Biodegradable film of carboxymethyl cellulose modified with red onion peel powder waste and boron nitride nanoparticles: Investigation of physicochemical properties and release of active substances.

The aim of this study was to modify carboxymethyl cellulose (CMC) films with onion peel extract (OPE) (0-2 g), onion peel powder (OPP) (0-2 g) and boron nitride nanoparticles (BN) (0-100 mg). 17 different CMC/OPE/OPP/BN films were provided and the physicochemical properties of films were studied. The release of active compounds of the composite film was investigated over time. The obtained results showed that OPE, OPP and BN increased the physical resistance and flexibility of the films. The percentage of moisture and solubility of the films decreased with the increase of OPE, OPP and BN. By adding BN, OPE and OPP, the structure of the film became stronger and the permeability to water vapor decreased. Addition of OPE and OPP significantly increased the antioxidant property of the film. In general, it can be said that the antioxidant substances of the onion peel are protected inside the film by preparing a CMC/OPE/OPP/BN film, which, in addition to stabilizing the antioxidants, can play an effective role in the controlled release of these antioxidant substances.

Microwave-assisted extraction of antioxidant compounds from by-products of Turkish hazelnut (Corylus avellana L.) using natural deep eutectic solvents: Modeling, optimization and phenolic characterization.

An environmentally friendly method using natural deep eutectic solvents (NADES) and microwave-assisted extraction (MAE) for the recovery of bioactive compounds from hazelnut pomace (a hazelnut oil process by-product) was developed to contribute to their sustainable valorization. Eight different NADES were prepared for the extraction of antioxidant constituents from hazelnut pomace, and choline chloride:1,2-propylene glycol (CC-PG) was determined as the most suitable NADES, considering their extraction efficiency and physicochemical properties. After selecting suitable NADES, operational parameters for the MAE process of antioxidants from hazelnut pomace were optimized and modeled using response surface methodology. For the highest recovery of antioxidants, the operational parameters of the MAE process were found to be 24% water, 38 min, 92 °C and 18 mL/0.1 g-DS. Under optimized conditions, extracts of both pomace as a by-product and unprocessed hazelnut flours of three different hazelnut samples (Tombul, Çakildak, and Palaz) were prepared, and their antioxidant capacities were evaluated by spectrophotometric methods. Antioxidant capacities of CC-PG extracts of all hazelnut samples were 2-3 times higher than those of ethanolic extracts. In addition, phenolic characterization of the prepared extracts was carried out using the UPLC-PDA-ESI-MS/MS system. The results of this study suggest that hazelnut by-products can potentially be considered an important and readily available source of natural antioxidants. Furthermore, the modeled MAE procedure has the potential to create an effective and sustainable alternative for pharmaceutical and food industries.

Fluorescence turn-off sensing of TNT by polyethylenimine capped carbon quantum dots.

In recent years, the determination of 2,4,6-trinitrotoluene (TNT) explosive residues in various matrices has attracted great interest from the perspective of national security and public health. Here, a fluorescent polyethylenimine capped carbon quantum dots (PEI-C-dots) probe was synthesized by a microwave-assisted technique using polyethylenimine and citric acid precursors and used to detect TNT. The sensing mechanism of TNT is based on fluorescence quenching as a result of the donor-acceptor interaction between Meisenheimer anion form of TNT and PEI on the PEI-C-dots surface. The fluorescence quantum yield of the synthesized PEI-C-dots was 54% and the detection limit for TNT was 93 µg/L. It was observed that neither the nitramine group (HMX and RDX) explosives with similar structures nor common soil ions and camouflage agents interfered with the determination of TNT. The interference effect of picric acid was eliminated by removing it with a basic anion exchanger before the determination. This nanosensor allows rapid, simple, selective, and sensitive determination of TNT residues in complex matrices and has the potential to be converted into a kit format.

A Simple Determination of Trinitrotoluene (TNT) Based on Fluorescence Quenching of Rhodamine 110 with FRET Mechanism.

Sensitive and selective detection of nitroaromatic explosives is an important issue in regard to human health, environment, public security and military issues. In this study, a simple and sensitive fluorescence quenching - based assay utilizing Rhodamine 110 as fluorophore probe was developed for the determination of trinitrotoluene (TNT). This sensitive fluorometric method could measure the decrease in fluorescence of Rhodamine 110 (λex = 490 nm, λem = 521 nm) owing to the primary amine groups of Rhodamine 110 (different from other rhodamines) capable of donor-acceptor interaction with TNT. The resulting TNT-amine complex can strongly quench the fluorescence emission of Rhodamine 110 by fluorescence resonance energy transfer (FRET) which occurs as the excited Rhodamine 110 fluorophore (donor) transfers its energy to TNT (acceptor) by non-radiative dipole-dipole interaction. Fluorescence quenching varied linearly with TNT concentration, with LOD and the LOQ of 0.71 and 2.38 mg L- 1 TNT, respectively. Similar explosives, common soil ions, and possible camouflage materials were found not to interfere with the proposed method, offering significant advantages with its easy methodology, low-cost, sensitivity, and rapidity of analysis. FRET mechanism based on dye donor-TNT acceptor interaction.

Redox-based colorimetric sensing of H2O2 after removal of antioxidants with ABTS radical oxidation.

Monitoring and determining H2O2 in many industries, treatment plants and biochemical media is important because of its harmful effects even at low concentrations. This work proposes a redox-based colorimetric sensor for the determination of hydrogen peroxide in the presence of antioxidants which are known interferents causing positive errors. On the other hand, the widely used peroxidase-based methods are interfered by enzyme inhibitors. The proposed method consists of two stages, namely antioxidant removal and H2O2 determination. In the first step, antioxidants were removed simply using ABTS radical (ABTS+) oxidant produced by persulfate. After antioxidant elimination, H2O2 in samples was determined by using the CUPRAC colorimetric sensor. The CUPRAC reagent, copper (II)-neocuproine (Cu(II)-Nc), immobilized on a Nafion persulfonate membrane was used for sensor preparation. The light blue Cu(II)-Nc was reduced by H2O2 to the yellow-orange colored Cu(I)-Nc chelate on the sensor, and the absorbance increase at 450 nm was recorded. The LOD and the LOQ values obtained for H2O2 were 0.33 and 1.10 µM, respectively. The proposed assay was validated in terms of linearity, additivity, precision and recovery. The H2O2 contents of spiked food extracts, synthetic serum and certain commercial products (i.e. food sterilization solution, whitening toothpaste and hair bleaching solution) were found to be comparable to the results of peroxidase-ABTS and titanyl sulfate reference assays. In addition, peroxide-type explosive triacetone triperoxide (TATP) was successfully determined in the presence of amine-type antioxidants. The proposed simple and low-cost assay is not inhibited by environmental agents (heavy metals, pesticides, sulfhydryl agents, etc.) adversely affecting enzymatic methods. It is additionally insensitive to turbidity and colored components of complex samples.

A novel gold nanocluster-based fluorometric biosensor for measuring prooxidant activity with a large Stokes shift.

A chicken egg white protein-protected gold nanocluster (CEW-AuNC) based fluorogenic biosensor, where protein was used as both reducing and protecting agent, was developed to determine the Cu(II)-induced prooxidant activity of natural antioxidants abundant in food and biological samples. Gold nanoclusters, prepared using egg white proteins, exhibited strong fluorescence. The prooxidant activity of the tested antioxidants was indirectly measured by their reducing action on Cu(II) to Cu(I), and the reduced cuprous ion was bound to the thiol groups in the CEW-AuNC structure, causing a decrease in fluorescence intensity. Epicatechin, catechin, epigallocatechin gallate, morin, rutin, quercetin, gallic, chlorogenic, and rosmarinic acids, glutathione, cysteine, N-acetyl cysteine, bilirubin, resveratrol, and α-tocopherol were studied as natural antioxidants. A fluorometric method showing a large Stokes shift with excitation/emission maxima at 360∕640 nm was developed to sensitively measure the decrease in the fluorescence of CEW-AuNC associated with the binding of copper(I) to the protein structure. Total prooxidant activities of the binary, ternary, and quaternary synthetic mixtures and of some food and synthetic serum samples were determined. The biosensor response was statistically compared to that of its spectrophotometric counterpart. This method can be used for the control of the oxidative stability of foods with a prolonged shelf life.

Novel pararosaniline based optical sensor for the determination of sulfite in food extracts.

Sulfite, which is a protective agent in various food industries, also is known as an allergen. Therefore, sulfite content in food must be monitored and controlled. In this context, a novel optical sensor is designed for simple, rapid and sensitive determination of the sulfite content in food samples. Acidified pararosaniline (PRA) hydrochloride reagent in cationic form was immobilized on the surface of the Nafion cation exchanger membrane by electrostatic interactions. In formaldehyde medium, the pale purple PRA-Nafion film was converted to rich purple due to the highly conjugated alkyl amino sulfonic acid formation in the presence of sulfite and the absorbance change at 588 nm was recorded. The proposed optical sensor gave a linear response in a wide concentration range for sulfite. The limit of detection (LOD) and the limit of quantification (LOQ) values obtained for sulfite were 0.084 and 0.280 ppm SO2 equivalent, respectively. The proposed optical sensor was validated in terms of linearity, additivity, precision and recovery parameters. The sulfite contents obtained for real food extracts were found to be comparable to the conventional iodometric titration results (with the exception of highly colored samples containing reducing agents, where iodometry was shown to exhibit a systematic error while the proposed sensor could measure the true value). The proposed optical sensor is insensitive to positive interferences from turbidity and colored components of the sample. Sulfite determination in a complex food matrix can be performed using the rapid, simple and sensitive PRA-based sensor without a need for pre-treatment.

Protein-Protected Gold Nanocluster-Based Biosensor for Determining the Prooxidant Activity of Natural Antioxidant Compounds.

In this work, chicken egg white protein (CEW)-protected gold nanoclusters (CEW-AuNCs) were prepared from CEW and HAuCl4 to measure the Cu(II)-induced prooxidant activity of antioxidant compounds such as epicatechin, epigallocatechin gallate, catechin, rosmarinic acid, resveratrol, ascorbic acid, and glutathione. These compounds reduced Cu(II) to Cu(I), and the latter was mainly bound to thiol groups in the CEW-AuNC structure. As the protein-bound Cu(I) may act as a catalytic center for generating reactive oxygen species, the Cu(II) reducing ability of antioxidants is an indirect measure of their prooxidant potency. The bound Cu(I) may be released with the cuprous-selective ligand neocuproine (Nc), forming the basis of a spectrophotometric method measuring absorbance at 450 nm wavelength of the Cu(I)-Nc chelate. The developed method involved a one-pot synthesis and determination without preseparation and was applied to binary synthetic mixtures of studied antioxidant compounds and to certain herbal plant (green tea, linden, echinacea, and artichoke leaf) extracts to determine the total prooxidant activities. The obtained results were statistically compared with those of the literature Cu(II)-Nc assay using a calcium proteinate-based solid biosensor. The developed biosensor was durable, reliable, easily applicable, and of low cost and wide linear range and could determine the prooxidant activities of natural antioxidant samples with high reproducibility.

Heparin-stabilized gold nanoparticles-based CUPRAC colorimetric sensor for antioxidant capacity measurement.

Sensing of total antioxidant capacity (TAC) as an integrated parameter showing the collective action of various antioxidants is an important challenge in food, biochemical and drug analysis. A novel heparin-stabilized gold nanoparticles (AuNPs)-based 'cupric reducing antioxidant capacity' (CUPRAC) colorimetric sensor was designed for TAC measurement. Heparin, a sulfated polysaccharide, was both the reducing and stabilizing agent for distinct negatively-charged AuNPs synthesis. The stabilized AuNPs were added to the copper(I)-neocuproine (Cu(I)-Nc) solution formed from the reaction of Cu(II)-Nc with antioxidants, and the absorbance of the resulting Cu(I)-Nc-AuNPs (Cu(I)-Nc cationic chelate electrostatically adsorbed on gold nanoparticles) was measured at 455 nm. As opposed to other similar AuNPs-based sensors, the proposed nano-sensor exhibited excellent (1000-fold) tolerance toward inert electrolytes without aggregation. The linear range was wider than that of conventional CUPRAC, with lower LOD (0.2 µM for trolox) and higher molar absorptivity (8.36â€¯× 104 M-1 cm-1 for quercetin). The 'trolox equivalent antioxidant capacity' (TEAC) values and activity order for a number of antioxidants were in accordance with those of the reference CUPRAC assay. Antioxidant additions to black tea extract gave recoveries of 93-97% and RSD 2-6%. This green sensor significantly reduced reagent consumption, and operated in complex food samples with a simple, reliable and robust methodology.