Chiral Ag and Au Nanomaterials Based Optical Approaches for Analytical Applications

Sensing of chiral compounds has gained great attentions for many decades. Chiral nanomaterials with a greater surface area, optical properties, and stability have however not been well realized in this field. Herein, strategies for the preparation of chiral Ag and Au nanomaterials are focused upon, including Ag and Au nanoparticles conjugated with chiral molecules with/without containing fluorophores, chiral nanoassemblies of Ag and Au nanoparticles, and chiral Ag and Au nanoclusters. The chirality of nanomaterials originates from their core and/or ligand, meanwhile that for nanoassemblies results from their complex spatial configuration. An emphasis is given to circular dichroism, colorimetry/UV–vis absorption, and fluorescence detection modes for sensing enantiomers and achiral analytes using the chiral Ag and Au nanomaterials. Several interesting examples for quantitation of DNA, proteins, peptides, drugs, and pollutants are provided to highlight their potential as sensitive and selective nanomaterials for enantiomer recognition and sensing of achiral analytes. Several important issues to be solved when using chiral nanomaterials for chiral recognition are specified. Some strategies for improving the sensitivity and selectivity of chiral nanomaterials for chiral recognition are suggested. The aim is to bring more attention to the potential of chiral nanomaterials for sensing important analytes such as chiral drugs.     

Chiral plasmonics and enhanced chiral light-matter interactions

Chirality, which describes the broken mirror symmetry in geometric structures, exists macroscopically in our daily life as well as microscopically down to molecular levels. Correspondingly, chiral molecules interact differently with circularly polarized light exhibiting opposite handedness(left-handed and right-handed). However, the interaction between chiral molecules and chiral light is very weak. In contrast, artificial chiral plasmonic structures can generate "super-chiral" plasmonic near-field, leading to enhanced chiral light-matter(or chiroptical) interactions. The "super-chiral" near-field presents different amplitude and phase under opposite handedness incidence, which can be utilized to engineer linear and nonlinear chiroptical interactions. Specifically,in the interaction between quantum emitters and chiral plasmonic structures, the chiral hot spots can favour the emission with a specific handedness. This article reviews the state-of-the-art research on the design, fabrication and chiroptical response of different chiral plasmonic nanostructures or metasurfaces. This review also discusses enhanced chiral light-matter interactions that are essential for applications like chirality sensing, chiral selective light emitting and harvesting. In the final part, the review ends with a perspective on future directions of chiral plasmonics.     

On the quantification of asymmetry in nature

A new concept of quantitative measure of the amount of structural asymmetry is introduced and defined by maximal overlap between two enantiomers of the same chiral body. This concept is to be called chiral coefficient, and it can readily be extended to physical properties such as mass or electronic wave-function distributions over chiral objects such as molecules or unit cells in crystals. The mathematical aspects of these coefficients are discussed. There exist two cases of maximal overlaps, symmetric and asymmetric, where for the asymmetric case there exist two positions of maximal overlap. It is also shown that there always exists a natural directionz for every asymmetric body for any physical property treated. The possibility of quantizing structural asymmetry is discussed, and, if it exists, it may be associated with the naturalz axis of the chiral system. Possible applications of asymmetry quantification are discussed.     

Self-assembly 2D plasmonic nanorice film for surface-enhanced Raman spectroscopy

As an ultrasensitive sensing technology, the application of surface enhanced Raman spectroscopy (SERS) is one interesting topic of nano-optics, which has huge application prospectives in plenty of research fields. In recent years, the bottleneck in SERS application could be the fabrication of SERS substrate with excellent enhancement. In this work, a two-dimensional (2D) Ag nanorice film is fabricated by self-assembly method as a SERS substrate. The collected SERS spectra of various molecules on this 2D plasmonic film demonstrate quantitative detection could be performed on this SERS substrate. The experiment data also demonstrate this 2D plasmonic film consisted of anisotropic nanostructures has no obvious SERS polarization dependence. The simulated electric field distribution points out the SERS enhancement comes from the surface plasmon coupling between nanorices. And the SERS signals is dominated by molecules adsorbed at different regions of nanorice surface at various wavelengths, which could be a good near IR SERS substrate for bioanalysis. Our work not only enlarges the surface plasmon properties of metal nanostructure, but also exhibits the good application prospect in SERS related fields.     

Controllable and switchable chiral near-fields in symmetric graphene metasurfaces

A strong chiral near-field plays significant roles in the detection, separation and sensing of chiral molecules. In this paper, a simple and symmetric metasurface is proposed to generate strong chiral near-fields with both circularly polarized light and linearly polarized light illuminations in the mid-infrared region. Owing to the near-field interaction between plasmonic resonant modes of two nanosheets excited by circularly polarized light, there is a strong single-handed chiral near-field in the gap between the two graphene nanosheets and the maximum enhancement of the optical chirality could reach two orders of magnitude. As expected, the intensity and the response wavelength of the chiral near-fields could be controlled by the Fermi level and geometrical parameters of the graphene nanosheets, as well as the permittivity of the substrate. Meanwhile, based on the interaction between the incident field and scattered field, the one-handed chiral near-field in the gap also could be generated by the linearly polarized light excitation. For the two cases, the handedness of the chiral near-field could be switched by the polarized direction of the incident light. These results have potential opportunities for applications in molecular detection and sensing.     

Development of new classes of plasmon active nano-structures and their application in bio-sensing and energy guiding

Metal nanostructures exhibit special optical resonance modes originating fronl tile subwavelengt.h confinement of conductive electrons in the material. These resonance modes represent a strong research focus due to their application potential in optics and sensing application, in this short review recent achievements of our group in this field are highlighted. A wet-chemistry approach synthesis of advanced metallic nanostruetures will be introduced and their exact positioning and manipulation by electric field is shown. Next. the application of these nanostructures for a detection of small molecules will be described in several examples. Also, it will be shown that inetal nanostruetures can be used for sub-wavelength light focusing and for efficient energy coupling into polymer chains.     

Chirality of molecular nanostructures on surfaces via molecular assembly and reaction: manifestation and control

The formation of chiral nanostructures via molecular assembly and reaction on solid surfaces is a ubiquitous surface process due to the symmetry-breaking at 2D surface. Studying chirality during the adsorption, assembly, and reaction of molecules on 2D solid surfaces at molecular level not only sheds deep insights into the enantioselective heterogeneous catalysis, chiral recognition, origin and evolution of chirality, and many important physical chemistry processes but also provides an important strategy to create chiral nanostructures. Here, we give a survey of recent advances in chiral expression and control in molecular assemblies and reactions on surfaces. We firstly give a brief introduction to the general concepts of chiral molecular nanostructures on surfaces. And then we focus on the induction and control of chirality expressed in molecular assemblies. The recent developments in the control strategies such as chiral co-adsorber, chiral auxiliary, chiral solvent, chiral templated surfaces, as well as the underlying mechanism to achieve the chiral induction and amplification, are reviewed. After that, we review the studies of chirality expressed in on-surface synthesis which has been proved to be a promising strategy to fabricate covalently bonded low-dimensional nanostructures and materials. In this respect, we introduce the chiral expression in the intramolecular and intermolecular coupling reactions on surfaces. In addition, we survey the methods to steer the stereoselectivity of on-surface reactions including the design of precursor structure, steric hindrance effect, substrate, kinetic parameters et al. Finally, the future outlook in this field is discussed.     

New Terms for Compact Form of Electroweak Chiral Lagrangian

The compact form of the electroweak chiral Lagrangian is a reformulation of its original form and is expressed in terms of chiral rotated electroweak gauge fields, which is crucial for relating the information of underlying theories to the coefficients of the low-energy effective Lagrangian. However the compact form obtained in previous works is not complete. In this letter we add several new chiral invariant terms to it and discuss the contributions of these terms to the original electroweak chiral Lagrangian.     

Biophysical and electrochemical properties of Self-assembled noncovalent SWNT/DNA hybrid and electroactive nanostructure

DNA self-assembled hybrid nanostructures are widely used in recent research in nanobiotechnology. Combination of DNA with carbon based nanoparticles such as single-walled carbon nanotube (SWNT), multi-walled carbon nanotube (MWNT) and carbon quantum dot were applied in important biological applications. Many examples of biosensors, nanowires and nanoelectronic devices, nanomachine and drug delivery systems are fabricated by these hybrid nanostructures. In this study, a new hybrid nanostructure has been fabricated by noncovalent interactions between single or double stranded DNA and SWNT nanoparticles and biophysical properties of these structures were studied comparatively. Biophysical properties of hybrid nanostructures studied by circular dichroism, UV–vis and fluorescence spectroscopy techniques. Also, electrochemical properties studied by cyclic voltammetry, linear sweep voltammetry, square wave voltammetry, choronoamperometry and impedance spectroscopy (EIS). Results revealed that the biophysical and electrochemical properties of SWNT/DNA hybrid nanostructures were different compare to ss-DNA, ds-DNA and SWNT singly. Circular dichroism results showed that ss-DNA wrapped around the nanotubes through π-π stacking interactions. The results indicated that after adding SWNT to ss-DNA and ds-DNA intensity of CD and UV–vis spectrum peaks were decreased. Electrochemical experiments indicated that the modification of single-walled carbon nanotubes by ss-DNA improves the electron transfer rate of hybrid nanostructures. It was demonstrated SWNT/DNA hybrid nanostructures should be a good electroactive nanostructure that can be used for electrochemical detection or sensing.     

Chiral lateral optical force near plasmonic ring induced by Laguerre-Gaussian beam

Owing to the good adjustability and the strong near-field enhancement, surface plasmons are widely used in optical force trap, thus the optical force trap can achieve excellent performance. Here, we use the Laguerre-Gaussian beam and a plasmonic gold ring to separate enantiomers by the chiral optical force. Along with the radial optical force that traps the particles, there is also a chirality-sign-sensitive lateral force arising from the optical spin angular momentum, which is caused by the interaction between optical orbit angular momentum and gold ring structure. By selecting a specific incident wavelength, the strong angular scattering and non-chiral related azimuthal optical force can be suppressed. Thus the chiral related azimuthal optical force can induce an opposite orbital rotation of the trapped particles with chirality of different sign near the gold ring. This work proposes an effective approach for catchingand separating chiral enantiomers.     

Chiral separation in microflows

Molecules that only differ by their chirality, so-called enantiomers, often possess different properties with respect to their biological function. Therefore, the separation of enantiomers presents a prominent challenge in molecular biology and has long been a main pursuit of organic chemistry. We suggest a new separation technique for chiral molecules that is based on the transport properties in a microfluidic flow with spatially variable vorticity. Because of their size the thermal fluctuating motion of the molecules must be taken into account. These fluctuations play a decisive role in the proposed separation mechanism.     

Isoniazid drug adsorption on the pristine and Al-doped zinc oxide nanosheets: a molecular modeling

Experimental works have exposed that Al-doping in the structure of ZnO nanostructures intensely increases their electronic sensitivity toward various chemicals. Herein, density functional theory calculations were employed to inspect the Al-doping effect on the sensitivity of a ZnO nanosheet (ZnOS) to the isoniazid (IS) drug. The pristine ZnOS physically adsorbs an IS molecule with adsorption energy (E _ad) of ?6.8?kcal/mol, and the sensing response value of 2.3 at 298?K. Replacing a Zn atom by an Al atom strengthens the interaction, increasing the E _ad to ?20.8?kcal/mol. Also, the Al-doping significantly increases the sensing response value to 150.3 by rising the electrical conductivity of the sheet. A short recovery time of 11.3 s is predicted for the Al-ZnOS-based sensor. The water solvent somewhat strengthens the interaction of IS drug with the Al-ZnOS, increasing the sensing response from 150.3 to 175.8. We concluded that the Al-doping makes the ZnOS a promising sensor for IS drug detection.     

Manipulation of light at the nanoscale for high-performance spectroscopic and optical applications

In this paper, we explore the use of nanostructures for a number of fascinating applications. These applications based on nanostructures include (1) optical sensors, (2) nanopixel printing, (3) improving the resolution of imaging techniques, and (4) lithography. In the sensing field, nanostructures are exploited for advanced sensor performance, namely, the label-free and enhanced sensitivity of (1) the surface plasmon resonance sensor and (2) the extraordinary optical transmission sensor and (3) the high sensitivity and selectivity of surface-enhanced Raman spectroscopy. In addition, research using nanostructures for visual applications was introduced for (1) harnessing nanostructures for full-color pixel printing and (2) exploiting metallic nanostructures to enhance the imaging resolution under diffraction limits based on the plasmonic effect. Finally, we introduce low cost, high accuracy, and fast lithographic methods based on the plasmonic effect by exploiting metallic nanostructures.     

表面纳米结构的自组装生长

无论是对低维基本物理以及其中新奇量子现象的探索与认识,还是微电子工业水平的持续发展,都迫切地需要掌握一种能够精确、可靠地操控表面纳米结构的方法.自组织生长,即粒子聚集时由于介观尺度力场或受限运动作用而导致的自发有序现象,在原子尺度上可以实现对纳米结构的精确控制,而在介观尺度上又可以调节这些微观结构单元的组织构型.文章结合作者近年来在表面纳米结构生长与物理性质研究方面所做过的工作,从自组织生长的原理出发,介绍了对金属纳米线、有序分子薄膜以及合金量子点阵列生长进行人工操控的方法.     

基于功能化的金纳米的共振瑞利散射方法手性识别肉碱对映体

一种不经分离而同时测定手性对映体的简便方案是非常有趣和有用的.提出一种基于共振瑞利散射(RRS)光谱技术手性识别新方法,利用功能化的金纳米粒子(Au NPs)同时检测肉碱对映体.Au NPs的RRS强度很弱,但当Cu2+存在时,RRS强度显著增加.更有趣的是,肉碱对映体均可以降低Cu2+-Au NPs体系的RRS强度,但D-肉碱使RRS降低更多.在最优实验条件下,均有良好的线性关系并有很好的相关系数以及较低的检出限.由此,这种方法可以计算出肉碱对映体的对映体比率和对映体分数.并应用于胶囊样品中肉碱对映体混合物手性识别的研究.该方法不需要复杂的手性修饰处理,并具有简捷低消耗、灵敏度高、选择性好等优点.     

Detecting nanoparticles by “listening”

In the macroscopic world, we can obtain some important information through the vibration of objects, that is, listening to the sound. Likewise, we can also get some information of the nanoparticles that we want to know by the means of “listening” in the microscopic world. In this review, we will introduce two sensing methods (cavity optomechanical sensing and surface-enhanced Raman scattering sensing) which can be used to detect the nanoparticles. The cavity optomechanical systems are mainly used to detect sub-gigahertz nano particle or cavity vibrations, while surface-enhanced Raman scattering is a well-known technique to detect molecular vibrations whose frequency generally exceeds terahertz. Therefore, the vibrational information of nanoparticles from low-frequency to high-frequency could be obtained by these two methods. The size of the viruses is at the nanoscale and we can regard it as a kind of nanoparticles. Rapid and ultrasensitive detection of the viruses is the key strategies to break the spread of the viruses in the community. Cavity optomechanical sensing enables rapid, ultrasensitive detection of nanoparticles through the interaction of light and mechanical oscillators and surface-enhanced Raman scattering is an attractive qualitatively analytical technique for chemical sensing and biomedical applications, which has been used to detect the SARS-CoV-2 infected. Hence, investigation in these two fields is of vital importance in preventing the spread of the virus from affecting human’s life and health.     

Transport in graphene nanostructures

Graphene nanostructures are promising candidates for future nanoelectronics and solid-state quantum information technology. In this review we provide an overview of a number of electron transport experiments on etched graphene nanostructures. We briefly revisit the electronic properties and the transport characteristics of bulk, i.e., two-dimensional graphene. The fabrication techniques for making graphene nanostructures such as nanoribbons, single electron transistors and quantum dots, mainly based on a dry etching ??paper-cutting?? technique are discussed in detail. The limitations of the current fabrication technology are discussed when we outline the quantum transport properties of the nanostructured devices. In particular we focus here on transport through graphene nanoribbons and constrictions, single electron transistors as well as on graphene quantum dots including double quantum dots. These quasi-one-dimensional (nanoribbons) and quasi-zero-dimensional (quantum dots) graphene nanostructures show a clear route of how to overcome the gapless nature of graphene allowing the confinement of individual carriers and their control by lateral graphene gates and charge detectors. In particular, we emphasize that graphene quantum dots and double quantum dots are very promising systems for spin-based solid state quantum computation, since they are believed to have exceptionally long spin coherence times due to weak spin-orbit coupling and weak hyperfine interaction in graphene.     

Optimised Dirac operators on the lattice: construction,properties and applications

We review a number of topics related to block variable renormalisation group transformations of quantum fields on the lattice, and to the emerging perfect lattice actions. We first illustrate this procedure by considering scalar fields. Then we proceed to lattice fermions, where we discuss perfect actions for free fields, for the Gross‐Neveu model and for a supersymmetric spin model. We also consider the extension to perfect lattice perturbation theory, in particular regarding the axial anomaly and the quark gluon vertex function. Next we deal with properties and applications of truncated perfect fermions, and their chiral correction by means of the overlap formula. This yields a formulation of lattice fermions, which combines exact chiral symmetry with an optimisation of further essential properties. We summarise simulation results for these so‐called overlap‐hypercube fermions in the two‐flavour Schwinger model and in quenched QCD. In the latter framework we establish a link to Chiral Perturbation Theory, both, in the p‐regime and in the ϵ‐regime. In particular we present an evaluation of the leading Low Energy Constants of the chiral Lagrangian – the chiral condensate and the pion decay constant – from QCD simulations with extremely light quarks.     

Spin state selective coherence transfer: a method for discrimination and complete analyses of the overlapped and unresolved 1H NMR spectra of enantiomers

In general, the proton NMR spectra of chiral molecules aligned in the chiral liquid crystalline media are broad and featureless. The analyses of such intricate NMR spectra and their routine use for spectral discrimination of R and S optical enantiomers are hindered. A method is developed in the present study which involves spin state selective two dimensional correlation of higher quantum coherence to its single quantum coherence of a chemically isolated group of coupled protons. This enables the spin state selective detection of proton single quantum transitions based on the spin states of the passive nuclei. The technique provides the relative signs and magnitudes of the couplings by overcoming the problems of enantiomer discrimination, spectral complexity and poor resolution, permitting the complete analyses of the otherwise broad and featureless spectra. A non-selective 180 degrees pulse in the middle of MQ dimension retains all the remote passive couplings. This accompanied by spin selective MQ-SQ conversion leads to spin state selective coherence transfer. The removal of field inhomogeneity contributes to dramatically enhanced resolution. The difference in the cumulative additive values of chemical shift anisotropies and the passive couplings, between the enantiomers, achieved by detecting Nth quantum coherence of N magnetically equivalent spins provides enhanced separation of enantiomer peaks. The developed methodology has been demonstrated on four different chiral molecules with varied number of interacting spins, each having a chiral centre.     

等离子体纳米结构中的Fano共振效应及其应用

Fano共振效应是一种具有非对称线型的共振散射现象,起源于共振过程和非共振过程的量子干涉效应。近年来,在等离子体纳米结构中Fano共振现象也被发现,并成为纳米光子学的一个研究热点。等离子体Fano共振通常具有较窄的光谱线宽,且不能直接与入射光耦合,只能局域在近场,强的近场局域特性可以获得巨大的表面电磁场增强。由于等离子体Fano共振独特的光学特性,已经被应用到单分子探测、高灵敏度传感、增强光谱、完美吸收、电磁诱导透明和慢光光子学器件等众多领域当中。