Tautomerism alters the structure and properties of materials, which can be exploited to control their chemical and biological activities. The role of pH-induced tautomerism of polyvinylpyrrolidone (PVP) was determined by measuring the size, stability, and antioxidant and antibacterial properties of microwave synthesized-silver nanoparticles (AgNPs). TEM and XRD analyses confirmed the formation of face-centered cubic silver nanoparticles. PVP stabilized the AgNPs by interaction with the carbonyl or hydroxyl groups depending on the tautomerization under different pH conditions. At pH 4, PVP was stable in the keto tautomer, stabilizing Ag through electron donation of oxygen atoms in the carbonyl group, producing smaller AgNPs with a higher zeta potential. At pH 7 and 9, the enol tautomer PVP stabilized the AgNPs via oxygen atoms in the hydroxyl group, forming large nanoparticles. The keto form of PVP improved the stability and antioxidant and antibacterial properties of AgNPs compared with the enol form. This study also excluded the antioxidant contribution of PVP via hydrogen donation to free radicals. A facile method for controlling the size of AgNPs by adapting the pH-induced tautomerism of PVP that affects their stability and antioxidant and antibacterial activities is thus reported.
To consider silver nanoparticles (AgNPs) as a colorimetric sensor for H2O2 we require investigation of the effects of the homogeneity of the nanoparticle size and morphology on the sensor parameters. Uniformly-sized Ag nanoparticles with diameters of ∼18.8 ± 2.8 nm were produced using microwave irradiation (AgNP1) but non-uniform particles with diameters of ∼71.2 ± 19.4 nm (AgNP2) were formed without microwave irradiation. Microwave synthesis produced AgNP1 with superiority in terms of repeatability, selectivity and sensor stability for up to eight months of storage over AgNP2. AgNP1 exhibited higher sensitivity and detection limits in the working range of 0.01-40000 μM as compared to AgNP2. The application of the AgNP sensor to milk samples provided recovery values of 99.09-100.56% for AgNP1 and 98.18-101.90% for AgNP2. Microwave irradiation resulted in strong and uniform PVP-Ag interactions for isotropic growth into small nanoparticles. Size and morphology uniformity determined the characteristics of the AgNP sensor that can be applied for H2O2 detection in a wide range of concentrations and real-time evaluation, with the potential for industrial applications.
Saponin is a plant-derived chemical with an amphiphilic glycoconjugate structure extracted from sapindaceae plants like Sapindus rarak. This study investigated saponin extract of Sapindus rarak as a natural template for formation of mesoporous zeolite Y. Surface area and mesoporosity of zeolite Y were improved with optimization of Sapindus rarak extract (SRE) concentration (Y-Ln; n = 2, 5, 10 or 15 mL), reaching 216.26 m2 mesoporous area and 0.214 cm3 g-1 mesoporous volume for Y-L10 samples. A different loading of Ni was impregnated onto Y-L10 zeolite to improve Lewis/Brønsted acidity as catalysts in the deoxygenation of Reutealis trisperma oil (RTO) into hydrocarbon fuels. Impregnating 15% Ni on NaY zeolite enhanced Lewis acidity to 0.4556 mmol g-1, producing 48.8% liquid oil with 85.43% degree of deoxygenation. A high selectivity towards C15 and C17 hydrocarbon was analyzed from liquid yield, indicating the contributing factor from Lewis acidity and mesoporosity to enhance deoxygenation and prevent the hydrocracking reaction.
Conversion of red mud (RM) that contains a high level of silica, alumina and iron minerals into heterogenous catalysts, offers a route for the utilization of abundant toxic by-products of bauxite refining. In this study, the conversion of red mud into mesoporous Fe-aluminosilicate produced selective catalysts for the deoxygenation of waste cooking oil to green diesel hydrocarbons. Direct conversion of red mud in the presence cetyltrimethylammonium bromide into Fe-aluminosilicate (RM-CTA) produced a highly mesoporous structure with oligomeric Fe2O3 clusters within the pores. When red mud was treated with citric acid (RM-CA-CTA), a wide distribution of Fe2O3 particles was obtained on the aluminosilicate external surface. TEM analysis showed a well-defined hexagonal mesoporosity of Fe-aluminosilicate obtained from untreated red mud, while the treated red mud produced lower regularity mesopores. RM-CTA exhibits 60% WCO conversion and 83.72% selectivity towards liquid products with 80.44% diesel hydrocarbon (C11-C18) yield. The high selectivity was due to the high acidity of Fe-aluminosilicate to dissociate the C-O bond and the regularity of mesostructure for efficient hydrocarbon diffusion, preventing a cracking reaction.
Vanadia (V2O5)-incorporated fibrous silica-titania (V/FST) catalysts, which were successfully synthesized using a hydrothermal method followed by the impregnation of V2O5. The catalysts were then characterized using numerous techniques, including X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption analyses, ultraviolet-visible diffuse reflectance spectroscopy, Fourier-transform infrared, X-ray photoelectron spectroscopy, and photoluminescence (PL) analyses. The study found that varying the amount of V2O5 (1-10 wt%) had a significant impact on the physicochemical properties of the FST, which in turn improved the photodegradation efficiency of two organic compounds, ciprofloxacin (CIP) and congo red (CR). 5V/FST demonstrated the best performance in degrading 10 mg L-1 of CIP (83%) and CR (100%) at pH 3 using 0.375 g L-1 catalyst under visible light irradiation within 180 min. The highest photoactivity of 5V/FST is mainly due to higher crystallinity and the highest number of V2O5-FST interactions. Furthermore, as demonstrated by PL analysis, the 5V/FST catalyst has the most significant impact on interfacial charge transfer and reduces electron-hole recombination. The photodegradation of both contaminants follows the Langmuir-Hinshelwood pseudo-first-order model, according to the kinetic study. The scavenger investigation demonstrated that hydroxyl radicals and holes dominated species in the system, indicating that the catalyst effectively generated reactive species for pollutant degradation. A possible mechanism was also identified for FST and 5V/FST. Interestingly, V2O5 acts as an electron-hole recombination inhibitor on FST for selective hole oxidation of ciprofloxacin and congo red photodegradation. Finally, the degradation efficiency of the catalyst remained relatively stable even after five cyclic experiments, indicating its potential for long-term use in environmental remediation.