Material research for environmental sustainability in Thailand: current trends

This article covers recent developments of material research in Thailand with a focus on environmental sustainability. Data on Thailand’s consumption and economic growth are briefly discussed to present a relevant snapshot of its economy. A selection of research work is classified into three topics, namely, (a) resource utilization, (b) material engineering and manufacturing, and (c) life cycle efficiency. Material technologies have been developed and implemented to reduce the consumption of materials, energy, and other valuable resources, thus reducing the burden we place on our ecological system. At the same time, product life cycle study allows us to understand the extent of the environmental impact we impart to our planet.     

Light-assisted synthesis of Pt-Zn porphyrin nanocomposites and their use for electrochemical detection of organohalides

Pt-Zn porphyrin nanocomposites have been synthesized using zinc porphyrin and dihydrogen hexachloroplatinate in the presence of light and ascorbic acid. TEM and AFM imaging revealed that Pt nanoparticles with an average diameter of approximately 3.5 nm were embedded within the Zn porphyrin matrix. The glassy carbon electrode was modified with Nafion-stabilized Pt-Zn porphyrin nanocomposites and used for dehalogenation of carbon tetrachloride, chloroform, pentachlorophenol, chlorobenzene, and hexachlorobenzene as five test models. The Pt-Zn porphyrin nanocomposite-modified electrode exhibited catalytic activity for the reduction of organohalides at -1.0 V versus Ag/AgCl. Raman signatures confirmed the dehalogenation of chlorobenzene by the nanocomposite-modified electrode. The above two aliphatic and three aromatic organohalides had detection limits of 0.5 microM with linearity up to 8 microM. The modified electrode was good for at least 80 repeated measurements of 4 microM chlorobenzene with a storage stability of 1 month at room temperature. The deactivation of the electrode activity was associated with the loss of platinum nanoparticles from the nanocomposite structure.     

Voltammetric sensor for general purpose organohalide detection at picogram per liter concentrations based on a simple collector-generator method

With the aim of producing a general purpose sensor for environmental analysis, we describe a simple and sensitive method for organohalide detection, based on an electrochemical collector-generator process. The sensor consists of four coplanar electrodes contacting a solution volume of 300 microL, containing organohalide. At the first working electrode (a Zn/PTFE composite), the analyte is electrolyzed to liberate halide ions. At the second working electrode (Ag), the halide ions are detected by cathodic stripping voltammetry. Using a preconcentration time of 600 s, with differential pulse voltammetry for stripping, the responses to 1-chloropropane, chloroform, carbon tetrachloride, iodoethane, and bromoethane can be plotted on a common calibration curve, with a detection limit of 0.1 nM (1.3 pg L(-1) or less depending on the organohalide). To the best of our knowledge, this is the lowest reported organohalide detection limit by an electrochemical method and is so far the only general purpose electrochemical method sensitive enough for regulatory requirements. The sensor response was invariant for approximately 40 measurements. Analysis of tap water, spiked with chloroform or carbon tetrachloride, gave recoveries within 1.0-2.6% of the recoveries by the standard GC method.     

Sub-femtomolar electrochemical detection of DNA hybridization based on latex/gold nanoparticle-assisted signal amplification

We report a relatively simple electrostatic method for modifying submicrometer-size latex spheres with gold nanoparticles (AuNPs) based on layer-by-layer modification of the latex by polyelectrolytes. The AuNP coverages for 343- and 501-nm-diameter spheres were 4.0 x 10 (10) +/- 1.3 x 10 (10) and 8.2 x 10 (10) +/- 2.7 x 10 (10) particles cm (-2), respectively, which is an increase of 1 order of magnitude on the previously reported coverage at latex-AuNPs using streptavidin-biotin binding (Kawde, A.N.; Wang, J. Electroanalysis 2004, 16, 101-107). Due to the fact that the AuNPs used here are also of a larger size (mean diameter 15.5 +/- 1.6 nm, cf. 5 nm), this represents an increase of 2 orders of magnitude in the number of Au atoms delivered per sphere. The spheres were attached to DNA probes specific to E. coli and used to detect probe hybridization by dissolution of the AuNPs, followed by measurement of Au (3+) ions by anodic stripping voltammetry (ASV). Use of differential pulse voltammetry for the stripping step, along with optimization of the ASV conditions, enabled a detection limit of 0.5 fM, which is, to the best of our knowledge, equal or lower than previous voltammetric nanoparticle methods for detection of DNA hybridization.     

Ultralong aligned multi-walled carbon nanotube for electrochemical sensing

We have investigated electrochemical sensing properties of electrodes fabricated with ultralong aligned multi-walled carbon nanotube (MWNT) bundles synthesized using water-assisted chemical vapor deposition on aluminum (Al) and iron (Fe) coated silicon wafer with ethylene and argon/hydrogen gas as carbon source and buffer gas respectively. Cyclic voltammograms performed on these electrodes show diffusion-controlled-reversible reaction. The dominance of radial diffusion mass transport at these electrodes was also indicated by sigmoidal-shaped voltammograms obtained at various scan rates. These electrodes were able to sense very low concentration of ascorbic acid (approximately 0.7 microM) and dopamine (approximately 1.87 microM), two model species often used in electro-analysis. The excellent electrochemical properties along with good single species detection ability suggest that these MWNTs are promising electrode materials for developing very sensitive chemical and/or biological sensors.     

Straightforward Immunosensing Platform Based on Graphene Oxide‐Decorated Nanopaper: A Highly Sensitive and Fast Biosensing Approach

Immunoassays are nowadays a crucial tool for diagnostics and drug development. However, they often involve time‐consuming procedures and need at least two antibodies in charge of the capture and detection processes, respectively. This study reports a nanocomposite based on graphene oxide‐coated nanopaper (GONAP) facilitating an advantageous immunosensing platform using a single antibody and without the need for washing steps. The hydrophilic, porous, and photoluminescence‐quenching character of GONAP allows for the adsorption and quenching of photoluminescent quantum dots nanocrystals complexed with antibodies (Ab‐QDs), enabling a ready‐to‐use immunosensing platform. The photoluminescence is recovered upon immunocomplex (antibody‐antigen) formation which embraces a series of interactions (hydrogen bonding, electrostatic, hydrophobic, and Van der Waals interactions) that trigger desorption of the antigen‐Ab‐QD complex from GONAP surface. However, the antigen is then attached onto the GONAP surface by electrostatic interactions leading to a spacer (greater than ≈20 nm) between Ab‐QDs and GONAP and thus hindering nonradiative energy transfer. It is demonstrated that this simple—yet highly sensitive—platform represents a virtually universal immunosensing approach by using small‐sized and big‐sized targets as model analytes, those are, human‐IgG protein and Escherichia coli bacteria. In addition, the assay is proved effective in real matrices analysis, including human serum, poultry meat, and river water. GONAP opens the way to conceptually new paper‐based devices for immunosensing, which are amenable to point of care applications and automated diagnostics.     

A lightweight and secure NFC‐base mobile payment protocol ensuring fair exchange based on a hybrid encryption algorithm with formal verification

During the past few years, many near‐field communication (NFC) mobile payment protocols have been widely used and received more and more attentions. This could be an essential factor for the growth of the world economy and leads to the improvement of the quality of life for human beings. The NFC mobile payment is one prominent approach in allowing m‐commerce to conduct a sales transaction. However, fair exchange and information security are significant concerns in creating trust among the parties participating in the transaction. Many NFC mobile payment protocols have been introduced by researchers. But, most of them still lack some crucial properties of information security and fair exchange, and this can be an obstacle to their uses. In this article, we propose an NFC mobile payment protocol that possesses comprehensive properties of both information security and fair exchange for sales transaction processing. The protocol employs both symmetric and asymmetric encryptions, hash function, and the technique of offline session key generation, in order to improve the security while maintaining the lightweight property. The fairness analysis shows that the proposed protocol is more competent and effective than others. It can resolve any dispute in case one party misbehaves. Finally, the proposed protocol's security has been successfully verified using both Burrows, Abadi and Needham (BAN logic) and the Scyther tool.     

Kinetic and analytical comparison of horseradish peroxidase on bare- and redox-modified single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) were coated first with methylene blue (MB) by noncovalent adsorption and then by horseradish peroxidase (HRP) by cross-linking with glutaraldehyde. The MB-SWNT/HRP composites formed stable films on glassy carbon electrodes. MB was probably present with a coverage of a monolayer or less. The MB voltammetry was consistent with fast electron transfer to a surface-confined species. The presence of HRP did not significantly affect the MB electrochemistry. MB could mediate electron transfer from HRP in the presence of H₂O₂. Cyclic voltammograms of this process were used to determine the rate constants for the reactions of the native ferriperoxidase with H₂O₂ and of the oxyferryl Compound II with the reduced form of MB. For comparison purposes, the rate constant for the direct electrode reduction of the HRP oxyferryl π-cation radical Compound I was determined in MB-free SWNTs. The results indicate a considerably faster regeneration rate for native ferriperoxidase by the mediated reaction than by direct electrochemistry. Using the MB-SWNT/HRP composites, H₂O₂ could be calibrated by amperometry at −0.3 V vs. SCE. The optimized response (at pH 7.0) had a sensitivity of 661.0 μA mM⁻¹ cm⁻² and a limit of detection (3 × S/N) of 0.1 μM.     

Electrocatalytic tetracycline oxidation at a mixed-valent ruthenium oxide--ruthenium cyanide-modified glassy carbon electrode and determination of tetracyclines by liquid chromatography with electrochemical detection

Mixed-valent films of ruthenium oxide-ruthenium cyanide were electrodeposited onto glassy carbon and characterized for the electrocatalytic oxidation of tetracycline. The currents produced by tetracycline were higher than from previously reported electrode modifications or pretreatments. In H(2)SO(4) pH 1.0 + 0.5 M K(2)SO(4), the second-order rate constant for the reaction between tetracycline and the Ru(III/IV) couple of ruthenium oxide was 3 x 10(5) +/- 1 x 10(5) mol(-1) cm(3) s(-1), and the rate of charge diffusion through the films was 4.5 x 10(-7) +/- 3.5 x 10(-7) cm(2) s(-1). Reaction was localized at the film-solution interface. When used as detectors in liquid chromatography (in H(3)PO(4) pH 2.5 + 0.1 M KH(2)PO(4) + 20% CH(3)CN, E = 1.10 V vs SCE), the electrodes gave limits of detection (>3 S/N) of 0.1 ppm for tetracycline and oxytetracycline and 0.5 ppm for doxycycline and chlorotetracycline. These limits were suitable for FDA and Codex Alimentarius guidelines for tetracyclines in food. Recoveries of the four tetracyclines from sea and freshwater shrimp were in the range 73-111%, which was higher or similar to the previously reported recoveries from shrimp.     

Electrochemical sensors for hemoglobin and myoglobin detection based on methylene blue-multiwalled carbon nanotubes nanohybrid-modified glassy carbon electrode

An effective electrochemical sensors for hemoglobin (Hb) and myoglobin (Mb) detection was firstly developed using a simple procedure of self-assembled methylene blue-multiwalled carbon nanotubes (MB-MWNTs) nanohybrid modified on glassy carbon electrode without using any enzymes immobilization. The direct electrochemical and electrocatalytic behaviors of the modified electrode were studied using cyclic voltammetry (CV) and flow injection analysis (FIA) with amperometry. The performance of the sensor was investigated and optimized and the system was evaluated by monitoring Hb and Mb concentrations. The developed MB-MWNTs nanohybrid modified electrode showed excellent electrocatalytic activity for reduction of Hb and Mb with good stability, sensitivity and reproducibility (RSD = 3.05% and 4.5% for 50 successive injections of Hb and Mb, respectively). Under optimal conditions, the catalytic currents are linearly proportional to the concentrations of Hb and Mb in the wide range from 5 nM to 2 μM and 0.1 to 3 μM, and the corresponding detection limits are 1.5 nM and 20 nM (S/N = 3), respectively. This approach provides improved detection limit over other previous works and may provide a novel and efficient platform for the fabrication of sensors for other heme proteins.