Chirality Switching Via Rotation of Bilayer Fourfold Meta-Structure

Chiral effects have been observed from the interaction of chiral plasmonics nanostructures with light. Such nanostructures enhance the chiral response of molecules and provide an ideal platform for biological and chemical sensing. Here, we investigate the chiral switching effects of an array of subwavelength nanostructures with a unit cell composed of four double-layered nanostrips arranged to be rotationally symmetric. We observe chiral switching leading to a change in circular dichroism (CD) signature when the mutual angle between the first and second layer increases from 0° to 90° with respect to each other. This mutual angle can be manipulated to switch the handedness of the nanostructure and cause a change in the outgoing light. We also investigated the field distribution of each mode when circularly polarized light is normally incident into the structure. These modes can be categorized into longitudinal and transverse modes depending on the orientation of their dipole moments. The mode studies clearly show the nature of each plasmonics mode.     

Change of handedness in cholesteric liquid crystalline phase for N-phthaloylchitosan solutions in organic solvents

The influence of concentration on the helicoidal change of N-phthaloylchitosan (PhCh) solutions in Me2SO, DMAc and DMF was investigated by means of circular dichroism (CD). The critical concentrations to form liquid crystal phase in these three solvents were 43, 45 and 48 wt.%, respectively as measured with polarized optical microscope. There were two kinds of CD peaks, sharp peaks with absorption maximum at about 330 nm induced by the helical conformation of molecular chain, and very broad peaks covering almost whole visible region induced by the cholesteric helix of mesophase. The later only appeared in concentrated solutions with the concentration higher than the critical concentration. The handedness of both levels of helicoidal structures changed from left- to right-handed with the increase of concentration for PhCh/Me2SO solutions. The chirality transfer occurred between these two chiral levels. For PhCh/DMAc and PhCh/DMF systems, only the handedness of helical conformation reversed, but the cholesteric helix did not change. As a method to measure critical concentration, CD is more sensitive than polarized optical microscopy (POM).     

Helicity of perfluoroalkyl chains controlled by the self‐assembly of the Ala‐Ala dipeptides

Four Ala‐Ala dipeptides with a perfluoroalkyl chain at the N‐terminal were synthesized. They were able to self‐assemble into helical nanofibers and/or twisted nanobelts in a mixture of DMSO/H₂O. The handedness of nanofibers and nanobelts was controlled by the chirality of the alanine at the N‐terminal. The stacking handedness of the phenylene groups and the helicity of the perfluoroalkyl chain were studied using circular dichroism spectroscopy and vibrational circular dichroism, respectively. The chirality of the alanine at N‐terminal controlled the stacking handedness of the neighboring phenylene groups. Moreover, due to the low potential barrier between M‐ and P‐helices of the perfluorocarbon chain, the handedness of the organic self‐assemblies eventually controlled the helicity of the perfluorocarbon chain. X‐ray diffraction indicated that a lamellar structure was formed by the dimers of the dipeptides.     

Profile Simulation and Fabrication of Gold Nanostructures by Separated Nanospheres with Oblique Deposition and Perpendicular Etching

This paper investigates in detail the profiles of the nanostructures fabricated by nanosphere lithography through oblique deposition and perpendicular etching. 2D or 3D nanostructures can be achieved by this cost-effective method. Because the optical response of a particular nanoparticle depends on its size and shape, this angle deposition method can produce various shapes of nanostructures, which are suitable for localized surface plasmon resonance biosensor applications. The nanostructure profiles under various deposition and etching conditions are simulated in our work. The calculated 3D profiles are verified by the 3D nanostructures fabricated in our experiments, and the calculated 2D profiles are in good agreement with the fabricated nanocrescents reported by another research group. This paper gives a full theoretical solution of the obtainable nanostructure shapes by nanosphere lithography utilizing oblique deposition and perpendicular etching.     

Crystallization and solid-state reaction as a route to asymmetric synthesis from achiral starting materials

Many molecules which are achiral can crystallize in chiral (enantiomorphic) crystals and, under suitable conditions, crystals of only one chirality may be obtained. The formation of right- or left-handed crystals in excess is equally probable. Lattice-controlled (topochemical) photochemical or thermal solid-state reactions may then afford stable, optically active products. In the presence of the chiral products, achiral reactants may preferentially produce crystals of one chirality, leading to a feedback mechanism for the generation and amplification of optical activity. Amplification of optical activity can also be achieved by solid-state reactions. The optical synthesis of biologically relevant compounds by such routes may be envisaged.     

Remote Excited Raman Optical Activity of Adenine Along Ag Plasmonic Waveguide

We report the remote excited Raman optical activity (ROA) of adenine along Ag plasmonic waveguide. First, the surface plasmons that propagate along Ag nanowire is demonstrated experimentally. Second, the Raman spectra of adenine are measured experimentally. Third, the remote exited ROA by plasmonic waveguide are measured and compared. It is found that the plasmon chirality strongly influenced the molecular ORA by the local surface plasmon and remote plasmon waveguide. The plasmon chirality of nanostructures and the chirality plasmon waveguide should be considered in the experiments for the local and remote measurement.     

Plasmonic Circular Dichroism Study of DNA–Gold Nanoparticles Bioconjugates

Plasmonic circular dichroism (CD) responses of hybrid nanostructures containing noble metal nanoparticles and chiral molecules have received increasing interest with various applications in nanophotonics. Chiral biomolecules show strong CD signals typically found in the ultraviolet region, whereas, in the visible range, they produce a weak signal. Strengthening the CD signal in the visible region is of high importance, which could be achieved through fabrication of novel hybrid nanostructures. Herein, gold nanoparticles (GNPs) have been assembled via DNA linker to investigate the possibility of enhancing plasmonic CD signal in the visible range. DNA-linked assemblies with pre- and postannealed conditions were characterized by ultraviolet–visible spectroscopy, dynamic light scattering (DLS), and CD spectropolarimetry. In the presence of DNA linker with sticky ends, the aggregation phenomenon was traced by red shifts of surface plasmon resonance of nanoparticles. Time-dependent hybridization of single-stranded “sticky ends” with DNA-conjugated GNPs and increased probability of hydrogen bond formation lead to enhancement of CD signals in the ultraviolet region. Complexation of biomolecule and nanoparticle assemblies induced enhanced CD signals in the visible range, which was noticed both before and after purification. DLS characterization of the assemblies also confirmed the difference in the size of aggregates, which could be controlled by the linker molecules. This investigation encourages possibility of utilizing plasmonic CD technique as a tool for tracing fabricated nanostructure assemblies with enhanced characterization possibility.     

Stereostructural Implication by the Differential Bond Polarizability: ROA Intensity Study of Chiral S 2‐Amino 1‐Propanol

The bond polarizability and differential bond polarizability are introduced to interpret the Raman and Raman optical activity (ROA) intensities, calculated by the ab initio method. Chiral S 2‐amino 1‐propanol is taken as a model molecule. Through these bond polarizabilities, we observe that symmetric and antisymmetric coordinates are, respectively, more significant in Raman and ROA. It is noted that in S 2‐amino 1‐propanol those bonds lying on a common plane share the same differential bond polarizability sign while that of the asymmetric C‐H bond which protrudes out of the plane possesses the opposite sign. We conclude that ROA can offer more stereostructural implications than Raman and that the differential bond polarizability is potentially the appropriate parameter in interpreting the 3D configuration of a molecule. Chirality 26:255–259, 2014. © 2014 Wiley Periodicals, Inc.     

A Helical Polyphenylacetylene Having Amino Alcohol Moieties Without Chiral Side Groups as a Chiral Ligand for the Asymmetric Addition of Diethylzinc to Benzaldehyde

One‐handed helical polyphenylacetylenes having achiral amino alcohol moieties, but no chiral side groups, were synthesized by the helix‐sense‐selective copolymerization of an achiral phenylacetylene having an amino alcohol side group with a phenylacetylene having two hydroxyl groups. Since the resulting helical copolymers were successfully utilized as chiral ligands for the enantioselective alkylation of benzaldehyde with diethylzinc, we can conclude that the main‐chain chirality based on the one‐handed helical conformation is useful for the chiral catalysis of an asymmetric reaction for the first time. The enantioselectivities of the reaction were controlled by the optical purities of the helical polymer ligands. In addition, the polymer ligands could be easily recovered by precipitation after the reaction. Chirality 27:454–458, 2015. © 2015 Wiley Periodicals, Inc.     

Study of Circular Dichroism Modes Through Decomposition of Planar Nanostructures

We extend the plasmon hybridization method from a single nanoparticle to a complex planar nanostructure, decomposing the complex nanostructure into fundamental nanoparticle building blocks. Using gammadion nanostructure as an example, we validated the theory by comparing the field profile in the gammadion’s arms under the influence of an incident circularly polarized wave. This allows us to address the origin of the plasmonics modes in the circular dichroism (CD) spectrum. The use of this hybridization method provides a simple and intuitive explanation on how conductive and inductive coupling may result from complex planar nanostructures, allowing us to study its optical properties. Using our approach, top down hybridization studies can be applied to other complex planar structures to gain further insight on the origin of the CD modes and enhance ultrasensitive sensing of chiral micro and macro molecules.     

Characterization of zinc oxide nanocrystals with different morphology for application in ultraviolet‐light photocatalytic performances on rhodamine B

ZnO nanostructures of different morphology (nanorods, nano‐leaf, nanotubes) were favourably grown using a chemical precipitation process. The prepared ZnO nanostructures were characterized systematically using absorption spectroscopy, emission spectroscopy, X‐ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared studies. XRD results showed the hexagonal wurtzite phase of the synthesized ZnO nanostructures. Structural properties such as average crystallite size, lattice constants, volume of the unit cell, atomic fraction, and structural bonds were also studied. The optical band gap of the synthesized ZnO nanocrystals varied from 3.52 eV to 3.69 eV with high quantum yield of the blue emission (~420 nm). Urbach energy for ZnO nanocrystals was calculated to be 0.702 eV, 0.901 eV, and 0.993 eV for nanorods, nano‐leaf, and tube like ZnO crystals, respectively. Morphology of the fabricated nanostructures was investigated using SEM. Photocatalytic degradation of rhodamine B (Rh B) in solution under UV irradiation was explored with different ZnO morphology. Photocatalytic experiments showed that ZnO nano‐leaf had a higher degradation rate of photocatalytic activity of photodegrading Rh B compared with the other tube shape and rods shape nanostructures. The Rh B dye degraded considerably by ～79.05%, 74.41%, and 69.8% within 120 min in the presence of the as‐fabricated fern nano‐leaf, nanotubes, and nanorods of the ZnO nanocrystals at room temperature.     

Revisiting polarimetry near the isotropic point of an optically active,non‐enantiomorphous,molecular crystal

Accurate polarimetric measurements of the optical activity of crystals along low symmetry directions are facilitated by isotropic points, frequencies where dispersion curves of eigenrays cross and the linear birefringence disappears. We report here the optical properties and structure of achiral, uniaxial (point group D_2d) potassium trihydrogen di‐(cis‐4‐cyclohexene‐1,2‐dicarboxylate) dihydrate, whose isotropic point was previously detected (S. A. Kim, C. Grieswatch, H. Küppers, Zeit. Krist. 1993; 208:219–222) and exploited for a singular measurement of optical activity normal to the optic axis. The crystal structure associated with the aforementioned study was never published. We report it here, confirming the space group assignment I c2, along with the frequency dependence of the fundamental optical properties and the constitutive tensors by fitting optical dispersion relations to measured Mueller matrix spectra. k‐Space maps of circular birefringence and of the Mueller matrix near the isotropic wavelength are measured and simulated. The signs of optical rotation are correlated with the absolute crystallographic directions.     

C3-symmetrical self-assembled structures investigated by vibrational circular dichroism

We demonstrate by using vibrational circular dichroism (VCD) spectroscopy that it is possible to investigate the chirality of a supramolecular polymeric system in relatively dilute solutions. Chiral C(3)-symmetrical discotic molecules, based on a trialkylbenzene-1,3,5-carboxamide, form supramolecular columnar stacks with a right-handed helical structure in solution due to intermolecular hydrogen bonds. The handedness of the supramolecular chirality is determined using electronic spectroscopy measurements. Under dilute conditions (at 10(-3) M concentrations), it was also possible to probe the hydrogen bonding moieties with IR and VCD spectroscopy on these self-assembled structures. In combination with density functional theory (DFT) calculations, we could verify the preference for a right-handed chirality in the helical stacks and the nonplanar orientation of the carbonyl groups present in the molecule. This chiral arrangement is in agreement with the structure determined for a related benzene-1,3,5-tricarboxamide by X-ray diffraction. Chirality, 2008. (c) 2008 Wiley-Liss, Inc.     

Conformational study on poly [gamma-(alpha-phenethyl)-L-glutamate] using vibrational circular dichroism spectroscopy

Vibrational circular dichroism (VCD) and IR absorption spectra are obtained in a chloroform solution for poly[gamma-((R)-alpha-phenethyl)-L-glutamate] (PRPLG) and poly[gamma-((S)-alpha-phenethyl)-L-glutamate] (PSPLG), whose only structural difference is an opposite chiral center in the side chain. Their characteristic amide A, I, and II bands show VCD patterns quite similar to those of poly[gamma-benzyl-L-glutamate] (PBLG), indicating that the secondary structure of these polypeptides is a right-handed alpha-helix. The VCD spectra in the CH stretching region exhibit different patterns for PRPLG and PSPLG, reflecting the chirality difference in the side chains. This difference is interpreted on the basis of the additivity of optical activity contributions from the main chain conformation and the chirality difference in the side chains. The results indicate that a VCD difference spectrum of the CH stretching region is a useful diagnostic tool for elucidating local chirality differences.     

Control of peptide conformation by the Thorpe-Ingold effect (C alpha-tetrasubstitution)

The preferred conformations of peptides heavily based on the currently extensively exploited achiral and chiral alpha-amino acids with a quaternary alpha-carbon atom, as determined by conformational energy computations, crystal-state (x-ray diffraction) analyses, and solution ((1)H-NMR and spectroscopic) investigations, are reviewed. It is concluded that 3(10)/alpha-helical structures and the fully extended (C(5)) conformation are preferentially adopted by peptide sequences characterized by this family of amino acids, depending upon overall bulkiness and nature (e.g., whether acyclic or C(alpha) (i) <--> C(alpha) (i) cyclized) of their side chains. The intriguing relationship between alpha-carbon chirality and bend/helix handedness is also illustrated. gamma-Bends and semiextended conformations are rarely observed. Formation of beta-sheet structures is prevented.     

Optically active porous hybrid particles constructed by alkynylated cellulose nanocrystals,helical substituted polyacetylene,and inorganic silica for enantio-differentiating towards naproxen

This article reports on a novel type of ternary chiral porous hybrid particles (TCPHPs) constructed by alkynylated cellulose nanocrystals (A-CNCs), helical substituted polyacetylene, and inorganic silica. The resulting TCPHPs combine the respective advantages of the three components. A-CNCs serve as stabilizer, co-monomer, and chiral source simultaneously and transfer their chirality to the resulting helical substituted polyacetylenes in the course of copolymerization with achiral acetylenic monomer following “sergeants and soldiers rule”. Helical substituted polyacetylenes form chiral helical structures and thus endow TCPHPs with the anticipated optical activity. Inorganic silica constitutes the rigid framework and is covalently bonded with the organic components through hydrolysis of Si-O-Et groups. Phase separation between the organic and inorganic components renders TCPHPs with abundant pores. Scanning electron microscope (SEM) images confirm the formation of spherical particles with porous structures. Circular dichroism spectra demonstrate the optical activity of the chiral hybrid particles. The as-prepared TCPHPs exhibit capacity for enantio-differentiating performance towards chiral naproxen.     

Circular dichroism of surface complexes based on quantum dots and azo dye

Chiral properties of surface complexes based on CdSe/ZnS quantum dots (QDs) and 1‐(2‐pyridylazo)‐2‐naphthol (PAN) azo dye were investigated by circular dichroism spectroscopy. The use of L‐, D‐cysteine (Lcys, Dcys) capping ligands allowed us to obtain water‐soluble chiral QD‐PAN complexes. The characterization of the complexes was performed by UV‐vis, FTIR, and CD spectroscopy. Quantum chemical TDDFT calculated CD spectra reproduced the experimentally observed sign patterns, which originate from binding Lcys or Dcys and PAN molecules to the same Zn atom on the QD surface. The resulting complex is characterized by a large circular dichroism in comparison with an ordinary QD chirality induced by cysteine molecules. The pattern of CD signal is the same for Lcys and Dcys ligands in chiral QD‐PAN complex.     

Inner Surface Chirality of Single‐Handed Twisted Carbonaceous Tubular Nanoribbons

Single‐handed twisted 4,4′‐biphenylene‐bridged polybissilsesquioxane tubular nanoribbons and single‐layered nanoribbons were prepared by tuning the water/ethanol volume ratio in the reaction mixture at pH = 11.6 through a supramolecular templating approach. The single‐layered nanoribbons were formed by shrinking tubular nanoribbons after the removal of the templates. In addition, solvent‐induced handedness inversion was achieved. The handedness of the polybissilsesquioxanes could be controlled by changing the ethanol/water volume ratio in the reaction mixture. After carbonization at 900 °C for 4.0 h and removal of silica, single‐handed twisted carbonaceous tubular nanoribbons and single‐layered nanoribbons with micropores in the walls were obtained. X‐ray diffraction and Raman spectroscopy analyses indicated that the carbon is predominantly amorphous. The circular dichroism spectra show that the twisted tubular nanoribbons exhibit optical activity, while the twisted single‐layered nanoribbons do not. The results shown here indicate that chirality is transferred from the organic self‐assemblies to the inner surfaces of the 4,4′‐biphenylene‐bridged polybissilsesquioxane tubular nanoribbons and subsequently to those of the carbonaceous tubular nanoribbons. Chirality 27:809–815, 2015. © 2015 Wiley Periodicals, Inc.     

TiO2‐coated fluoride nanoparticles for dental multimodal optical imaging

Core‐shell nanostructures associated with photonics techniques have found innumerous applications in diagnostics and therapy. In this work, we introduce a novel core‐shell nanostructure design that serves as a multimodal optical imaging contrast agent for dental adhesion evaluation. This nanostructure consists of a rare‐earth‐doped (NaYF₄:Yb 60%, Tm 0.5%)/NaYF₄ particle as the core (hexagonal prism, ~51 nm base side length) and the highly refractive TiO₂ material as the shell (~thickness of 15 nm). We show that the TiO₂ shell provides enhanced contrast for optical coherence tomography (OCT), while the rare‐earth‐doped core upconverts excitation light from 975 nm to an emission peaked at 800 nm for photoluminescence imaging. The OCT and the photoluminescence wide‐field images of human tooth were demonstrated with this nanoparticle core‐shell contrast agent. In addition, the described core‐shell nanoparticles (CSNps) were dispersed in the primer of a commercially available dental bonding system, allowing clear identification of dental adhesive layers with OCT. We evaluated that the presence of the CSNp in the adhesive induced an enhancement of 67% scattering coefficient to significantly increase the OCT contrast. Moreover, our results highlight that the upconversion photoluminescence in the near‐infrared spectrum region is suitable for image of deep dental tissue.      

Daunomycin inverts the long-range chirality of DNA condensed states

The effect of daunomycin upon DNA condensed states induced by poly(ethylene glycol) (PEG) was studied by circular dichroism (CD) and circular intensity differential scattering (CIDS). The CD spectra of these aggregates showed psi-type anomalies and intensities 10-100 times greater than those obtained with the dispersed DNA solutions in the absence of PEG. Increasing concentrations of daunomycin, added to the DNA solution prior to its aggregation, led, in the presence of PEG, to CD and CIDS signals which gradually decreased in magnitude and eventually inverted sign. The coincidence of the transition point of both signals and a careful characterization of the CD spectrum at the transition point clearly indicated that the inversion observed corresponds to an inversion of the handedness of the aggregates. The latter result suggests that the structure of the aggregates at the inversion point should resemble that of a nematic liquid-crystalline structure. The characteristic B-DNA spectrum obtained in this case further suggests that the packing process does not affect the secondary structure of the DNA molecules and that small changes in their local structure can induce dramatic changes in their long-range tertiary packing. The results obtained in this study represent a confirmation of a recent theory of psi-type CD in which the anomalous signals are interpreted as a manifestation of the long-range chirality of the aggregates.