天然Alboatisin电子结构和圆二色谱的密度泛函理论研究

采用蒙特卡罗MMFF94分子力学力场方法搜索一类新发现的生物活性分子Alboatisin A～C的稳定构象,用梯度校正的B3LYP方法,计算其稳定构象的旋光度、振动圆二色谱(VCD)、电子圆二色谱(ECD)等光学活性,并从微观的角度对VCD谱和ECD谱中强或弱的正或负康登效应进行归属．从分子结构、电子结构和分子振动分析了分子手性的微观起源．结果表明,计算与实验的旋光度值相吻合,OH的取代位置与数目可调控旋光度发生在手性骨架上的振动或电子跃迁转移是手性光谱产生的重要原因．Alboatisin的圆二色谱是手性骨架变形振动的光谱响应,是不对称电子跃迁的光谱响应结果．     

云南松松塔中两种新木脂素圆二色谱的密度泛函研究

采用梯度校正的密度泛函理论方法,计算了云南松松塔中分离的2种新木脂素的绝对结构为7S,8R的手性结构、电子吸收光谱、电子圆二色谱、红外振动光谱和振动圆二色谱,计算值与实验值相符. 分子轨道和振动模式分析,两种新木质素具有相似的手性光谱. 电荷密度转移对电子圆二色谱具有主要贡献;而振动圆二色谱主要源于分子骨架运动.     

云南松松塔中两种新木脂素圆二色谱的密度泛函研究

采用梯度校正的密度泛函理论方法,计算了云南松松塔中分离的2种新木脂素的绝对结构为7S,8R的手性结构、电子吸收光谱、电子圆二色谱、红外振动光谱和振动圆二色谱,计算值与实验值相符. 分子轨道和振动模式分析,两种新木质素具有相似的手性光谱. 电荷密度转移对电子圆二色谱具有主要贡献;而振动圆二色谱主要源于分子骨架运动.     

圆二色技术及应用

 近几十年以来,生物大分子结构的测定逐渐成为生命科学领域的热门课题．许多生物大分子,如蛋白质、核酸、多糖等都是手性分子,所谓手性（Ｃｈｉｒａｌｉｔｙ）就是具有不能重叠的三维镜像对应异构体．一般说来,凡具有手性的分子就具有旋光活性．旋光活性很早就为人们所认识并广泛应用于研究分子的非对称性结构．１８９６年科顿效应（ＣｏｔｔｏｎＥｆｆｅｃｔ）的发现为族光色散（ＯｐｔｉｃａｌＲｏｔａｔｏｒｙＤｉｓｐｅｒｓｉｏｎ）和圆二色（ＣｉｒｃｕｌａｒＤｉｃｈｒｉｓｍ）的出现奠定了理论基础．这些灵敏方法的出现,使得人们有可能从这些实验技术中得到一些新的结构信息,为更深入的研究立体化学和电子结构提供了条件．     

电子激发和溶剂效应对芴酮-甲醇分子间氢键增强现象的理论研究 (cited: 1)

理论研究了电子激发和溶剂效应导致的芴酮-甲醇复合体系中分子间氢键增强现象．通过基态和激发态性质的计算,不仅展示了分子间氢键键长的变化以及变化在振动光谱中的影响,而且揭示了导致氢键变化的内在物理机制：溶质分子的电子激发及溶剂化效应引起的电子重新分布,增大了溶质和溶剂分子的偶极矩,导致了它们之间的相互作用的增大,并最终加强了分子间氢键的强度．还分别对处于液相及气相中的复合体的基态和激发态的几何结构、红外谱、复合体及构成分子的偶极矩进行了理论计算,结果阐明了电子激发与溶剂化效应对氢键变化的贡献,同时还发现只有进一步引入溶剂化效应,复合体的基态、激发态的性质才能与实验达到精确一致．所有激发态均采用所开发的基于含时密度泛函理论解析计算一阶、二阶激发态能量导数的方法．     

固体手性材料的研制及其特性测试

利用溶胶凝胶低温合成非晶态技术,以正硅酸乙酯、γ缩水甘油醚基丙基三甲氧基硅烷和乙醇为前驱体,将手性分子葡萄糖均匀地掺入到上述体系的溶胶与凝胶中,成功地研制出无机固体手性材料样品,并对其光学极化特性、光谱特性及材料的热稳定性进行了测试.测试结果表明,样品的旋光率为-095°cm,计算所得的手征参数为155×10-7. 关键词： 溶胶-凝胶 手性分子 旋光率 手征参数     

基于溶剂化效应的BDE-15分子振动光谱增强特征振动研究

利用密度泛函与自洽反应场理论在B3LYP/6-31+G(d)水平下分别计算气态及24种不同极性溶剂中4,4’-二溴二苯醚(4,4’-dibrominated diphenyl ethers, BDE-15)的分子振动光谱(红外光谱、拉曼光谱),以气态分子振动光谱为基准,筛选出对溶剂极性敏感的特征振动作为指标构建溶剂对BDE-15振动光谱溶剂化效应指标体系,探究溶剂对BDE-15分子振动频率、红外/拉曼峰强溶剂化效应及综合效应,并寻求显著增强BDE-15分子特征振动频移/强度的溶剂。研究表明：从分子振动频率角度,溶剂极性敏感的(频移>1 cm-1)分子特征振动均为伸缩振和面外弯曲振,但24种溶剂对BDE-15分子振动频率溶剂化效应并不显著;从分子振动峰强角度,24种溶剂对BDE-15分子振动光谱峰强的增强效应主要发生在红外光谱的中低频区及拉曼光谱的高频区,其中起显著增强(红外/拉曼效应指标值分别大于6与5)的溶剂为醇类、乙腈、二甲亚砜、硝基苯;不同极性溶剂对BDE-15拉曼峰强溶剂化效应及综合效应指标值均表现出随溶剂介电常数增长由线性到对数的增长趋势,而红外峰强只保留低介电常数溶剂时的线性关系。利用上述BDE-15分子振动光谱峰强增强方法对BDE-153,BDE-154和BDE-209进行验证,醇类、乙腈、二甲亚砜、硝基苯对三者的振动光谱红外/拉曼峰强的效应指标值分别大于6与5,且最大峰强增倍数皆大于33,说明所建BDE-15分子振动光谱增强特征振动方法有助于进一步开展基于分子振动光谱的PBDEs同系物间辨识研究。     

D-A型二噻吩并磷杂茂衍生物分子的双光子吸收性质

在密度泛函理论理论水平上,采用响应理论方法计算了一系列2,6-donor-acceptor 二噻吩并磷杂茂衍生物分子的单、双光子吸收性质. 理论计算结果表明该系列分子都具有较大的双光子吸收截面,并且分子中心的磷原子无论被氧化还是金属配合,其双光子吸收截面几乎保持不变. 此外,还考虑了溶剂效应对分子光学性质的影响,研究表明分子能级发生了溶剂化蓝移,并且分子的单光子和双光子吸收性质随着溶剂极性表现出非单调变化.     

D-A型二噻吩并磷杂茂衍生物分子的双光子吸收性质

在密度泛函理论理论水平上,采用响应理论方法计算了一系列2,6-donor-acceptor二噻吩并磷杂茂衍生物分子的单、双光子吸收性质.理论计算结果表明该系列分子都具有较大的双光子吸收截面,并且分子中心的磷原子无论被氧化还是金属配合,其双光子吸收截面几乎保持不变.此外,还考虑了溶剂效应对分子光学性质的影响,研究表明分子能级发生了溶剂化蓝移,并且分子的单光子和双光子吸收性质随着溶剂极性表现出非单调变化.     

溶剂效应对β胡萝卜素分子电子振动耦合的影响

测量了10种典型溶剂中β胡萝卜素分子的紫外-可见吸收谱和共振拉曼光谱.结果表明:溶剂的极化率、介电常数都对β胡萝卜素分子的电子-振动耦合有影响;随着极化率的增大,β胡萝卜素分子的黄昆因子、电子-振动耦合常数减小,拉曼截面增加,且这些影响与溶剂极性无关;随着溶剂介电常数的增加,对于非极性溶剂,β胡萝卜素分子的黄昆因子、电子-振动耦合常数减小,拉曼截面增加,对于极性溶剂,没有获得比较好的规律.给出了溶剂性质对电子-振动耦合的影响规律,为分子的电子-振动耦合研究中溶剂的选择提供了参考.     

Density functional study on chirospectra of hydrogen-bonded systems X-（H2O）3（X=F,Cl,Br,I）

This paper calculates the molecular structures,infrared,Raman,circular dichroism spectra and optical rotatory powers of some hydrogen-bonded supramolecular systems as a cyclic water trimer,(H2O)3 and its pyramidal halide complexes,X-(H2O)3(X = F,Cl,Br,I) with the gradient-corrected density functional theory method at the B3LYP/6-311++G(2d,2p) and B3LYP/Aug-cc-pVTZ levels.It finds that the complexation of halide anions with the water trimer can efficiently modulate the chirally optical behaviors.The calculated vibrational circular dichroism spectrum illuminates that the vibrational rotational strength of S(+)-(H2O)3 mostly originates from the O-H rocking modes,whereas chirality of S(-)-X-(H2O)3(X = F,Cl,Br,I) has its important origin in the O-H stretching modes.The calculated optical rotatory power demonstrates that S(+)-(H2O)3 and S(+)-F(H2O)3 are positively chiral,whereas S(-)-X-(H2O)3(X = Cl,Br,I) are negatively chiral.With the polarizable continuum model,calculated bulk solvent effect in the solvents water and carbontetrachloride and argon shows that the positive chirality of S(+)-(H2O)3 is enhanced and the negative chirality of S(-)-X-(H2O)3(X = Cl,Br,I) and the positive chirality of S(+)-F(H2O)3 are reduced with an augmentation of the solvent dielectric constant.     

联萘基-芘衍生物结构和ECD光谱性质的理论研究

采用密度泛函理论方法研究s-联萘基-芘分子结构、联萘二面角、能隙、电子的圆二色(electronic circular dichroism, ECD)光谱等性质，系统考察其溶剂效应和取代基效应.研究发现，在苯、四氯化碳、氯仿、环己烷和水五种溶剂中，s-联萘基-芘分子的结构和ECD光谱等性质均相似.然而，在氯基、甲基、羟基、甲氧基和苯基五种取代基中，苯基取代基可以调节s-联萘基-芘分子的结构和ECD光谱等性质.     

Giant Asymmetric Transmission and Circular Dichroism with Angular Tunability in Chiral Terahertz Metamaterials

Inspired by the chiral structure from mode interaction, a chiral terahertz metamaterial and its complementary structure with the coexistence of asymmetric transmission and circular dichroism response are designed. The asymmetric transmission happens in the presence of electric and magnetic modes perpendicular to each other, resulting from intrinsic chirality under normal incidence. Circular dichroism exists in the presence of electric and magnetic modes parallel to each other under oblique incidence because of extrinsic chirality. Both asymmetric transmission and circular dichroism are enhanced by complementary structures, benefitting from the coupling between adjacent units. The maximum of chiral parameter κ can achieve 450, which is one hundred times higher than previously reported. The chiral response can be tuned by the incident angle and is sensitive to the environmental refractive index. The results highlight the potential applications of these metamaterials in chiral sensing and polarization transformation devices.     

Second-harmonic generation circular dichroism spectroscopy from tripod-like chiral molecular films

The second-harmonic generation (SHG) circular dichroism in the light of reflection from chiral films of tripod-like chiral molecules is investigated.The expressions of the second-harmonic generation circular dichroism are derived from our presented three-coupled-oscillator model for the tripod-like chiral molecules.Spectral dependence of the circular dichroism of SHG from film surface composed of tripod-like chiral molecules is simulated numerically and analysed.Influence of chiral parameters on the second-harmonic generation circular dichroism spectrum in chiral films is studied.The result shows that the second-harmonic generation circular dichroism is a sensitive method of detecting chirality compared with the ordinary circular dichroism in linear optics.All of our work indicates that the classical molecular models are very effective to explain the second-harmonic generation circular dichroism of chiral molecular system.The classical molecular model theory can give us a clear physical picture and brings us very instructive information about the link between the molecular configuration and the nonlinear processes.     

Structural characteristics and spectral behaviours of the preferred conformation of a cyclic pentapeptide,cycloaspeptide G from Cordyceps-colonising fungus Isoria farinose

The density functional theory (DFT) is exploited to search the stable conformations of a cyclic pentapeptide called cycloaspeptide G from Cordyceps-colonising fungus Isoria farinose. Its time-dependent version is employed to describe the profiles of electronic circular dichroism (ECD) of the preferred conformation, where the solvent effect in methanol is taken into account on the basis of the polarisable continuum model computation. Four stable conformers are optimised, and the results of the harmonically vibrational frequency calculations illustrate that they are the true minima. In the vibrational CD spectrum at the B3LYP/6-31G* level, the negative peak at 3334 cm^?1 has its origin of the NH stretches of the peptide ring. In the ECD spectrum at the B3LYP/6-31G* level, three strong bands are negative, positive, and negative. Since the ECD spectrum at the B3LYP/6-31G* level is remarkably different from that at the B3LYP/6-31G level, it is necessary for the expended functions to be added to the 6-31G basis set.     

Helical twisting power and circular dichroism in nematic liquid crystals doped with chiral molecules

Explicit expressions for the helical twisting power of a chiral dopant in the nematic phase have been obtained in the mean field approximation taking into account chiral dispersion intermolecular interactions. The results of the theory enable one to explain a correlation between the signs of helical twisting power and circular dichroism of selected electronic transitions which have recently been established experimentally for some mono- and bis-aminoantroquinones. Helical twisting power is proportional to the pseudoscalar parameter that specifies the chirality of the dopant molecule in terms of its dipole and quadrupole matrix elements. This expression is simplified for a special class of molecules in which chirality is induced by a perturbing achiral group into an achiral skeleton. In this case both helical twisting power and circular dichroism are approximately proportional to some simple pseudoscalar functions that specify the location of the achiral perturbing group with respect to the symmetry planes of the unperturbed achiral skeleton. Simple sector rules have been proposed to determine the sign change of the helical twisting power associated with the change of location of the perturbing group.     

Chiroptical spectra of molecules with nearly degenerate electronic states

The influence of vibronic interactions on the chiroptical spectra associated with pairs of nearly degenerate electronic transitions in chiral systems is examined on a formal theoretical model. We consider the special case in which two nearly degenerate electronic states are coupled by a single non-totally symmetric vibrational mode. Formal expressions are developed for the rotatory strengths of individual vibronic transitions in this coupled system. Calculations based on these expressions are carried out for a large number of parameter sets appropriate for various energy spacings between the unperturbed electronic states, vibronic coupling strengths, oscillator (vibrational mode) frequencies, and electronic rotatory strengths. The calculated results demonstrate the profound influence of vibronic interactions on the sign patterns and intensity distributions within the rotatory strength spectrum associated with the two coupled electronic states. The implications of these results for interpretations of circular dichroism spectra are discussed.     

Optical Chirality from Dark‐Field Illumination of Planar Plasmonic Nanostructures

Dark‐field illumination is shown to make planar chiral nanoparticle arrangements exhibit circular dichroism in extinction, analogous to true chiral scatterers. Single oligomers, consisting rotationally symmetric arrangements of gold nanorods, are experimentally observed to exhibit circular dichrosim at their maximum scattering with strong agreement to numerical simulation. A dipole model is developed to show that this effect is caused by a difference in the projection of a nanorod onto the handed orientation of electric fields created by a circularly polarized dark‐field normally incident on a glass‐air interface. Owing to this geometric origin, the wavelength of the peak chiral response is experimentally shown to shift depending on the separation between nanoparticles. All presented oligomers have physical dimensions less than the operating wavelength, and the applicable extension to closely packed planar arrays of oligomers is demonstrated to amplify the magnitude of circular dichroism. This realization of strong chirality in these oligomers demonstrates a new path to engineer optical chirality from planar devices using dark‐field illumination.     

Specific chiroptical sensing of cysteine via ultrasound-assisted formation of disulfide bonds in aqueous solution

Cysteine (Cys) can serve as a biomarker to indicate diseases or disorders, and its chiral sensing has attracted increasing attention. Herein, we established an ultrasound-facilitated chiral sensing method for Cys using 4-chloro-7-nitro-1,2,3-benzoxadiazole (NBD-Cl) and electronic circular dichroism (ECD) spectroscopy. The formation of chiral disulfide bonds induced degenerate exciton coupling between two NBD chromophores, resulting in intense Cotton effects (CEs) of the sensing product. The anisotropy factor (g) was linearly correlated with the enantiomeric excess of Cys across the visible region (400–500 nm), and other natural amino acids or biothiols did not interfere with the detection. This ultrasound-promoted efficient and specific chiral sensing method of Cys has potential for application in the diagnosis of related diseases.     

Electronic circular dichroism of some double-helical alkynyl cyclophanes with 1,1′-binaphthyl auxiliaries investigated using time-dependent density functional calculations

For several double-helical molecules, the dependence of electronic circular dichroism (ECD) spectra on the molecular and electronic structures is investigated on the basis of TDDFT computations with the B3LYP hybrid functional. The calculations of a model molecule reveal that an acute-angled rotational dihedral angle other than an obtuse-angled rotational dihedral angle between two naphthyls implies Davydov splitting of exciton coupling. For the R enantiomers, the acute-angled rotational dihedral angle implies a negative lowest-energy Cotton effect, which is induced by electron density transfer from binaphthyls to phenyethynyls in the S_0?→?S₄ excitations. Due to the large positive rotational strength of the S_0?→?S₁ transition, the lowest-energy Cotton effect of the simplest cyclophane R-1 is positive, where the electron density transfer from phenyethynyls to binaphthyls plays an important role.