Far-Field Detection of Near-Field Circular Dichroism Enhancements Induced by a Nanoantenna

Nanophotonics can enhance the inherent weak signal exhibited by chiral molecules in circular dichroism (CD) spectroscopy experiments. One mechanism to achieve this CD enhancement is based on increasing the optical chirality produced by nanophotonics antennas in their near-field, where chiral molecules are placed. However, ascertaining whether this CD enhancement is reached presents significant experimental challenges due to the complexity of measuring near-field optical chirality. Here, it is demonstrated that a local and single measurement of the degree of circular polarization in the far-field enables quantifying near-field CD enhancements. Thereby, based on this far-field measurement, the optimal response of the antenna is predicted for enhanced chiral sensing. Experimental validation of this near-to-far-field relation is provided for silicon spherical nanoantennas. The experimental results, supported by analytical theory and exact numerical simulations, can be interesting for the experimental characterization of devices capable of enhancing CD from a single far-field Stokes measurement.     

Alkyl Derivatives of Boehmite Having the Second Stage Structure

Abstract

The reaction of aluminum alkoxide in straight-chain primary alcohols at elevated temperatures yielded the alkyl derivatives of boehmite [AlO(OH)_1-x (OR) _x ], a class of intercalation compound where the guest moieties are covalently bonded to the host boehmite layers. The addition of small amounts of water to the reaction system yielded another phase having a larger basal spacing. XRD, IR, and elemental analysis showed that the products had the boehmite layer structure with the alkyl moieties incorporated between the boehmite layers. IR spectra of the products also exhibited bands due to hydrogen bonding between the boehmite layers. These results suggest that the products are the alkyl derivatives of boehmite having the second stage structure. Because water in the reaction medium facilitated the hydrolysis of intermediate aluminum alkoxides, the product with the second stage structure had smaller alkyl/Al ratio and therefore had smaller basal spacing than that expected from the corresponding first stage product.     

C-O-bond cleavage of esters with a naphthyl group in the higher triplet excited state during two-color two-laser flash photolysis

A C-O-bond cleavage of esters having a naphthyl group, NpCO-OR and RCO-ONp (Np=alpha- and beta-naphthyl ((alpha)Np and (beta)Np, respectively), R=Ph and Me), was found during the two-color two-laser flash photolysis in acetonitrile. The C-O-bond cleavage occurred when NpCO-OR and RCO-ONp were excited to the singlet excited states (S1). On the other hand, no reaction occurred from the lowest triplet excited states (T1). When NpCO-OR(T1) and RCO-ONp(T1) were excited to the higher triplet excited states (Tn) using the second laser during the two-color two-laser flash photolysis, the C-O-bond cleavage occurred. The C-O-bond cleavage quantum yield (Phi) was estimated from the plots of the T1-state esters disappeared within a laser flash versus the second laser intensities. The C-O-bond cleavage in (beta)NpCO-OPh(Tn) occurred more efficiently than in (alpha)NpCO-OPh(Tn) and that in PhCO-O(beta)Np(Tn) occurred more efficiently than in PhCO-O(alpha)Np(Tn). The Phi value for ester with Ph and beta-Np groups was larger than that for ester with Ph and alpha-Np groups. The Phi value for MeCO-O(alpha)Np(Tn) was similar to those for PhCO-ONp(Tn), while that for MeCO-O(beta)Np(Tn) was much smaller than those for PhCO-ONp(Tn) and MeCO-O(alpha)Np(Tn). On the other hand, no C-O-bond cleavage was observed in NpCO-OMe(Tn). The Phi value depended on the characters of the groups (Np, Ph, and Me) on the ester. Whether R is Ph or Me with or without pi electron, respectively, is important for the C-O-bond cleavage. In other words, electronic delocalization of the T(n) state including Np and ester groups is necessary for the occurrence of the C-O-bond cleavage in NpCO-OR(Tn) and RCO-ONp(Tn).     

Electric-field oriented polymer blend film for proton conduction

A novel proton conductor has been realized by employing a ternary polymer blend system in combination with an electric-field orientation technique. A polymer film recast from a solution containing poly(acrylic acid), poly(vinyl butyral), and fluoroalkyl graft polymer under 2 kV.cm(-1) exhibited 10 times higher proton conductivity than that prepared without the external electric field. However, when the film was prepared under a field higher than 4 kV.cm(-1), proton conductivity decreased. The membranous character has been investigated by SEM and AFM observations. As a result, it has been proven that an electric-field treatment of 2 kV.cm(-1) forms the largest hydrophilic domains for proton conduction in the film. The alteration of the phase separation morphology induced by the electric field well explains the proton conductivity change.     

The liquid-liquid extraction using hydrophilic solvents occluded to an oil-adsorbent as an organic phase: extraction of 8-quinolinolato complexes of alkaline earth metals into tetrahydrofuran.

In order to use a hydrophilic solvent as an organic phase in liquid-liquid extraction by retaining it to a solid support, the occlusion and desorption of nine hydrophilic solvents, such as methanol, to three kinds of commercially available oil-adsorbent were examined. The combination of tetrahydrofuran and WOSEP made by fibrous polypropylene was finally selected, and was subjected to the extraction of alkaline Earth metals with 8-quinolinol. It was proved that Mg2+, Ca2+, and Sr2+ ions could be successfully extracted into the tetrahydrofuran phase in the form of 8-quinolinolato complexes, which could not be extracted into CHCl3.     

ASYMPTOTIC FORMULAE OF EIGENVALUE-COUNTING FUNCTION FOR ELLIPTIC EIGENVALUE PROBLEMS ON A BOUNDED DOMAIN WITH A FRACTAL BOUNDARY

IIntroductlonLet fi be a bounded open set In the n－dimensional Euclldean space R”withtheboundaryo0．In this paper,we shallessentiallydeal with thefollowingeigenvalue problem:,nD 一)。o…4km)螂川川J”人川川,x〔u,丸 人k＝1\“’“)llillj＝U．U b UI[。where丸 meanso/axj,and we suPPose that coeaclents aj。(x),J;k＝ 1,2;…,。satisfy the following conditions:(1)aj。(x)is real function and belong to Cm(R”);(2)There exists an M＞0;such that Iajk(x)l＜M;;;k二 1,2,…,n;148 Ann ofDiff Eqs Vol…     

Design Method for Optical Waveguide Filters Having Corrugation Structures by Corrugation Width Modulation

A method to design a corrugated optical waveguide filter by modulating the corrugation width profile is proposed. This method is based on combined applications of the Fourier transformation and the F-matrix formalism. The method achieves the spatial profile of the corrugation width required to design a filter with any specified spectral profile of the reflection coefficient. The idea of the technique is that the spatial variation of the effective refractive index can be transformed, with the help of the F-matrix formalism, to variation of the corrugation width while maintaining a constant amplitude of the refractive index variation. Two examples are given applying the technique to the design of optical waveguide filters with reflectivity profiles of two- and four-rejection bands.     

Control-free air vent system for ultra-low volume sample injection on a microfabricated device.

An improved method of sample injection was demonstrated for introducing ultra-low volume liquid on a microfabricated device. In our previous study, a pressure-driven injection method has been introduced and was applied to on-chip electrophoresis. In this study, the need for control of the air vent, which was indispensable for sample injection in the previous study, was completely eliminated, facilitating sample injection with great simplicity and high accuracy. This was realized by altering the topology of the air vent channel, which is connected to a hydrophobic and narrow channel (called a passive valve). Several types of air vent channels were designed and their injection performances were tested. In addition, by modifying the shape and the position of air vent channel and passive valve, the residual liquid volume inside the passive valve after sample injection was decreased to approximately 0.5% of the injected volume, a value which showed high reproducibility.     

Quantitative analysis of triphenylboron in environmental water samples by liquid chromatography/mass spectrometry.

Liquid chromatography/mass spectrometry (LC/MS) has been applied to the analysis of triphenylboron, which has been produced as a substitute for organotin compounds, in water. Although commercial triphenylboron compounds are produced as pyridinyl complexes, the chemical form in water is supposed to be mainly triphenylboron after liberating pyridine. The triphenylborons were extracted from water with an Empore C18 extraction disk under acidic condition, and the extracts were introduced directly into a liquid chromatograph-mass spectrometer equipped with a negative ion electrospray ionization interface. Identification of the compounds was performed with specific ions produced from the triphenylboron, and a quantitative analysis was carried out using the peak areas. The average recoveries from distilled water, seawater and river water at 0.30 ng/ml were 92.3, 100 and 85.3%, respectively. A detection limit of 0.023 ng/ml for triphenylboron was achieved.