一种基于十字镂空结构的低频超材料吸波体的设计与制备

设计了一种十字镂空的超材料结构,与传统的铁磁吸波材料相结合,实现了低频吸收频带的扩宽.仿真结果显示,吸波体在2-4 GHz范围可以实现-10 dB以下的吸收,相比于没有加载超材料的情况,吸收带宽扩展了0.5 GHz.实验结果在2.5-5.1 GHz范围内也显示了相似的吸收曲线,低于-9 dB的吸收频带有0.48 GHz的扩宽,扩展了23%.不同结构的能量损耗密度分布表明,相比于无镂空的十字结构,镂空十字结构可以增加磁场能量损耗,加强单元结构之间的耦合,降低超材料对传统吸波材料性能的破坏.探索了传统铁磁吸波材料厚度的变化对吸波体吸收性能的影响,发现由超材料引入的附加峰位置不随着吸波材料厚度的改变而明显地移动.根据这个结果,进一步设计了由两种超材料叠加组合而成的吸波体,仿真结果和实验结果均显示,在降低了1.1 mm铁磁吸波材料层厚度的情况下,使低频吸收带宽又扩展了0.9 GHz.