Adsorption-photocatalytic degradation abilities of γ-irradiated chitosan-ZnO-AgNP composite for organic dye removal and antibacterial activity.

We synthesized a γ-irradiated chitosan-ZnO-AgNPs (ICZA) composite by using a simple hydrogels method. We evaluated its adsorption/photocatalytic degradation abilities for the removal of an organic dye and its antibacterial activity. The XRD, SEM, TEM, EDS, and FTIR techniques were used to characterize the obtained samples. Based on the adsorption and degradation of methylene blue (MB) in the dark and under UV light irradiation, the adsorption and the photocatalytic activity of the as-obtained samples were evaluated. The optimum conditions for synthesizing the composite were as follows: contact time of 210 min, a dosage of 2 g/L, MB concentration of 40 mg/L, and a solution pH of 8.0. The ICZA had a high adsorption capacity, which was suitable for removing MB from the aqueous solutions; it showed a maximum adsorption capacity (qm) of 92.59 mg/g. The fit of the adsorption isotherms with the Langmuir model was satisfactory. The photocatalytic degradation ability of the composite was also better than that of other catalysts in the presence of UV light, with an apparent rate constant (kapp) of 3.08 × 10-2. The synthesized ICZA also showed good antibacterial activity against Staphylococcus aureus, with a minimum inhibitory concentration (MIC) and a minimum bactericidal concentration (MBC) of 12.5 g/mL and 50 g/mL under light-incubation and dark-incubation conditions. Finally, we discussed the hypothesized mechanism of the adsorption/photocatalytic activity and antibacterial activity of the ICZA composite in this study.

Photocatalytic degradation of organic dyes on magnetically separable barium hexaferrite as photocatalyst under conditions of visible light irradiation.

In this paper, we present the first attempt to evaluate the role of carboxymethyl cellulose (CMC) as a chelating agent in the sol-gel auto-combustion method of producing barium hexaferrite (BaFe12O19). We also report the application of the system as a photocatalyst for dye degradation. The formation, morphology, and crystalline structure of the synthesized nanoparticles are determined using XRD, SEM, EDS, VSM, FTIR, and TEM techniques. High efficiency under visible light, with a band gap of 1.62 eV and a BET surface of 17.93 m2/g, has been observed for the BaFe12O19 catalyst. The operating parameters, such as reaction time, initial dye concentration, light intensity, reusability, and dye type, are studied. Degradation rates as high as 98.26% (Kapp = 0.082 min-1) and 89.07% (Kapp = 0.0743 min-1) were obtained for cases of methylene blue and malachite green under conditions of visible light irradiations when BaFe12O19 was used. The BaFe12O19 catalyst has been shown to exhibit a high degradation performance for cationic dyes. Furthermore, BaFe12O19 magnetic nanoparticles show excellent reusability for dye degradation because the photocatalyst did not exhibit a significant decrease in its activity even after five runs (81.56%). As a result, the current study confirmed that photocatalytic degradation was a promising technology for saving water and treating wastewater formed from textile dye industries. The technique can be used to study the efficiency of photocatalytic degradation and understand the process of recycling waste effluents under conditions of minimized water use.

Effect of Na and Al doping on ZnO nanoparticles for potential application in sunscreens.

This study investigated the environment-friendly production and characterization of zinc oxide nanoparticles (ZnO NPs) doped with sodium (Na) and aluminum (Al) metals to decrease the photocatalytic activity of ZnO for use in sunscreen. The metal-doped zinc oxide (ZnO) materials were prepared by the microwave method using extracts of Averrhoa carambola, also known as star fruit, as a reducing agent. The effects of metal-ion doping on the crystal structure, morphology, and optical characteristics of ZnO were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX), transmission electron microscopy (TEM), and ultraviolet-visible (UV-Vis) spectroscopy. The sun protection factor (SPF) of the sunscreen formulations containing undoped ZnO, Na-doped ZnO (Na/ZnO), and Al-doped ZnO (Al/ZnO) NPs were found to be 10.10, 25.10, and 43.08, respectively. Therefore, Na/ZnO and Al/ZnO showed increased SPF. Additionally, the prepared nanomaterials and sunscreens were effective against Gram-positive and Gram-negative bacteria and showed antioxidant activities. The methylene blue (MB) degradation was used to evaluate the photocatalytic activities of the undoped ZnO, Na/ZnO, and Al/ZnO NPs, which were found to be 66%, 46%, and 38%, respectively. Therefore, due to the structural defects of ZnO NPs, their photocatalytic activity was decreased with Na- and Al- doping. Additionally, Al/ZnO is an ideal candidate as an ingredient in sunscreens.

Selective Fe(ii)-fluorescence sensor with validated two-consecutive working range using N,S,I-GQDs associated with garlic extract as an auxiliary green chelating agent.

The goal of this work was to use the pyrolysis process to synthesize graphene quantum dots doped with garlic extract (as N,S-GQDs) and simultaneously co-doped with iodine (as I-GQDs). XPS, HR-TEM, FE-SEM/EDX, FT-IR, fluorescence, and UV-visible absorption spectroscopy were used to characterize the N,S,I-GQDs and analyze their morphological images. The quantum yield of N,S,I-GQDs was found to be 45%, greater than that of undoped GQDs (31%). When stimulated at 363 nm, the N,S,I-GQDs display a strong fluorescence intensity at a maximum wavelength of 454 nm. Using N,S,I-GQDs as a fluorescence quenching sensor for screening tests with various metal ions, it was discovered that they are extremely selective towards Fe2+ over Fe3+ and other ions. Thus, solution pH, concentration of N,S,I-GQDs, quantity of garlic extract, EDTA and AgNO3 concentration as masking agents, reaction duration under ultrasonic aid, and tolerable limit of Fe3+ presence in the target analyte were all optimized for Fe2+ detection. A highly sensitive detection of Fe2+ was obtained using a linear curve with y = 141.34x + 5.5855, R 2 = 0.9961, LOD = 0.11 mg L-1, and LOQ = 0.35 mg L-1. The method precision, given as RSDs, was determined to be satisfactory at 1.04% for intra-day analysis and 3.22% for inter-day analysis, respectively. As a result, the selective determination of trace amounts of Fe2+ in real water samples using such labile multi-element doped GQDs in conjunction with garlic extract as a green chelating agent to maintain its enhanced sensitivity was successfully applied with good recoveries ranging from 89.16 to 121.45%.

Microwave-assisted synthesis of Ag/ZnO nanoparticles using Averrhoa carambola fruit extract as the reducing agent and their application in cotton fabrics with antibacterial and UV-protection properties.

This is the first time Averrhoa carambola fruit extract has been used as a reducing agent to synthesize Ag/ZnO composites for coating cotton to develop antibacterial activity and UV protection under domestic microwave irradiation. The effects of the molar concentration of silver nitrate solutions, applied power, reaction duration, and pH on the yield of nanoparticles were determined. The treated fabrics were subjected to the investigation of surface morphology and chemical structure using SEM and EDX techniques, respectively. The antibacterial activity of the ZnO NPs and the Ag/ZnO nanocomposite coated on cotton fabric was evaluated against E. coli and S. aureus using the agar well diffusion method. The results revealed good antibacterial activity in the cotton fabric treated with the Ag-doped ZnO composite. The stability of the Ag/ZnO nanocomposite coated fabrics was determined by a wash durability test, the results of which demonstrated that this fabric could retain good antibacterial activity even after 20 wash cycles. The UV-blocking capacity of the treated fabrics was evaluated based on the ultraviolet protection factor (UPF) value determined in the range of 280-400 nm. The UPF value determined for the Ag/ZnO-coated fabric was 69.67 ± 1.53, which indicated an excellent ability to block UV radiation. Collectively, these results demonstrated the Ag/ZnO nanocomposite prepared in the present study as a promising material for preparing textiles with good antibacterial activity and UV protection.

Ultratrace Detection of Nickel(II) Ions in Water Samples Using Dimethylglyoxime-Doped GQDs as the Induced Metal Complex Nanoparticles by a Resonance Light Scattering Sensor.

This study aimed to synthesize dimethylglyoxime (DMG) (N-source)-doped graphene quantum dots (N-GQDs) via simultaneous pyrolysis of citric acid and 1.0% (w/v) DMG. The maximum excitation wavelength (λmax, ex = 380 nm) of the N-GQD solution (49% quantum yield (QY)) was a red shift with respect to that of bare GQDs (λmax, ex = 365 nm) (46% QY); at the same maximum emission wavelength (λmax, em = 460 nm), their resonance light scattering (RLS) intensity peak was observed at λmax, ex/em = 530/533 nm. FTIR, X-ray photoelectron spectroscopy, XRD, energy-dispersive X-ray spectroscopy, and transmission electron microscopy analyses were performed to examine the synthesized materials. The selective and sensitive detection of Ni2+ using the RLS intensity was performed at 533 nm under the optimum conditions consisting of both 25 mg L-1 N-GQDs and 2.5 mg L-1 DMG in the ammonium buffer solution of pH 9.0. The linearity of Ni2+ was 50.0-200.0 µg L-1 with a regression line, y = 5.031x - 190.4 (r 2 = 0.9948). The limit of detection (LOD) and the limit of quantitation (LOQ) were determined to be 20.0 and 60.0 µg L-1, respectively. The method precision expressed as % RSDs was 4.90 for intraday (n = 3 × 3) and 7.65 for interday (n = 5 × 3). This developed method afforded good recoveries of Ni2+ in a range of 85-108% when spiked with real water samples. Overall, this innovative method illustrated the identification and detection of Ni2+ as a DMG complex with N-GQDs, and the detection was highly sensitive and selective.

A Fluorescence Switching Sensor for Sensitive and Selective Detections of Cyanide and Ferricyanide Using Mercuric Cation-Graphene Quantum Dots.

This study aims to use graphene quantum dots (GQDs) as a fluorescence switching sensor (turn on-off) for the simultaneous detection of cyanide (CN-) and ferricyanide [Fe(CN)6]3- in wastewater samples. The GQDs were synthesized by pyrolyzing solid citric acid. The intrinsic blue color of the solution was observed under ultraviolet irradiation. The fluorescence spectrum was maximized at both excitation and emission wavelengths of 370 and 460 nm, respectively. The fluorescence intensity of GQDs decorated with Hg2+ (turn-off mode as the starting baseline) could be selectively turned on in the presence of CN- and once back to turn-off mode by [Fe(CN)6]3-. The fluorescence switching properties were used to develop a fluorescence turn-on-off sensor that could be used to detect trace amounts of CN- and [Fe(CN)6]3- in water samples. For highly sensitive detection under optimum conditions (Britton-Robinson buffer solution in the pH range of 8.0-9.0, linearity ranges of 5.0-15.0 µM (R 2 = 0.9976) and 10.0-50.0 µM (R 2 = 0.9994), respectively, and detection limits of 3.10 and 9.48 µM, respectively), good recoveries in the ranges of 85.89-112.66% and 84.88-113.92% for CN- and [Fe(CN)6]3-, respectively, were recorded. The developed methods were successfully used for the simultaneous and selective detection of CN- and [Fe(CN)6]3- in wastewater samples obtained from local municipal water reservoirs.

Ultrasound-irradiated synthesis of 3-mercaptopropyl trimethoxysilane-modified hydroxyapatite derived from fish-scale residues followed by ultrasound-assisted organic dyes removal.

We report a novel method for the synthesis of 3-mercaptopropyl trimethoxysilane-modified hydroxyapatite (FHAP-SH) derived from fish-scale residues by using ultrasound irradiation. Scanning electron microscopy, transmission electron microscopy, energy-dispersive spectroscopy, X-ray diffraction, and Fourier transform infrared spectroscopy were used for the FHAP-SH characterization. Then, the organic dye adsorption on the FHAP-SH was monitored through an ultrasound process. After the dye removal optimization, significant improvements were observed in the maximum adsorption capacities for Congo Red (CR, 500 mg g-1), Coomassie Brilliant Blue G 250 (CB, 235 mg g-1), and Malachite Green (MG, 625 mg g-1). The adsorption behaviors of these dyes were fitted by using the Langmuir isotherm model with a high coefficient of determination values ranging from 0.9985 to 0.9969. The adsorption of the three dyes onto FHAP-SH was an endothermic process based on the adsorption thermodynamics model, while the adsorption kinetics analysis of the dyes presented a good alignment with the pseudo-second-order kinetics. The FHAP-SH exhibits a remarkably high adsorption capacity, is inexpensive, and fulfills the ecofriendly requirements of dye wastewater treatment, especially in the textile industry.

Ultrasonic-assisted recycling of Nile tilapia fish scale biowaste into low-cost nano-hydroxyapatite: Ultrasonic-assisted adsorption for Hg2+ removal from aqueous solution followed by "turn-off" fluorescent sensor based on Hg2+-graphene quantum dots.

This study was planned to recycle calcium and the phosphorus-rich Nile tilapia fish scale biowaste into nano-hydroxyapatite (FHAP), using ultrasonic-assisted extraction of calcium and phosphorus from fish scales, which was optimized in term of extraction time, acid concentration, extraction temperature, and ultrasonic power. These two elements were determined simultaneously by inductively coupled plasma atomic emission spectrometry and the FHAP phase was formed upon addition of the extracted element solution in alkaline medium using homogenous precipitation assisted with ultrasound energy. The FHAP adsorbent was characterized by x-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller. A combination of FHAP and the ultrasonic method was then used to remove Hg2+ from aqueous solution. Four significant variables affecting Hg2+ removal, namely, adsorbent dosage, pH, ultrasonic power, and adsorption time, were studied. The results exhibited that the optimal conditions for maximizing the removal of Hg2+ were 0.02 g adsorbent dosage, pH 8, 0.4 kW ultrasonic power, 20 min adsorption time, and 30 °C adsorption temperature. The sorption mechanism of Hg2+ was revealed by isotherm modeling, indicating that FHAP adsorbent has a potential for Hg2+ removal in aqueous media with the maximum adsorption capacity being 227.27 mg g-1. This adsorption behavior is in agreement with the Langmuir model as reflected by a satisfactory R2 value of 0.9967, when the kinetics data were fitted with pseudo-second-order. Therefore, the FHAP could be an alternative adsorbent for the ultrasonic-assisted removal of Hg2+ at very high efficiency and within a very short period of time.

Green and facile synthesis of water-soluble carbon dots from ethanolic shallot extract for chromium ion sensing in milk, fruit juices, and wastewater samples.

Self-functionalized carbon dots (CDs) were prepared from ethanolic shallot extract to obtain a total phenolic precursor. The total phenolic extract was then heated at 180 °C for four hours in an autoclave. Only 1 mg L-1 of CDs had high fluorescence emission at 430 nm after excitation at 340 nm and manifested a high selectivity for Cr(vi) ions. The inter- and intra-day emission stability, pH, ionic strength, solvent effect, Stern-Volmer constant, incubation time, speciation of Cr(iii) and Cr(vi) ions, and ion selectivity of the as-prepared CDs were investigated in detail. The proposed method was validated in 20-100 µM linearity with y = 2.2346x as the set-zero intercept linear equation, 0.9981 as the correlation coefficient, 3.5 µM as the limit of detection (LOD), 11.7 µM as the limit of quantification (LOQ), and 2.78% and 5.29% as the intra-day and inter-day relative standard deviations (RSD), respectively. The recovery of drinking water, milk, soymilk, fruit juices (apple and coconut), tap water, and chromium-coated industrial waste water by the investigated Cr sensor was found to be 78.58-119.69%. Therefore, the proposed Cr(vi) sensor had superior advantages of sensitivity, selectivity, rapidity, and reproducibility.

Resonance light scattering sensor of the metal complex nanoparticles using diethyl dithiocarbamate doped graphene quantum dots for highly Pb(II)-sensitive detection in water sample.

This study was aimed to detect Pb2+ using diethyl dithiocarbamate-doped graphene quantum dots (DDTC-GQDs) based pyrolysis of citric acid. The excitation maximum wavelength (λmax, ex = 337 nm) of the DDTC-GQDs solution was blue shift from bare GQDs (λmax, ex = 365 nm), with the same emission maximum wavelength (λmax, em = 459 nm) indicating differences in the desired N, S matrices decorating in the nanoparticles. Their resonance light scattering intensities were peaked at the same λmax, ex/em = 551/553 nm without any background effect of both ionic strength and masking agent. Under optimal conditions, the linear range was 1.0-10.0 µg L-1 (R2 = 0.9899), limit of detection was 0.8 µg L-1 and limit of quantification was 1.5 µg L-1. The precision, expressed as the relative standard deviations, for intra-day and inter-day analyses was 0.87% and 4.47%, respectively. The recovery study of Pb2+ for real water samples was ranged between 80.8% and 109.5%. The proposed method was also proved with certified water sample containing 60 µg L-1 Pb2+ giving an excellent accuracy and was then implied satisfactorily for ultra-trace determination of Pb2+ in drinking water and tap water samples.

GSH-doped GQDs using citric acid rich-lime oil extract for highly selective and sensitive determination and discrimination of Fe3+ and Fe2+ in the presence of H2O2 by a fluorescence "turn-off" sensor.

Synthesis and characterization of graphene quantum dots (GQDs) simultaneously doped with 1% glutathione (GSH-GQDs) by pyrolysis using citric acid rich-lime oil extract as a starting material. The excitation wavelength (λ max = 337 nm) of the obtained GSH-GQD solution is blue shifted from that of bare GQDs (λ max = 345 nm), with the same emission wavelength (λ max = 430 nm) indicating differences in the desired N and S matrices decorating the carbon based nanoparticles, without any background effect of both ionic strength and masking agent. For highly Fe3+-sensitive detection under optimum conditions, acetate buffer at pH 4.0 in the presence of 50 µM H2O2, the linearity range was 1.0-150 µM (R 2 = 0.9984), giving its calibration curve: y = 34.934x + 169.61. The LOD and LOQ were found to be 0.10 and 0.34 µM, respectively. The method's precisions expressed in terms of RSDs for repeatability (n = 3 × 3 for intra-day analysis) were 2.03 and 3.17% and for reproducibility (n = 5 × 3 for inter-day analysis) were 3.11 and 4.55% for Fe2+ and Fe3+, respectively. The recoveries of the method expressed as the mean percentage (n = 3) were found in the ranges of 100.1-104.1 and 98.08-102.7% for Fe2+ and Fe3+, respectively. The proposed method was then implemented satisfactorily for trace determination of iron speciation in drinking water.

The use of S2O8 2- and H2O2 as novel specific masking agents for highly selective "turn-on" fluorescent switching recognition of CN- and I- based on Hg2+-graphene quantum dots.

In this study, we report that both CN- and I- can enhance the fluorescent intensity of Hg2+-graphene quantum dots (Hg2+-GQDs). However, the selectivity of the sensor was poor. Accordingly, simple specific masking agents can be directly used to solve this problem. Here, for the first time, we report the use of persulfate ion (S2O8 2-) as a turn-on fluorescent probe of Hg2+-GQDs for selective CN- detection, while hydrogen peroxide (H2O2) was selected for its sensing ability towards I- ion detection. Interestingly, the signal was immediately measured after addition of the masking agent to Hg2+-GQDs and the sample because its interaction was very fast and efficient. The method had a linear response in the concentration ranges of 0.5-8 µM (R 2 = 0.9994) and 1-12 µM (R 2 = 0.9998) with detection limits of 0.17 and 0.20 µM for CN- and I-, respectively. The sensor was successfully used for the dual detection of both CN- and I- in real water samples with satisfactory results. In conclusion, the specific masking agents in a Hg2+-GQDs system appeared to be good candidates for fluorometric "turn-on" sensors for CN- and I- with excellent selectivity over other ions.

Fe3O4/hydroxyapatite/graphene quantum dots as a novel nano-sorbent for preconcentration of copper residue in Thai food ingredients: Optimization of ultrasound-assisted magnetic solid phase extraction.

Fe3O4/hydroxyapatite/graphene quantum dots (Fe3O4/HAP/GQDs) nanocomposite was synthesized and used as a novel magnetic adsorbent. This nanocomposite was characterized using scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, and magnetization property. The Fe3O4/HAP/GQDs was applied to pre-concentrate copper residues in Thai food ingredients (so-called "Tom Yum Kung") prior to determination by inductively coupled plasma-atomic emission spectrometry. Based on ultrasound-assisted extraction optimization, various parameters affecting the magnetic solid-phase extraction, such as solution pH, amount of magnetic nanoparticles, adsorption and desorption time, and type of elution solvent and its concentration were evaluated. Under optimal conditions, the linear range was 0.05-1500ngmL-1 (R2>0.999), limit of detection was 0.58ngmL-1, and limit of quantification was 1.94ngmL-1. The precision, expressed as the relative standard deviation of the calibration curve slope (n=5), for intra-day and inter-day analyses was 0.87% and 4.47%, respectively. The recovery study of Cu for real samples was ranged between 83.5% and 104.8%. This approach gave the enrichment factor of 39.2, which guarantees trace analysis of Cu residues. Therefore, Fe3O4/HAP/GQDs can be a potential and suitable candidate for the pre-concentration and separation of Cu from food samples. It can easily be reused after treatment with deionized water.

Preconcentration and trace determination of copper (II) in Thai food recipes using Fe3O4@Chi-GQDs nanocomposites as a new magnetic adsorbent.

This study describes the preparation, characterization, and application of a new magnetic chitosan-graphene quantum dots (Fe3O4@Chi-GQDs) nanocomposite as an adsorbent for the preconcentration of Cu(II) in Thai food recipes or the so-called "Som Tam" (green papaya salad) prior to determination by inductively coupled plasma-optical emission spectrometry. The spectroscopic and magnetic properties along with the morphology and thermal property were analyzed using FTIR, EDX, XRD, TGA, VSM, and TEM. Preconcentration optimizations including pH, dosage of adsorbent, adsorption-desorption time, concentration and volume of elution solvent, sample volume and enrichment factor, and reusing time were investigated. Good linearity was obtained ranging from 0.05 to 1500µgL-1 with correlation coefficient of 0.999. Limit of detection was 0.015µgL-1. Relative recoveries of 85.4-107.5% were satisfactorily obtained. This Fe3O4@Chi-GQDs has high potential to be used as preconcentration method and can be reused 7times with high extraction efficiency.