Investigating the synthesis parameters of durian skin-based activated carbon and the effects of silver nanocatalysts on its recyclability in methylene blue removal.

Activated carbon (AC) is the most common and economically viable adsorbent for eliminating toxic organic pollutants, particularly dyes, from wastewater. Its widespread adoption is due to the simplicity and affordable production of AC, wherein low-cost agricultural wastes, such as durian skin can be used. Converting durian skin into AC presents a promising solution for its solid waste management. However, inherent drawbacks such as its non-selectivity, relatively short lifespan and laborious replacement and recovery processes diminish the overall efficacy of AC as an adsorbent. To address these challenges, the immobilisation of metal nanocatalysts such as silver nanoparticles (AgNPs) is one of the emerging solutions. AgNPs can facilitate the regeneration of the adsorption sites of AC by catalysing the conversion of the adsorbed dyes into harmless and simpler molecules. Nevertheless, the immobilisation of AgNPs on AC surface can be challenging as the pore size formation of AC is hard to control and the nanomaterials can easily leach out from the AC surface. Hence, in this study, we synthesised AC from durian skin (DS) and immobilised AgNPs on the AC-DS surface. Then, we used methylene blue (MB) removal for studying the adsorption capability and recyclability of the AC-DS. In the synthesis of AC-DS, the influences of reaction temperature, activating agent, and acid-washing to its capability in adsorptive removal of  MB in solution were first determined. It was found that 400 °C, KOH activating agent, and the presence of acid-washing (50% of HNO3) resulted in AC-DS with the highest percentage of MB removal (91.49 ± 2.86%). Then, the overall results from three recyclability experiments demonstrate that AC-DS with immobilised AgNPs exhibited higher MB removal after several cycles (up to 6 cycles) as compared to AC-DS alone, proving the benefit of AgNPs for the recyclability of AC-DS. We also found that AgNPs/Citrate@AC-DS exhibited better adsorption capability and recyclability as compared to AgNPs/PVP@AC-DS indicating significant influences of type of stabilisers in this study. This study also demonstrates that the presence of more oxygen-containing functional groups (i.e., carboxyl and hydroxyl functional groups) after acid-washing on AC-DS and in citrate molecules, has greater influence to the performance of AC-DS and AgNPs/Citrate@AC-DS in the removal of MB as compared to the influences of their BET surface area and pore structure. The findings in this study have the potential to promote and serve as a guideline for harnessing the advantages of nanomaterials, such as AgNPs, to enhance the properties of AC for environmental applications.

Alginate and alginate composites for biomedical applications.

Alginate is an edible heteropolysaccharide that abundantly available in the brown seaweed and the capsule of bacteria such as Azotobacter sp. and Pseudomonas sp. Owing to alginate gel forming capability, it is widely used in food, textile and paper industries; and to a lesser extent in biomedical applications as biomaterial to promote wound healing and tissue regeneration. This is evident from the rising use of alginate-based dressing for heavily exuding wound and their mass availability in the market nowadays. However, alginate also has limitation. When in contact with physiological environment, alginate could gelate into softer structure, consequently limits its potential in the soft tissue regeneration and becomes inappropriate for the usage related to load bearing body parts. To cater this problem, wide range of materials have been added to alginate structure, producing sturdy composite materials. For instance, the incorporation of adhesive peptide and natural polymer or synthetic polymer to alginate moieties creates an improved composite material, which not only possesses better mechanical properties compared to native alginate, but also grants additional healing capability and promote better tissue regeneration. In addition, drug release kinetic and cell viability can be further improved when alginate composite is used as encapsulating agent. In this review, preparation of alginate and alginate composite in various forms (fibre, bead, hydrogel, and 3D-printed matrices) used for biomedical application is described first, followed by the discussion of latest trend related to alginate composite utilization in wound dressing, drug delivery, and tissue engineering applications.

Electrospray Ionization Mass Spectrometry: A Powerful Platform for Noble-Metal Nanocluster Analysis.

Electrospray ionization mass spectrometry (ESI-MS) is an analytical technique that measures the mass of a sample through "soft" ionization. Recent years have witnessed a rapid growth of its application in noble-metal nanocluster (NC) analysis. ESI-MS is able to provide the mass of a noble-metal NC analyte for the analysis of their composition (n, m, q values in a general formula [Mn Lm ]q ), which is crucial in understanding their properties. This review attempts to present various developed techniques for the determination of the composition of noble metal NCs by ESI-MS. Additionally, advanced applications that use ESI-MS to further understand the reaction mechanism, complexation behavior, and structure of noble metal NCs are introduced. From the comprehensive applications of ESI-MS on noble-metal NCs, more possibilities in nanochemistry can be opened up by this powerful technique.

Hydride-induced ligand dynamic and structural transformation of gold nanoclusters during a catalytic reaction.

Quasi-homogeneous ligand-protected gold nanoclusters (Au NCs) with atomic precision and well-defined structure offer great opportunity for exploring the catalytic nature of nanogold catalysts at a molecular level. Herein, using real-time electrospray ionization mass spectrometry (ESI-MS), we have successfully identified the desorption and re-adsorption of p-mercaptobenzoic acid (p-MBA) ligands from Au25(p-MBA)18 NC catalysts during the hydrogenation of 4-nitrophenol in solution. This ligand dynamic (desorption and re-adsorption) would initiate structural transformation of Au25(p-MBA)18 NC catalysts during the reaction, forming a mixture of smaller Au NCs (Au23(p-MBA)16 as the major species) at the beginning of catalytic reaction, which could further be transformed into larger Au NCs (Au26(p-MBA)19 as the major species). The adsorption of hydrides (from NaBH4) is identified as the determining factor that could induce the ligand dynamic and structural transformation of NC catalysts. This study provides fundamental insights into the catalytic nature of Au NCs, including catalytic mechanism, active species and stability of Au NC catalysts during a catalytic reaction.

Tuning the Accessibility and Activity of Au25 (SR)18 Nanocluster Catalysts through Ligand Engineering.

In this work, the effects of thiolate ligands (-SR, e.g., chain length and functional moiety) on the accessibility and catalytic activity of thiolate-protected gold nanoclusters (e.g., Au25 (SR)18 ) for 4-nitrophenol hydrogenation is reported. The data suggest that Au25 (SR)18 bearing a shorter alkyl chain shows a better accessibility to the substrates (shown by shorter induction time, t0 ) and a higher catalytic activity (shown by higher apparent reaction rate constant, kapp ). The functional moiety of the ligands is another determinant factor, which clearly suggests that ligand engineering of Au25 (SR)18 would be an efficient platform for fine-tuning its catalytic properties.

Evaluation of solvent system for the enzymatic synthesis of ethanol-based biodiesel from sludge palm oil (SPO).

A green technology of biodiesel production focuses on the use of enzymes as the catalyst. In enzymatic biodiesel synthesis, suitable solvent system is very essential to reduce the inhibition effects of the solvent to the enzymes. This study produced ethanol-based biodiesel from a low-cost sludge palm oil (SPO) using locally-produced Candida cylindracea lipase from fermentation of palm oil mill effluent (POME) based medium. The optimum levels of ethanol-to-SPO molar ratio and enzyme loading were found to be 4:1 and 10 U/25 g of SPO respectively with 54.4% w/w SPO yield of biodiesel and 21.7% conversion of free fatty acid (FFA) into biodiesel. Addition of tert-butanol at 2:1 tert-butanol-to-SPO molar ratio into the ethanol-solvent system increased the yield of biodiesel to 71.6% w/w SPO and conversion of FFA into biodiesel to 28.8%. The SPO and ethanol have promising potential for the production of renewable biodiesel using enzymatic-catalyzed esterification and transesterification.