Advancements in effervescent-assisted dispersive micro-solid phase extraction for the analysis of emerging pollutants.

Emerging pollutants pose an increasing threat to the environment and human well-being, requiring substantial progress in analytical methodologies. Dispersive micro-solid phase extraction (µ-dSPE) has proven successful in detecting and measuring these contaminants, particularly in trace quantities. However, challenges persist in achieving a uniform sorbent distribution and efficient separation from the sample matrix. To address these issues, effervescent-assisted dispersive micro-solid phase extraction (EA-µ-dSPE) was developed. This method uses on-site produced carbon dioxide as a dispersing agent, eliminating the need for vortexing or ultrasonication. Due to the sorbent dispersion in the sample solution, the contact surface between the analyte and the sorbent increases, resulting in increased extraction efficiency, reduced extraction time, and promotes of sustainability. Several parameters are critical to the successful execution of this procedure to extract the analytes, including the type and structure of sorbent, composition of dispersing agents, sorbent separation procedure, and type and properties of desorption solvents. The sorbent plays a critical role in successful extraction of emerging pollutants. It is clear that for the extraction of the analyte on the sorbent, proper interaction must be established between the analyte and the sorbent via physical and chemical interactions. This review thoroughly evaluates the underlying principles of the approach, its potential, and the significant advancements that have been documented. It explores the method's capacity to analyse and identify emerging pollutants, emphasising its potential across various sample matrices for enhanced pollutant identification and quantification.

Deep eutectic solvents as sustainable extraction media for extraction of polysaccharides from natural sources: Status, challenges and prospects.

Deep eutectic solvents (DES) emerge as promising alternatives to conventional solvents, offering outstanding extraction capabilities, low toxicity, eco-friendliness, straightforward synthesis procedures, broad applicability, and impressive recyclability. DES are synthesized by combining two or more components through various synthesis procedures, such as heat-assisted mixing/stirring, grinding, freeze drying, and evaporation. Polysaccharides, as abundant natural materials, are highly valued for their biocompatibility, biodegradability, and sustainability. These versatile biopolymers can be derived from various natural sources such as plants, algae, animals, or microorganisms using diverse extraction techniques. This review explores the synthesis procedures of DES, their physicochemical properties, characterization analysis, and their application in polysaccharide extraction. The extraction optimization strategies, parameters affecting DES-based polysaccharide extraction, and separation mechanisms are comprehensively discussed. Additionally, this review provides insights into recently developed molecular guides for DES screening and the utilization of artificial neural networks for optimizing DES-based extraction processes. DES serve as excellent extraction media for polysaccharides from different sources, preserving their functional features. They are utilized both as extraction solvents and as supporting media to enhance the extraction abilities of other solvents. Continued research aims to improve DES-based extraction methods and achieve selective, energy-efficient processes to meet the demands of this expanding field.

Fabrication of Activated Carbon Derived from Glycerin Pitch for Desulfurization of Model Fuel Oil and Electrode Application.

One of the world's challenging energy issues is introducing practical and affordable technology for organosulfur removal in fuel. Adsorptive desulfurization (ADS) can address this issue if highly effective activated carbon (AC) derived from industrial waste with excellent textural properties is used. In this study, the derived ACs from glycerin pitch loaded with P and Fe (AC/P and AC/Fe) were used as adsorbents for the ADS of model fuel oils, such as dibenzothiophene (DBT) at mild operating conditions. Under the optimized experimental conditions, 0.3 g of adsorbent dosage, 60 min reaction time, 30 °C temperature, and pH 4, the maximal DBT removal of 96.28 and 43.64%, respectively, for AC/P and AC/Fe was realized. The results indicated that the phosphorus-doped AC/P increases the selectivity of the ADS mechanism for DBT removal. Kinetic investigations disclosed that the adsorption process follows second-pseudo-order kinetics and the Langmuir adsorption isotherm model. The adsorbents remained active for five successive reuses, indicating their robust real-world applications. The electrochemical properties of the fabricated carbon electrodes were analyzed via cyclic voltammetry by coating the ACs with polytetrafluoroethylene (PTFE) as a binder. The transition-metal-doped AC/Fe, though exhibiting 5 times lower surface area, showed the highest specific capacitance at a scan rate of 5 mVs-1 (0.65 µF cm-2). Similarly, the extended AC:PTFE capacitor at a 10% binder ratio offered the maximum capacitance value (1.13 µF cm-2). The synthesized ACs demonstrated potential application as an electrode material, and hence glycerin pitch could be a low-cost precursor to improve the feasibility of commercial production of AC.

Sampling and Sample Preparation Techniques for the Analysis of Organophosphorus Pesticides in Soil Matrices.

Despite organophosphorus pesticides (OPPs) benefits in controlling vector-borne diseases and noxious insects, the bioaccumulation and persistence in the soil system may metamorphose into new substances which could pose a serious threat to the ecosystems and human health. The generally low levels of OPPs residues and often the complexity of the soil matrix are the issues that researcher must deal with. Thus, it is essential to isolate and preconcentrate the OPPs from the matrix to reduce interference effects to obtain a reliable detection. Researchers have reported sample preparation techniques as a promising approach to improve analytical measurement of merits including recovery, precision, linearity, limit of detection, and limit of quantification. Under the selected conditions, limits of detection range between 0.001 and 143 ng/mL, and extraction recovery range between 5 and 154% were obtained. This review evaluates the challenges and opportunities, emphasizes the prospects of sampling techniques and various (micro)extraction coupled with chromatographic methods in different soil samples. Based on the finding, the extraction efficiency depended largely on the interaction between OPPs and extraction media. The fate, migration, toxicity impact, sampling procedure, and storage which influenced the sample preparation were comprehensively discussed.

Sodium Alginate/ß-Cyclodextrin Reinforced Carbon Nanotubes Hydrogel as Alternative Adsorbent for Nickel(II) Metal Ion Removal.

Water pollution issues, particularly those caused by heavy metal ions, have been significantly growing. This paper combined biopolymers such as sodium alginate (SA) and ß-cyclodextrin (ß-CD) to improve adsorption performance with the help of calcium ion as the cross-linked agent. Moreover, the addition of carbon nanotubes (CNTs) into the hybrid hydrogel matrix was examined. The adsorption of nickel(II) was thoroughly compared between pristine sodium alginate/ß-cyclodextrin (SA-ß-CD) and sodium alginate/ß-cyclodextrin immobilized carbon nanotubes (SA-ß-CD/CNTs) hydrogel. Both hydrogels were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) spectral analysis, field emission scanning electron microscopy (FESEM), electron dispersive spectroscopy (EDX), thermogravimetric analysis (TGA) and Brunauer-Emmett-Teller (BET) surface area analysis. The results showed SA-ß-CD/CNTs hydrogel exhibits excellent thermal stability, high specific surface area and large porosity compared with SA-ß-CD hydrogel. Batch experiments were performed to study the effect of several adsorptive variables such as initial concentration, pH, contact time and temperature. The adsorption performance of the prepared SA-ß-CD/CNTs hydrogel was comprehensively reported with maximum percentage removal of up to 79.86% for SA-ß-CD/CNTs and 69.54% for SA-ß-CD. The optimum adsorption conditions were reported when the concentration of Ni(II) solution was maintained at 100 ppm, pH 5, 303 K, and contacted for 120 min with a 1000 mg dosage. The Freundlich isotherm and pseudo-second order kinetic model are the best fits to describe the adsorption behavior. A thermodynamic study was also performed. The probable interaction mechanisms that enable the successful binding of Ni(II) on hydrogels, including electrostatic attraction, ion exchange, surface complexation, coordination binding and host-guest interaction between the cationic sites of Ni(II) on both SA-ß-CD and SA-ß-CD/CNTs hydrogel during the adsorption process, were discussed. The regeneration study also revealed the high efficiency of SA-ß-CD/CNTs hydrogel on four successive cycles compared with SA-ß-CD hydrogel. Therefore, this work signifies SA-ß-CD/CNTs hydrogel has great potential to remove Ni(II) from an aqueous environment compared with SA-ß-CD hydrogel.

Induced sample via transient isotachophoresis mediated with sweeping in micellar electrokinetic chromatography for the dual-stacking strategy of non-steroidal anti-inflammatory drugs in environmental water samples.

Realising the need to devise a simple, sensitive, and reliable detection method, this study investigated the development of a dual-stacking transient isotachophoresis (t-ITP) and sweeping in micellar electrokinetic chromatography with diode array detector (t-ITP/sweeping-MEKC-DAD) for the determination of selected non-steroidal anti-inflammatory drugs (NSAIDs); ketoprofen, diclofenac and naproxen from aqueous matrices. Prior to the system setup, various parameters were optimised to assess the potential use of the t-ITP paired with the sweeping stacking technique in micellar background electrolyte for dual preconcentration and separation of trace amounts of NSAIDs. Once the optimum conditions have been established, the method performance was validated and applied to 17 environmental water samples. Based on the results, the combined t-ITP and sweeping approach significantly improved the stacking and separation sensitivity. A large volume of samples could also be introduced and subsequently separated by MEKC with greater focusing effects due to the sweeping. Under optimised conditions, the developed method exhibited excellent linearity at a high range (0.1-500 ng/mL, r2 ≥ 0.998), low limits of detection (LODs) of 0.01-0.07 ng/mL, and a remarkable relative recovery (RR) of 99.6-101.9% with a relative standard deviation (RSD) of 1.4-8.6% (n = 9). Ultimately, the sensitivity enhancement factors improved up to 666-fold using the optimised method. Therefore, the proposed method presents a simplified yet effective and suitable for the determination of NSAIDs from aqueous matrices.

Antimicrobial and Cytotoxic Effects of Cannabinoids: An Updated Review with Future Perspectives and Current Challenges.

The development of new antibiotics is urgently needed to combat the threat of bacterial resistance. New classes of compounds that have novel properties are urgently needed for the development of effective antimicrobial agents. The extract of Cannabis sativa L. has been used to treat multiple ailments since ancient times. Its bioactivity is largely attributed to the cannabinoids found in its plant. Researchers are currently searching for new anti-infective agents that can treat various infections. Although its phytocannabinoid ingredients have a wide range of medical benefits beyond the treatment of infections, they are primarily associated to psychotropic effects. Different cannabinoids have been demonstrated to be helpful against harmful bacteria, including Gram-positive bacteria. Moreover, combination therapy involving the use of different antibiotics has shown synergism and broad-spectrum activity. The purpose of this review is to gather current data on the actions of Cannabis sativa (C. sativa) extracts and its primary constituents such as terpenes and cannabinoids towards pathogens in order to determine their antimicrobial properties and cytotoxic effects together with current challenges and future perspectives in biomedical application.

Competitive removal mechanism to simultaneously incarcerate bisphenol A, triclosan and 4-tert-octylphenol within beta-cyclodextrin crosslinked citric acid used for encapsulation in polypropylene membrane protected-micro-solid-phase extraction.

Endocrine disrupting compounds (EDCs) are extensively found in the environment and severely impacting human health. In addressing this issue, the beta-cyclodextrin crosslinked citric acid (BCD-CA) had been previously employed in membrane-protected micro-solid phase extraction for sequestering EDCs from water medium; and the findings revealed that BCD-CA possessed a selectivity property. On that account, the potential of BCD-CA towards competitive adsorption of selected EDCs was investigated in terms of adsorption mechanism and selectivity property. Factors that affected the removal efficiencies such as sample pH, sorbent dosage, contact time and initial concentration were evaluated. The characterization results revealed that the carbon percentage of BCD-CA had increased by 2.04%, while the hydrogen percentage had reduced by 1.83%, signifying the successful crosslinking of BCD-CA. Besides, the amount of active BCD was calculated to be 3.2 × 10-7 mol, while the amount of carboxyl group was 2.48 × 10-5 mol per 4 mg of BCD-CA. Moreover, BCD-CA was stable in an aqueous medium with the zeta potential obtained at -36.5 mV and had a high-water retention capacity (∼150%). The competitive adsorption mechanism by BCD-CA with EDCs followed the pseudo-second-order kinetics and Freundlich isotherm, suggesting that the adsorption process was dominated by chemisorption on the heterogeneous surface of the adsorbent. Thermodynamic results revealed that adsorption of 4-tert-octylphenol had the most negative ΔG value, indicating most favorable to be adsorbed by BCD-CA as opposed to triclosan and bisphenol A, which was coherent with the apparent formation constant results. These unique properties manifested the practicality of BCD-CA as a selective adsorbent to detect and remove EDCs from the water medium.

Exploring a novel silicone surfactant-based deep eutectic solvent functionalized magnetic iron particles for the extraction of organophosphorus pesticides in vegetable samples.

The current study discussed the use of silicone surfactant-based deep eutectic solvent as a surface modifier for magnetic iron particles (Fe3O4) to produce a novel adsorbent and its application for the extraction of organophosphorus pesticides (OPPs) in vegetable samples. A deep eutectic solvent (DES) was prepared using low toxic and inexpensive substances such as silicone surfactant (SS) and dodecanoic acid (DoAc). This new eco-friendly SS:DoAc based DES was explored as a substitution to traditional organic reagents for surface modification of Fe3O4 to increase the adsorption capacity and to reduce the matrix interferences, hazardous waste generation and environmental pollution. The newly synthesized SS:DoAc@Fe3O4 adsorbent was successfully characterized and applied in magnetic solid phase extraction (MSPE). Under optimized conditions, the proposed approach exhibited excellent linearity ranging from 0.1 to 200 µg/kg (R2 ≥ 0.9970), low detection limit (0.03-0.1 µg/kg) and acceptable relative recovery (80-119 %) for the studied OPPs.

Evaluation of green silicone surfactant-based vortex assisted dispersive liquid-liquid microextraction for sample preparation of organophosphorus pesticide residues in honey and fruit sample.

A vortex-assisted surfactant enhanced emulsification liquid-liquid microextraction based on non-ionic silicone surfactant was successfully developed for the determination of organophosphorus pesticides in food samples coupled to gas chromatography-mass spectrometry. A new type of non-ionic silicone surfactant composed of polysiloxane chains was employed as a green emulsifier to facilitate the emulsification of extraction solvent into the sample matrix, thereby intensifying the mass transfer of target analytes into the organic phase. The variables that affect the extraction were systematically optimized: 80 µl of hexane and 0.5% (v/v) of silicone surfactant were used as extraction solvent and surfactant respectively, the solution was mixed well under vortex agitation for 1 min with the addition of 4% (w/v) sodium sulfate. Under optimum conditions, the linearity of the method was obtained in the range of 0.1-200 µg/kg with a good coefficient of determination varying from 0.9986 to 0.9996. The limit of detection and the limit of quantitation were between 0.008-0.1 and 0.02-0.3 µg/kg, respectively. Application of the proposed method to real samples gave satisfactory recovery values (80%-118%) for the target analytes. The suggested approach has also proven to be convenient, expeditious, and environmentally benign.

Development of ß-cyclodextrin crosslinked citric acid encapsulated in polypropylene membrane protected-µ-solid-phase extraction device for enhancing the separation and preconcentration of endocrine disruptor compounds.

Endocrine disruptor compounds (EDCs) such as plasticisers, surfactants, pharmaceutical products, personal care products and pesticides are frequently released into the environmental waters. Therefore, a sensitive and environmentally friendly method is entailed to quantify these compounds at their trace level concentrations. This study encapsulated the ß-cyclodextrin crosslinked with citric acid in a polypropylene membrane protected-µ-solid phase extraction (BCD-CA µ-SPE) device for preconcentrating the EDCs (triclosan, triclocarban, 2-phenylphenol, 4-tert-octylphenols and bisphenol A) in real water samples before the analysis by high-performance liquid chromatography. FT-IR and TGA results indicated that BCD-CA was successfully synthesised with the formation of ester linkage (1078.33 cm-1) and O-H stretching from carboxylic acid (3434.70 cm-1) with higher thermal stability as compared with native CD with the remaining weight above 72.1% at 500 °C. Several critical parameters such as the sorbent loading, type and amount of salts, extraction time, sample volume, sample pH, type and volume of desorption solvents and desorption time were sequentially optimised and statistically validated. Under the optimum condition, the use of BCD-CA µ-SPE device had manifested good linearity (0.5-500 µg L-1) with the determination of the coefficient range of 0.9807-0.9979. The p-values for the F-test and t-test (6.60 × 10-8 - 1.77 × 10-5) were lesser than 0.05 and low detection limits ranging from 0.27 to 0.84 µg L-1 for all studied EDCs. The developed technique was also successfully applied for EDC analyses in four distinct real water samples, namely, wastewater, river water, tap water and mineral water, with good EDCs recoveries (80.2%-99.9%), low relative standard deviations (0.1%-3.8%, n = 3) with enrichment factor ranging from 9 to 82 folds. These results signified the potential of the BCD-CA µ-SPE device as an efficient, sensitive, and environmentally friendly approach for analyzing EDCs.

Heavy Metal Concentrations in Malaysian Adults' Hair and Associated Variables in Bukit Mertajam, Penang, Malaysia.

The presence of heavy metals in human hair is being tracked to predict health risk, forensics, and environmental monitoring. Heavy metals are typically non-biodegradable and have a lengthy half-life, allowing them to linger in humans and the environment for many years. Heavy metal exposure in hair has been attributed to multiple sources from the environment and food intake. In this study, copper (Cu), nickel (Ni), zinc (Zn), chromium (Cr), manganese (Mn), lead (Pb), and cadmium (Cd) levels were measured in the scalp hair of 50 individuals in Bukit Mertajam, Penang, Malaysia. In conjunction with sampling, subjects' age, gender, lifestyle, diet, and working environment were also obtained through the questionnaire. The Atomic Absorption Spectrometry (AAS) method was used to extract all the metals in the hair samples. The mean concentrations of heavy metals were found to be in the following order (unit of mg/kg): Cr > Zn > Pb > Ni > Cd > Cu. Manganese was detected below the limit of quantitation among the elements (< LOQ). All elements except Mn were higher and comparable to the previous studies' international limit values. Cadmium prevalence was substantially associated with age, smoking habit, dyed hair, and working environment in Pearson's correlation analysis (p ≤ 0.05). Zinc was also found to be related to the working environment. Some elements were observed to be statistically related between heavy metals, Cd/Zn, Cd/Ni, Cr/Ni, and Pb/Ni, whereas smoking habit/dyed hair and dyed hair/working environment were the associated factors for metal distribution that were statistically correlated (p ≤ 0.05). To recapitulate, this study found that the distribution of heavy metals in hair was influenced by associated factors and between heavy metals. It has been indicated that heavy metal exposure to humans is influenced by factors such as geographical location, lifestyle, and working environment.

Capillary electrophoresis-mass spectrometry analysis of bisphenol A and its analogues in bottled tea beverages with dynamic pH focusing.

A simple and sensitive method for the determination of bisphenol A and its analogues at the ng/mL level in bottled tea beverages is presented. This method utilized a dynamic pH junction to focus the analyte into a more concentrated zone, based on the electrophoretic mobility difference of analytes in the sample matrix and background electrolytes in capillary electrophoresis coupled to mass spectrometry (CE-MS). The optimised analyte focusing led to enhanced signal detection with average peak heights for five bisphenols of 53-170 folds higher than conventional injections. Under optimised conditions, the method showed good linearity in the range of 0.1-100 ng/mL, excellent limits of detection (0.03-0.04 ng/mL), good analyte recovery (80.3-118.1%) with acceptable relative standard deviations (<12%). The limits of quantifications were below the maximum permissible content of bisphenol A set by the European Commission for this product. This method was used to quantitatively analyse bisphenols in six different kinds of bottled tea beverages, making it a promising tool for practical applications.

Simultaneous preconcentration and determination of sulfonamide antibiotics in milk and yoghurt by dynamic pH junction focusing coupled with capillary electrophoresis.

A dynamic pH junction was used in capillary electrophoresis (CE-DAD) to on-line preconcentrate, separate, and determine trace amounts of sulfonamide antibiotics (SAs) in milk and yoghurt samples in this study. A sample matrix with 0.15% acetic acid and 10% methanol (MeOH) at a pH of 4.0, and a background electrolyte (BGE) that contained 35 mM sodium citrate with 10% MeOH at a pH of 8.5, and an acidic barrage of 0.4% acetic acid with 10% MeOH at a pH of 2.5 were utilised to achieve a stacking effect for SAs through a dynamic pH junction. Under optimised conditions, the proposed preconcentration method showed good linearity (30-500 ng/mL, r2 ≥ 0.9940), low limits of detection (LODs) of 4.1-6.3 ng/mL, and acceptable analytes recovery (81.2-106.9%) with relative standard deviations (RSDs) within 5.3-13.7 (n = 9). The limits of quantification (LOQs) were below the maximum residue limit approved by the European Union (EU) in this type of matrices. Sensitivity enhancement factors of up to 129 were reached with the optimised dynamic pH junction using CE with a diode array detector (DAD). The method was used to determine SAs in fresh milk, low-fat milk, full-cream milk, and yoghurt samples.

Catalytic oxidative desulfurisation over Co/Fe-γAl2O3 catalyst: performance, characterisation and computational study.

The world faces the challenge to produce ultra-low sulfur diesel with low-cost technology. Therefore, this research emphasised on production of low sulfur fuel utilising nanoparticle catalyst under mild condition. A small amount of cobalt oxide (10-30 wt%) was introduced into the Fe/Al2O3 catalyst through the wet impregnation method. Cobalt modification induces a positive effect on the performance of the iron catalyst. Hence, the insertion of cobalt species into Fe/Al2O3 led to the formation of lattice fringes in all directions which resulted in the formation of Co3O4 and Fe3O4 species. The optimised catalyst, Co/Fe-Al2O3, calcined at 400 °C with a dopant ratio of 10:90 indicating the highest desulfurisation activity by removing 96% of thiophene, 100% of dibenzothiophene (DBT) and 92% of 4,6-dimethyl dibenzothiophene (4,6-DMDBT). Based on the density functional theory (DFT) on Co/Fe-Al2O3, two pathways with the overall energy of -40.78 eV were suggested for the complete oxidation of DBT.

Exploring a novel deep eutectic solvents combined with vortex assisted dispersive liquid-liquid microextraction and its toxicity for organophosphorus pesticides analysis from honey and fruit samples.

A novel deep eutectic solvents (DES) was successfully applied as an emulsifier in vortex assisted liquid-liquid microextraction (VALLME) coupled with gas chromatography-mass spectrometry for the determination of organophosphorus pesticides in honey and fruit samples. Based on the result of toxicity study, DES provides new opportunities for the safe delivery and application. The predominant parameters affecting extraction efficiency were thoroughly optimized and studied in detail. Under optimum parameters, the calibration curve was determined in the concentration range of 0.1 to 200 µgL-1 with excellent determination coefficients values of 0.9989 to 0.9999. Limit of detection and limit of quantification were found to be 0.01 - 0.09 µgL-1 and 0.03 - 0.2 µgL-1, respectively. Application of the developed method to honey and fruit samples gave acceptable recovery values 83 - 109% with relative standard deviation below than 9.5%. The suggested approach has also proven to be simple, cost-effective, rapid, and non-toxic in nature.

Solid-Phase Extraction of Active Compounds from Natural Products by Molecularly Imprinted Polymers: Synthesis and Extraction Parameters.

Molecularly imprinted polymers (MIPs) are synthetic polymers with a predetermined selectivity for a particular analyte or group of structurally related compounds, making them ideal materials for separation processes. Hence, in sample preparation, MIPs are chosen as an excellent material to provide selectivity. Moreover, its use in solid-phase extraction, also referred to as molecular imprinted solid phase extraction (MISPE), is well regarded. In recent years, many papers have been published addressing the utilization of MIPs or MISPE as sorbents in natural product applications, such as synthesis. This review describes the synthesis and characterization of MIPs as a tool in natural product applications.

Biogenic Silver Nanoparticles of Clinacanthus nutans as Antioxidant with Antimicrobial and Cytotoxic Effects.

Silver nanoparticles (AgNPs) previously synthesised using leaf (AgNP-L) and stem (AgNP-S) extracts of Clinacanthus nutans (C. nutans) were tested to evaluate antimicrobial, antioxidant, and cytotoxicity activities. The AgNPs showed good inhibition against bacteria, but not fungi. The inhibition results showed the highest activity against Staphylococcus aureus (S. aureus) with 11.35 mm (AgNP-L) and 11.52 mm (AgNP-S), while the lowest inhibition was against Escherichia coli (E. coli) with 9.22 mm (AgNP-L) and 9.25 mm (AgNP-S) in the disc diffusion method. The same trend of results was noted in the well diffusion method. The IC50 of AgNP-L and AgNP-S in 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) assays was 417.05 µg/mL and 434.60 µg/mL, as well as 304.31 µg/mL and 326.83 µg/mL, respectively. Ferric reducing power (FRAP) assay showed that AgNP-L [872.389 µmol/L Fe(II)] and AgNP-S [612.770 µmol/L Fe(II)] exhibited significantly (p < 0.05) greater antioxidant activities than leaf extract (CNL) [152.260 µmol/L Fe(II)] and stem extract (CNS) [110.445 µmol/L Fe(II)] of C. nutans. The AgNPs were also proven to possess cytotoxic effects on the breast (MCF-7), cervical (HeLa), and colon (HT-29) cancer cells in a dose-dependent manner. AgNP-S and AgNP-L showed significantly (p < 0.05) higher cytotoxicity against MCF-7 (117.43 µg/mL) and HT-29 (78.47 µg/mL), respectively. In conclusion, the biosynthesised AgNPs from aqueous extract leaves and stem of C. nutans have demonstrated promising potential towards antioxidant, antimicrobial, and cytotoxicity activities.

Deep eutectic solvent-based emulsification liquid-liquid microextraction for the analysis of phenoxy acid herbicides in paddy field water samples.

An emulsification liquid-liquid microextraction (ELLME) method was successfully developed using phenolic-based deep eutectic solvent (DES) as an extraction solvent for the determination of phenoxy acid herbicides, 3,6-dichloro-2-methoxybenzoic acid (dicamba) and 2-methyl-4-chlorophenoxyacetic acid (MCPA) in environmental water samples. Five different phenolics-based DESs were successfully synthesized by using phenol (DES 1), 2-chlorophenol (DES 2), 3-chlorophenol (DES 3), 4-chlorophenol (DES 4) and 3,4-dichlorophenol (DES 6) as the hydrogen-bond donor (HBD) and choline chloride as the hydrogen-bond acceptor (HBA). The DESs were mixed at 1 : 2 ratio. A homogeneous solution (clear solution) was observed upon the completion of successful synthesis. The synthesized DESs were characterized by using Fourier transform infrared and nuclear magnetic resonance (NMR). Under optimum ELLME conditions (50 µl of DES 2 as extraction solvent; 100 µl of THF as emulsifier solvent; pH 2; extraction time 5 min), enrichment factor obtained for dicamba and MCPA were 43.1 and 59.7, respectively. The limit of detection and limit of quantification obtained for dicamba were 1.66 and 5.03 µg l-1, respectively, meanwhile for MCPA were 1.69 and 5.12 µg l-1, respectively. The developed ELLME-DES method was applied on paddy field water samples, with extraction recoveries in the range of 79-91% for dicamba and 82-96% for MCPA.

Floating ZnO QDs-Modified TiO2/LLDPE Hybrid Polymer Film for the Effective Photodegradation of Tetracycline under Fluorescent Light Irradiation: Synthesis and Characterisation.

In this work, mesoporous TiO2-modified ZnO quantum dots (QDs) were immobilised on a linear low-density polyethylene (LLDPE) polymer using a solution casting method for the photodegradation of tetracycline (TC) antibiotics under fluorescent light irradiation. Various spectroscopic and microscopic techniques were used to investigate the physicochemical properties of the floating hybrid polymer film catalyst (8%-ZT@LLDPE). The highest removal (89.5%) of TC (40 mg/L) was achieved within 90 min at pH 9 due to enhanced water uptake by the LDDPE film and the surface roughness of the hybrid film. The formation of heterojunctions increased the separation of photogenerated electron-hole pairs. The QDs size-dependent quantum confinement effect leads to the displacement of the conduction band potential of ZnO QDs to more negative energy values than TiO2. The displacement generates more reactive species with higher oxidation ability. The highly stable film photocatalyst can be separated easily and can be repeatedly used up to 8 cycles without significant loss in the photocatalytic ability. The scavenging test indicates that the main species responsible for the photodegradation was O2●-. The proposed photodegradation mechanism of TC was demonstrated in further detail based on the intermediates detected by LC-time-of-flight/mass spectrometry (LC/TOF-MS).