Enhanced Circular Dichroism of Z-Shaped Nanorod in Rectangular Nanohole Arrays

Chiral nanostructures have attracted much attention due to the valuable applications in biochemistry, medicine industries, and photonic devices. In this study, we propose an ease-of-fabrication planar nanostructure that consists of rectangular nanohole arrays in which the Z-shaped nanorod is arranged. Theoretically, such chiral nanostructure supports significant absorption circular dichroism (CD) compared with the Z-shaped nanorod because charge distributions are tuned after the introduction of the rectangular frame. Meanwhile, the Z-shaped nanorod directs the flow of current on the rectangular frame, thereby generating the effective quadruple electron oscillation in the Z-shaped nanorod. A novel mode also emerges when an identical Z-shaped nanorod is added into the rectangular hole. The studies will provide a novel approach to enhance the CD effect of planar structures. .

Enhanced circular dichroism based on the dual-chiral metamaterial in terahertz regime

The obvious circular dichroism（CD） and optical activity can be obtained based on the chiral metamaterial due to the plasmon-enhanced effect, which is very attractive for future compact devices with enhanced capabilities of light manipulation. In this paper, we propose a dual-chiral metamaterial composed of bilayer asymmetric split ring resonators（ASRR）that are in mirror-symmetry shape. It is demonstrated that the CD can get enhancement in the terahertz regime. Moreover,the CD can be further improved by modulating the asymmetry of ASRR. The enhanced CD effect in the terahertz regime has great potential applications in sensing, biomedical imaging, and molecular recognition.

Anomalous scattering-induced circular dichroism in continuously shaped metasurface

The interconnection of polarization and phase in electromagnetic scattering process has attracted both fundamental and practical interest.Here we propose the principle and experimental demonstration of a scatteringcontrol mechanism based on the simultaneous control of polarization and phase via a continuously shaped planar metasurface.Under circularly polarized illumination,the scattering is redirected to off-specular direction,leading to significant reduction of the scattering cross section.Theoretical investigation shows that the underlying physical mechanism is the spin-dependent phase modulation in the anisotropic scattering process.Our approach would provide valuable guidance for the full control of electromagnetic wave for diverse applications.

Circular dichroism spectra of α-lactose molecular measured by terahertz time-domain spectroscopy

Researchers have long studied circular dichroism(CD) for its enormous prospects in life sciences. Many biomolecules have vibration modes in the terahertz region, and terahertz CD spectra are robust to detect biomolecular structures. However,few studies explore the terahertz CD spectra on even natural materials due to technical challenges in both fields. Here, we report a setup of home-built terahertz time-domain spectroscopy to measure the polarization states of terahertz waves.By carefully measuring the transmission Jones matrix, we obtain terahertz CD spectra of α-lactose tablets and D-glucose tablets. Our results show that the terahertz CD spectra are sensitive to vibrational motions in biochemical compounds,which will find wide applications in biosensing and biomedical diagnostics.

The thermal and storage stability of bovine haemoglobin by ultraviolet-visible and circular dichroism spectroscopies

The effects of temperature,pH and long-term storage on the secondary structure and conformation changes of bovine haemoglobin（bHb） were studied using circular dichroism（CD） and ultraviolet-visible（UV-vis） spectroscopies.Neural network software was used to deconvolute the CD data to obtain the fractional content of the five secondary structures.The storage stability of bHb solutions in pH 6,7 and8 buffers was significantly higher at 4 ℃ than at 23 ℃ for the first 3 days.A complete denaturation of bHb was observed after 40 days irrespective of storage temperature or pH.The bHb solutions were also exposed to heating and cooling cycles between 25 and 65 ℃ and structural changes were followed by UVvis and CD spectroscopies.These experiments demonstrated that α-helix content of bHb decreased steadily with the increasing temperature above 35 ℃ at all pH values.The loss in a-helicity and gain in random coil conformations was pH-dependent and the greatest under alkaline conditions.Furthermore,there was minimal recovery of the secondary structure content upon cooling to 25 ℃.The use of bHb as a model drug is very common and this study elucidates the significance of storage and processing conditions on its stability.

Investigation of binding behaviour of procainamide hydrochloride with human serum albumin using synchronous,3D fluorescence and circular dichroism

Interaction of procainamide hydrochloride（PAH） with human serum albumin（HSA） is of great significance in understanding the pharmacokinetic and pharmacodynamic mechanisms of the drug. Multi-spectroscopic techniques were used to investigate the binding mode of PAH to HSA and results revealed the presence of static type of quenching mechanism. The number of binding sites, binding constants and thermodynamic parameters were calculated. The results showed a spontaneous binding of PAH to HSA and hydrophobic interactions played a major role. In addition, the distance between PAH and the Trp–214 was estimated employing the F？rster＇s theory. Site marker competitive experiments indicated that the binding of PAH to HSA primarily took place in subdomain IIA（Sudlow＇s site I）. The influence of interference of some common metal ions on the binding of PAH to HSA was studied. Synchronous fluorescence spectra（SFS）, 3D fluorescence spectra and circular dichroism（CD） results indicated the conformational changes in the structure of HSA.

Effect of microwave irradiation on secondary structure of α-amylase by circular dichroism

Based on the starch hydrolysis reaction accelerated by microwave irradiation with α-amylase,the circular dichroism(CD) and secondary structure changes of α-amylase under the condition of microwave irradiation and water bath were studied by circular dichroism spectra.The results showed that,both the peak heights(at λ=193 nm) of the CD spectra of the samples treated by microwave irradiation and water bath reduced.The reduced rate by microwave irradiation ranged from 140% to 220%,while the reduced rate by water bath ranged from 60% to 140%.The peak of the sample treated by microwave irradiation for 60 min disappeared at λ=193 nm,while the sample showed a wake peak by water bath.The peak position by microwave irradiation emerged a blue shift in the range of 5-8 nm at λ=204 nm and λ=220 nm,while it emerged in the range of 3-5 nm by water bath.With time going on,the microwave irradiation and water bath have prompted the secondary structure of α-helix,β-sheet,β-turn and the mutual transformations of random coil,but the trends were different.

Circular Dichroism and Fluorescence Spectroscopic Study of RNA-protein Folding Patterns in Human hnRNP A3 and Their Implications in Human Autoimmune Diseases

In human cells, the heterogeneous nuclear ribonucleoproteins (hnRNP) are represented by a group of polypeptides, with various molecular properties, comprizing the most abundant constituents of the cell nucleus. Autoantibodies to hnRNPs have been reported in patients suffering from different rheumatic dieseases since 1980s. Experimental evidence indicates that hnRNP complexes undergo substantial structural changes during mRNA formation and export. However, how this contributes to disease development still has to be elucidated. Here some preliminary physicochemical features of RNA-protein folding and stability patterns of newly characterized hnRNP A3 with further functional implications in development of systemic human autoimmune states are reported.

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 ehiral 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.

Enhanced and tunable circular dichroism in the visible waveband by coupling of the waveguide mode and local surface plasmon resonances in double-layer asymmetric metal grating

Circular dichroism(CD)has shown very interesting possibilities as a means to characterize the chiral signal of a chiral structure.Here,we theoretically demonstrated enhanced and tunable CD in the visible light regime using a composite structure consisting of a double-layer metal grating gaped by a dielectric waveguide layer.Based on the coupling of the waveguide modes and the localized plasmonic resonances,the CD could reach a maximum value as high as 0.52 at635 nm,which is four times higher than the CD value obtained in a conventional double-layer grating without the waveguide coupling effect.Furthermore,the spectral positions of the enhanced CD bands could be easily tuned by controlling the structural parameters.The proposed hybrid double-grating and waveguide structures could have potential applications in chiral selective imaging,sensing and spectroscopy,especially where the transmission measurement is required.

Enhanced circular dichroism of plasmonic system in the strong coupling regime

The circular dichroism(CD) signal of a molecule is usually weak,however,a strong CD signal in optical spectrum is desirable because of its wide range of applications in biosensing,chiral photo detection,and chiral catalysis.In this work,we show that a strong chiral response can be obtained in a hybridized system consisting of an artificial chiral molecule and a nanorod in the strong coupling regime.The artificial chiral molecule is composed of six quantum dots in a helix assembly,and its CD signal arises from internal Coulomb interactions between quantum dots.The CD signal of the hybridized system is highly dependent on the Coulomb interactions and the strong coupling progress through the electromagnetic interactions.We use the coupled oscillator model to analyze strong coupling phenomenon and address that the strong coupling progress can amplify the CD signal.This work provides a scenario for designing new plasmonic nanostructures with a strong chiral optical response.

Enhanced circular dichroism of TDBC in a metallic hole array structure

We investigate the enhanced chirality of chiral molecular J-aggregates(TDBC)by the propagating surface plasmons(PSPs)in the metallic hole array structure filled with TDBC.The two ends of the hole in the metal film form a low quality factor Fabry-Perot(FP)cavity,and this cavity confines PSPs.The resonant wavelength of the metallic hole array is tuned by the lattice constant and the size of the hole.Both the resonant wavelength of Ag hole array and the volume ratio of TDBC in the hybridized structure influence on the enhancement of the circular dichroism(CD)spectrum.The curve of CD spectrum shows Fano-like line-shape,due to the interaction between the non-radiative field in the FP cavity and the radiative field in chiral TDBC.The maximum of the CD spectrum of the hybridized structure is 0.025 times as the one of the extinction spectrum in a certain structure,while the maximum of the CD spectrum of TDBC is 1/3000 times as the one of the extinction spectrum.The enhanced factor is about 75.The resonant wavelength of the metallic hole array can be tuned in a large wavelength regime,and the chirality of a series of molecular J-aggregates with different resonant wavelengths can be enhanced.Our structure provides a new method to amplify the chirality of molecular J-aggregates in experiments.

Circular Dichroism and Derivative Spectra Study of the Excitonic Aggregation of Pinacyanol by Aerosol-OT

Different structures are proposed for the complexes formed from the interaction between the cationic cyanine dye 1, 1’-diethyl-2, 2’-carbocyanine chloride (Pinacyanol chloride) and the anionic surfactant sodium bis (2-ethylhexyl) sul- fosuccinate (Aerosol-OT) in ethanol-water solutions. UV/vis and electronic circular dichroism (CD) spectra provide tools to study the concentration and solvent dependence of this interaction. The aggregation spectra of the dye are dominated by a strongly blue-shifted, sharp and single visible band, which appears at concentrations much below the critical micelle concentration (cmc) of Aerosol-OT. Above the cmc, the spectra in pure aqueous solution indicate disso- ciation into monomer and dimer species, and the system becomes completely empty of chirality. Two different CD spectra with a distinct isosbestic point are observed for complexes with different surfactant to dye ratios. Both the addi- tion of ethanol (more than 7.5%) and increasing the temperature retards the metachromatic process between the dye and Aerosol-OT. By using the peakFit program, the two overlapping excitonic absorption bands together with the optically inactive absorption band for one spectrum (the most optimal one) at a specific Aerosol-OT concentration were sepa- rated.

Interaction of bovine serum albumi with two alkylimidazolium-based ionic liquids investigated by microcalorimetry and circular dichroism

The interactions of bovine serum albumin (BSA) with two alkylimidazolium-based ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF4) and 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF6), in buffer solutions at pH 7.0 were investigated by isothermal titration calorimetry (ITC) and circular dichroism (CD). CD spectra showed that the two ionic liquids changed the secondary structure of BSA. Data process was based on the supposition that there were several independent types of binding sites on each BSA molecule for the two ligand molecules. The results obtained by using this supposition combined with Langmuir adsorption model showed that there were two types of such binding sites. One was the high affinity binding site, and the other was the low affinity binding site. The binding constants, changes in enthalpy, entropy and Gibbs free energy for the two types of binding were obtained, which showed that the two types of binding were driven by a favorable entropy increase. Furthermore, for either the ionic liquids, the number of the high affinity binding sites is much smaller than that of the low affinity ones. These results were interpreted with the molecular structure of BSA and the different substituent groups on imidazole ring of the two ionic liquid molecules.

手性分子构象分析装置圆二色光谱仪的加强与改造

圆二色光谱仪是对手性分子进行构象分析和理化性质表征的重要仪器.然而长期高强度的使用会产生光谱仪光学元件劣化、检测器灵敏度降低等问题.通过优化分光系统的光学元件提升光传输效率,升级具有更高量子效率的大面积雪崩硅光电二极管检测器,进而大幅提高仪器信噪比,同时将测量波长范围从175~900 nm扩展到175~1150 nm.在氙灯被点燃之前用氮气彻底净化仪器,把氧气排除在光谱仪之外是非常重要的操作步骤.安装具有监视、计划、流量设置、报警和辅助控制等功能的活性氮监测系统,可以实时监测控制仪器内部氮气吹扫情况.通过升级改造,既加强了仪器的性能,又节省了氮气消耗成本,同时仪器使用寿命将进一步延长.

Ag(Ⅰ)与氯苯基苯并咪唑配合物的合成、圆二色性和荧光性质

本文合成了Ag(Ⅰ)与2-(o-氯苯基)苯并咪唑(OCBM)的配合物,采用元素分析、质谱、UV、IR、摩尔电导率等手段进行了表征。圆二色性研究发现,配合物在199nm处呈正科顿效应,而在208nm和247nm处呈负科顿效应。荧光性质研究表明,配合物的特征荧光发射峰出现在601nm和613nm处,荧光寿命τ601和τ613分别为0.40ns和0.35ns。Ag(Ⅰ)配合物可发射橙色荧光和红色荧光,是良好的荧光材料。

固体CD光谱研究及其应用于手性席夫碱M(II)配合物

结合课题组近期的相关研究,对固体CD光谱在手性配合物研究中的应用,特别是手性样品固体CD光谱的测试方法进行了概述,通过对四对手性席夫碱M(II)(M=Ni、Cu)配合物的固体和溶液CD光谱进行比较研究,发现配合物的手性构型在固液相中保持一致,但其固液CD光谱之间存在不同程度的差异,可能是由于相应配合物在固体和溶液相中的四面体扭曲或构象的微妙不同所致.

CD在木脂素类化合物绝对构型测定中的应用

目的介绍圆二色谱(circular dichroism,CD)在木脂素类化合物绝对构型测定中的应用规律。方法在查阅国内外相关文献的基础上,对CD在芳基萘类、联苯环辛烯类、二苄基丁内酯类、双四氢呋喃类、苯并呋喃类等木脂素类化合物绝对构型测定中的应用规律进行综述。结果 CD在木脂素类化合物绝对构型测定中的应用具有一定的规律性。结论初步总结了CD在木脂素类化合物绝对构型测定中的应用规律,以期为该类化合物绝对构型测定提供有益的参考。

Cd^(2+)离子诱导的DNA构象变化

Interactions between Cd 2+ ions and salmon sperm DNA were investigated via UV Vis, Circular Dichroism(CD) and FT Raman spectroscopies. The experimental results show that Cd 2+ ions can coordinate with the phosphate groups of DNA and thus induce conformation changes of the DNA from B to A type.