A simple approach for the ultrasensitive detection of paraquat residue in adzuki beans by surface-enhanced Raman scattering.

Paraquat (PQ), a broad-spectrum contact herbicide, has been used in many countries for controlling weed growth in agriculture because of its quick-acting and nonselective contact with green plant tissue. PQ is also toxic to humans, and even contributes to the development of neurodegenerative diseases. However, PQ is generally excluded from pesticide residue monitoring programs due to the lack of suitable determination methods. Thus, this study developed a detection method combined with simple extraction and surface-enhanced Raman spectroscopy (SERS) to rapidly determine and quantify the PQ residue on legumes without destructive procedures and high-cost instruments. Following the extraction procedure of the QuPPe-method, however, we took whole adzuki beans (Vigna angularis) extracted via a mixture of methanol and 1% formic acid at room temperature and followed by a 1 min cleanup by SPE. The PQ values for adzuki beans determined by LC/MSMS showed that regardless of whether extraction was followed by the QuPPe-method or the method we proposed, a consistent and low relative standard deviation (RSD) below <22% was found. In this study, we proposed to extract PQ on the surface of the beans by shaking briefly with solvent, and then the PQ molecules were detected and quantified by depositing Ag nanoparticles (AgNPs) and performing SERS within 10 min. Using a coating of deposited Ag nanoparticles, SERS can achieve a limit of detection (LOD) for PQ on the order of 1 µg L-1 (∼4 × 10-9 M) and a method detection limit (MDL) for adzuki beans of 0.8 µg kg-1 (∼3.3 × 10-9 M). This sensitivity at the ppb level absolutely met the maximum residue limit (MRL) for PQ in dried beans as declared by most countries, including the US (0.3 mg kg-1), Australia (1.0 mg kg-1) and Taiwan (0.2 mg kg-1). Taiwan will ban the use of PQ as a defoliating agent for harvest in adzuki bean fields in 2019; therefore, developing a method for detecting PQ residues in the field or in import markets is necessary for consumer health and for authorities. This study provided an opportunity to utilize SERS in the field of on-site pesticide residue screening.

Deposited metamaterial thin film with negative refractive index and permeability in the visible regime.

Thin films are fabricated from arrays of silver nanorods with thicknesses of 160 nm and 200 nm, to function as a metamaterial. The negative refractive index and negative permeability are retrieved from measured reflection and transmission coefficients using walk-off interferometer in the visible regime. A negative-index-material thin film with negative permittivity or (and) permeability can be produced by glancing angle deposition.

Optical configuration for unpolarized ultra-long-range surface-plasmon-polariton waves.

Multilayered structures were designed on both sides of a thin silver film to let both transverse-magnetic- and transverse-electric-polarized electromagnetic waves propagate along a thin metal film simultaneously in the same configuration, as so-called long-range surface-plasmon-polariton (LRSPP) waves. Based on the admittance analysis and design, the propagation length of an unpolarized LRSPP wave can be extended by more than 1 order of magnitude compared with previous results.

Effects of the equivalent coupling layer on ultra-long-range surface-plasmon-polariton waves.

The mechanism and design of p- and s- polarized ultra-long-range surface-plasmon-polariton (SPP) propagation in the configuration {prism/ equivalent coupling layer (ECL)/ silver film (20 nm)/ equivalent substrate (ES)} are investigated using a normalized admittance diagram (NAD). The excitation of ultra-long-range SPP waves is characterized as a huge open loop of the NAD of the metal film at a designated angle of incidence. We propose three kinds of ECLs to complete the multilayer ultra-long-range SPP design: the normalized admittance of the ECL is (i) real (ii) infinite (iii) imaginary. The ultra-long propagation lengths in the three designs are compared at a wavelength of 632.8 nm for p- and s-polarization states.

Vapor-deposited thin films with negative real refractive index in the visible regime.

A thin film comprising parallel tilted nanorods was deposited by directing silver vapor obliquely towards a plane substrate. The reflection and transmission coefficients of the thin film were measured at three wavelengths in the visible regime for normal-illumination conditions, using ellipsometry and walk-off interferometry. The thin film was found to display a negative real refractive index. Since vapor deposition is a well-established industrial technique to deposit thin films, this finding is promising for large-scale production of negatively refracting metamaterials.

Multilayered structures for p- and s-polarized long-range surface-plasmon-polariton propagation.

A normalized admittance diagram assists in describing and designing multilayered structures to excite long-range surface-plasmon-polariton (LRSPP) waves of either the p- or the s-polarization state. These structures comprise symmetric periodic multilayers on one or both sides of a metal thin film in either the Kretschmann or the Sarid configuration. The normalized admittance diagram even assists in designing structures that can be used to excite LRSPP waves of both polarization states simultaneously.

Biologically inspired achromatic waveplates for visible light.

Waveplates are planar devices used in optics and optoelectronics to change the polarization state of light. Made of anisotropic dielectric materials such as crystals and thin films, waveplates are not known to exhibit achromatic performance over the visible regime. Inspired by the microvillar structure of R8 cells functioning as polarization converters in the eyes of stomatopod crustaceans, we conceived, designed, fabricated and tested periodically multilayered structures comprising two different types of arrays of nanorods. Morphologically analogous to the ocular cells, here we show that the periodically multilayered structures can function as achromatic waveplates over the visible regime.

Modulation of the polarization state of light using a weak anisotropic thin film.

The polarization state of light is modulated by an anisotropic thin film. An anisotropic MgF(2) film is deposited onto a plate that is put in contact with a BK7 prism to form a BK7 prism/film/air configuration. It is shown that the polarization state of reflected light can be easily modulated from a linear state to a circular state by rotating the thin-film plate.