ZIF-8-wrapped AgNPs modified with ß-cyclodextrin for sensitive detection of thiacloprid and imidacloprid by SERS technology.

The high efficient surface-enhanced Raman scatterring (SERS) methods to detect thiacloprid and imidacloprid were established using ZIF-8-wrapped Ag nanoparticles (AgNPs) modified with ß-cyclodextrin (ß-CD). The substrate of ZIF-8/ß-CD@AgNPs was characterized by ultraviolet visible spectra (UV-vis), thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). The interaction between the substrate and thiacloprid/imidacloprid was also explored. The optimum measurement conditions were obtained by response surface model based on single-factor experiments. Enhancement factors (EFs) of thiacloprid and imidacloprid were respectively 2.29 × 106 and 2.60 × 106. A good linearity between the scattering intensity and the concentration of thiacloprid/imidacloprid within 3-1000 nmol L-1/6-400 nmol L-1 was established. The interference experiments indicated that the methods had good selectivity. The SERS methods were successfully applied to detect thiacloprid and imidacloprid in several vegetables samples. The recoveries ranged from 95.5 % to 105 % (n = 5). The detection limits (LODs) (S/N = 3) for thiacloprid and imidacloprid were 1.50 and 0.83 nmol L-1, respectively.

Interactions of traditional and biodegradable microplastics with neonicotinoid pesticides.

Neonicotinoid pesticides (NNPs) and microplastics (MPs) are two emerging contaminants in agricultural environment. However, the interaction between MPs (especially biodegradable plastics) and NNPs is currently unclear. Therefore, taking thiacloprid (THI) as an example of NNPs, this study explores the adsorption-desorption process and mechanism of NNPs on MPs (traditional and biodegradable plastics), and analyzed the main factors affecting the adsorption (pH, salinity and dissolved organic matter). In addition, by using diffusive gradients in thin-films device, this study assessed the impact of MPs on the bioavailability of NNPs in soil. The results showed that the maximum adsorption capacity of polyamide 6 (96.49 µg g-1) for THI was greater than that of poly (butylene adipate co-terephthalate) (88.78 µg g-1). Aging increased the adsorption amount of THI (5.53 %-15.8 %) due to the higher specific surface area and reduced contact angle of MPs, but the adsorption mechanism remained unchanged. The desorption amount of THI from MPs in simulated intestinal fluid is 1.30-1.36 times. The MPs in soil alter the distribution of THI in the soil, increasing the bioavailability of THI while inhibiting its degradation. The results highlighted the significance of examining the combined pollution caused by MPs and NNPs.

Acesulfame and other artificial sweeteners in a wastewater treatment plant in Alberta, Canada: Occurrence, degradation, and emission.

Acesulfame (ACE), sucralose (SUC), cyclamate (CYC), and saccharin (SAC) are widely used artificial sweeteners that undergo negligible metabolism in the human body, and thus ubiquitously exist in wastewater treatment plants (WWTPs). Due to their persistence in WWTPs, ACE and SUC are found in natural waters globally. Wastewater samples were collected from the primary influent, primary effluent, secondary effluent, and final effluent of a WWTP in Alberta, Canada between August 2022 and February 2023, and the artificial sweeteners concentrations were measured by LC-MS/MS. Using wastewater-based epidemiology, the daily per capita consumption of ACE in the studied wastewater treatment plant catchment was estimated to be the highest in the world. Similar to other studies, the removal efficiency in WWTP was high for SAC and CYC, but low or even negative for SUC. However, ACE removal remained surprisingly high (>96%), even in the cold Canadian winter months. This result may indicate a further adaptation of microorganisms capable of biodegrading ACE in WWTP. The estimated per capita discharge into the environment of ACE, CYC, and SAC is low in Alberta due to the prevalent utilization of secondary treatment throughout the province, but is 17.4-18.8 times higher in Canada, since only 70.3% of total discharged wastewater in Canada undergoes secondary treatment.

Domesticating aquatic plants in hydroponic systems to demonstrate and advance phytoremediation of the artificial sweetener acesulfame.

Artificial sweeteners (ASs) are ubiquitously detected in the global water system, among which acesulfame (ACE) is an emerging contaminant for its chemical and biological stability and unsatisfying removal by conventional or advanced treatment technologies. Phytoremediation is an effective and sustainable in-situ remediation technology that this study is the first to explore ACE removal by aquatic plants. The emergent plants, Scirpus Validus (S. validus), Phyllostachys heteroclada Oliver (P. heteroclada) and Acorus tatarinowii (A. tatarinowii) showed superior removal capability than eleven floating plants, and demonstrated high phytoremediation efficiencies (PEs) of up to 75 % after 28 d domestication. ACE removal by the three emergent plants increased during domestication, as the PEs after 28 d domestication were 5.6-6.5 times of 7 d domestication. Notably, the half-life of ACE was decreased from 20.0 to 33.1 d to 1.1-3.4 d in the plant-hydroponic system, compared with 481.0-1152.4 d in control water without plants. Moreover, A. tatarinowii demonstrated the highest removal capacity for ACE with 0.37 mg/g fresh biomass weight (FW), higher than S. validus (0.27 mg/g FW) and P. heteroclada (0.20 mg/g FW). It is worth noting that a mass balance analysis demonstrated that plant transpiration and plant uptake account for about 6.72 %-18.54 % and 9.69 %-21.67 % ACE removal, while hydrolysis only accounted for about 4 % and photolysis was negligible. The rest ACE may be used as a carbon source by endophytic bacteria and root microorganisms of plants. In addition, increased temperature, pH, and illumination intensity had a significant effect on phytoremediation. In the selected experimental range, the increase of temperature from 15 °C to 35 °C, illumination intensity from 1500 lx to 6000 lx, and pH from 5 to 9 generally accelerated the PEs of ACE during the domestication process. Though the mechanism still requires further investigation, the results provide scientific and feasible data for removal of ACE from water by diverse plants for the first time, and also revealed insights for in-situ treatment of ACE.

Role of Maspin, CK17 and Ki-67 Immunophenotyping in Diagnosing of Pancreatic Ductal Adenocarcinoma in Endoscopic Ultrasound-Guided Fine Needle Aspiration Cytology.

BACKGROUND AND STUDY AIM: One of the problems in diagnosing pancreatic ductal adenocarcinoma (PDAC) is differentiation between PDAC cells and benign pancreatic tissue cells in cytologic samples. This study aimed to evaluate the usefulness of Maspin, CK17 and Ki-67 immunocytochemistry (ICC) in differentiation between these two groups of cells. MATERIALS AND METHODS: This retrospective study was carried on 80 cases of PDAC and 25 cell blocks of benign pancreatic tissue cells as a control group for evaluation of Maspin, CK17 and Ki-67 ICC. PDAC cases were sampled by endoscopic ultrasound guided fine needle aspiration cytology (EUS-FNAC), while cell blocks of control group were aspirated from benign pancreatic tissues that were obtained from the pancreatic surgically resected specimens. Immunostaining patterns, sensitivity, specificity, positive predictive value (PPV), negative predictive value (NPV) and accuracy of each antibody as well as possible antibody combined panels of these markers in differentiation between the two groups were evaluated. RESULTS: Positive immunoreactivity for Maspin, CK17 and Ki-67 were 92.5%, 80% and 72.5% in PDAC cases, respectively. In contrast to PDAC cases, all the cell blocks of benign pancreatic tissue cells were negative for these markers. Regarding different panels, combined use of Maspin, CK17 and Ki-67 together as a triple test (at least one of them is positive) achieved the highest sensitivity of 98.8%, specificity of 100%, PPV of 100%, NPV of 96.2% and accuracy of 99% in the differentiation between PDAC and benign pancreatic tissue. CONCLUSION: Employing this short panel [Maspin, CK17 and Ki-67] is helpful for better differentiation between PDAC and benign pancreatic tissue.

The Effects of Nonnutritive Sweeteners on the Cariogenic Potential of Oral Microbiome.

Nonnutritive sweeteners (NNSs) are sugar substitutes widely used to reduce the negative health effects of excessive sugar consumption. Dental caries, one of the most prevalent chronic diseases globally, results from a pathogenic biofilm with microecological imbalance and frequent exposure to sugars. Some research has shown that certain NNSs possess less cariogenic potential than sucrose, indicating their putative effect on oral microbiome. To uncover the alterations of acidogenic pathogens and alkali-generating commensals, as well as the biofilm cariogenic potential under the influence of NNSs, we selected four common NNSs (acesulfame-K, aspartame, saccharin, and sucralose) and established single-, dual-, and multispecies in vitro culture model to assess their effects on Streptococcus mutans (S. mutans) and/or Streptococcus sanguinis (S. sanguinis) compared to sucrose with the same sweetness. The results showed that NNSs significantly suppressed the planktonic growth, acid production, and biofilm formation of S. mutans or S. sanguinis compared with sucrose in single-species cultures. Additionally, decreased S. mutans/S. sanguinis ratio, less EPS generation, and higher pH value were observed in dual-species and saliva-derived multispecies biofilms with supplementary NNSs. Collectively, this study demonstrates that NNSs inhibit the cariogenic potential of biofilms by maintaining microbial equilibrium, thus having a promising prospect as anticaries agents.

Establishment of import tolerance for the insecticide thiacloprid in strawberry.

To promote exports, import tolerance (IT) of thiacloprid in strawberry was proposed using the Organization for Economic Cooperation and Development (OECD) maximum residue limit (MRL) calculator after conducting three different field trials. The pre-harvest interval of residual pattern and degradation dynamics of thiacloprid in strawberry were determined using ultra-performance liquid chromatography-tandem mass spectrometry. Samples were extracted with acetonitrile and a mixture of salts and dilution was performed for purification. A six-point matrix-matched calibration curve was constructed which provided excellent linearity with coefficient of determination (R2 ) of 0.9998 or more. Detection and quantification limits were 0.003 and 0.01 mg/kg, respectively. The method was validated in quintuplicate at three different concentrations, which resulted in acceptable recovery ranging from 80.86% to 101.71% with relative standard deviation of 6.50 or less among the three field sites. The developed method was applied to the field-treated sample harvested at different intervals. In the pre-harvest interval trial, the amount of thiacloprid residues ranged from 0.24 to 0.70 mg/kg in field site 1 (Nonsan), 0.16 to 0.50 mg/kg in field site 2 (Sunchang), and 0.36 to 0.50 mg/kg in field site 3 (Sacheon). By contrast, in the degradation trial, the observed residues were 0.03-0.81 mg/kg in field site 1 and 0.02-0.48 mg/kg in field site 2. Consequently, the IT of thiacloprid in strawberry using the OECD MRL calculator was proposed as 2 mg/kg, which is exactly the same as the MRL established by the Republic of Korea. In conclusion, the residue study proposes 2.0 mg/kg as the MRL of thiacloprid in strawberries.

Determination of Neonicotinoid Pesticides in Propolis with Liquid Chromatography Coupled to Tandem Mass Spectrometry.

In this study, a method was developed for the determination of five neonicotinoid pesticides (acetamiprid, clothianidin, imidacloprid, thiacloprid, and thiamethoxam) in propolis. Two sample preparation methods were tested: solid-phase extraction and the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. The identities of analytes were confirmed using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in the selected reaction monitoring mode. Solid-phase extraction resulted in cleaner extracts; therefore, the SPE-LC-MS/MS method was validated according to the SANTE protocol in triplicate at two spiking levels (10 ng/g and 50 ng/g). The average recoveries of analytes ranged from 61% to 101%, except for clothianidin (10-20%). The LOD ranged from 0.2 ng/g to 4.4 ng/g, whereas the LOQ was in the range of 0.8 ng/g-14.7 ng/g. In order to compensate for the matrix effect, matrix-matched calibration was used. Good accuracy (relative error: 1.9-10.4%) and good linearity (R2 > 0.991) were obtained for all compounds. The optimised method was applied to 30 samples: 18 raw propolis and 12 ethanol tinctures. Acetamiprid, imidacloprid, and thiacloprid were detectable in seven samples but were still below the LOQ. This study is the first to report the determination of several neonicotinoid residues in propolis.

Artificial sweeteners in non-alcoholic beverages: Occurrence and exposure estimation of the Portuguese population.

Artificial sweeteners such as acesulfame-potassium (ACE-K). saccharin (SAC), and aspartame (ASP), play a vital role in the food industry. Despite apparent benefits, several studies report adverse reactions on consumers. EFSA is currently re-evaluating several individual sweeteners, including ASP, Ace-K and SAC that shall be completed by 31 December 2020. Our goal was to evaluate, by liquid chromatography with ultraviolet detection (LC-UV), their levels in non-alcoholic beverages from the Portuguese market (soft drinks, sport drinks, energy drinks, and nectars), and estimate the exposure of the Portuguese adolescent/adult population. ACE-K was found in 85.7% of the samples, in mean levels of 97.4 mg/L. ASP and SAC, detected in 37.5% and 33.9% of the samples, were found in averages of 161.5 and 55.0 mg/L, respectively. The maximum limits set for ASP were exceeded in one energy drink. SAC exceeded the maximum permitted level (MPL) level in 3 soft drinks based on tea extracts. In 4 samples SAC was found but not mentioned in the label, and in one of these samples exceeded the MPL. The estimated daily intake (EDI), calculated in mg per kilogram of body weight per day, of ACE-K, SAC and ASP was found to be below the acceptable daily intake (ADI), both for Portuguese adolescents and adult population. Traditional soft drinks accounted for the highest EDIs representing 1.8%, 2.3% and 0.6% for ACE-K, SAC and ASP, respectively, of the ADI. Considering the previous report in Portugal it is observed that the population is currently exposed to a greater amount of artificial sweeteners, which may indicate a trend for more artificial sweeteners' usage in order to reduce sugar intake.

Capillary liquid chromatography as an effective method for the determination of seven neonicotinoid residues in honey samples.

A new analytical method based on capillary liquid chromatography with diode array detection has been developed for the simultaneous quantification of seven neonicotinoid insecticides commercially available (imidacloprid, thiacloprid, clothianidin, thiamethoxam, acetamiprid, nitenpyram, and dinotefuran) in honey samples. The separation was achieved in a Zorbax XDB-C18 column (150 × 0.5 mm id, 5 µm), with a mobile phase consisting of ultrapure water (solvent A) and acetonitrile (solvent B) at a flow rate of 10 µL/min. Capillary column was thermostated at 25°C during the analysis and 254 or 270 nm was established as detection wavelength, depending on the analyte. Furthermore, full loop injection mode (8 µL) was selected, using water as injection solvent. Finally, the optimized method was applied to the analysis of neonicotinoid residues in honey of different floral origins using dispersive liquid-liquid microextraction as sample treatment. Variables affecting the extraction efficiency were optimized, choosing methanol and dichloromethane as dispersive and extraction solvents, respectively. The method was characterized in terms of linearity ( R 2 ≥ 0.9948), repeatability, reproducibility (relative standard deviation below 4.5 and 6.3% respectively), and recoveries (≥80.5%). Detection and quantification limits were lower than 6.6 and 22.0 µg/kg for the studied analytes, respectively.

Appearance of Thiacloprid in the Guttation Liquid of Coated Maize Seeds.

Thiacloprid (TCL) uptake by maize plants that emerge from coated seeds has been investigated and characterized via measurements of the compound in the guttation liquid. TCL levels were determined in the guttation liquid: (a) under field and semi-field conditions, (b) for different maize varieties, (c) applying different dosages, and (d) as affected by cross-contamination between maize seeds via soil. Cross-contamination was described by uptake interactions between seeds coated with TCL and neighboring seeds not coated or coated with other neonicotinoids, e.g., either thiamethoxam (TMX) or clothianidin (CLO). TCL levels remained under 100 µg/mL in the guttation liquid under field conditions, and were quantifiable even on the 39th day after planting of coated seeds. Higher levels up to 188.6 µg/mL were detected in plants grown under semi-field conditions in pots. Levels in the guttation liquid were also found to be influenced by the applied dosages. The uptake of TCL was found to vary for different maize varieties. Appearance of TCL as a cross-contaminant in the guttation liquid of neighboring plants emerging from non-coated maize seeds indicates translocation of the compound via soil. Peak levels of TCL cross-contamination were found to be lower (43.6 µg/mL) than the corresponding levels in the parent maize plants emerging from coated seeds (107.5 µg/mL), but values converge to each other. Similar trends were observed with neighboring seeds coated with other neonicotinoids (TMX or CLO). The translocation rate of TCL and its uptake by other plants seem to be lower than that of TMX or CLO.

[Separation and determination of acesulfame-K in soy sauce by capillary electrophoresis with contactless conductivity detection using liquid-liquid extraction and field-amplified sample injection].

A new method was established for the sensitive determination of artificial synthetic sweetener acesulfame-K in soy sauce by capillary electrophoresis (CE) with field-amplified sample injection (FASI)and capacitively coupled contactless conductivity detection (C4D). Liquid-liquid extraction (LLE) technology was employed to eliminate the complex matrix interference co-existing in soy sauce. Ethyl acetate was used as the extraction solution. The pH of the sample solution was adjusted to 1.7, and both inorganic salts and organic compounds causing interferences were effectively removed by LLE. The type and volume of the extraction solvents, pH of the sample solutions, extraction method and extraction time were investigated in detail. Under the optimized experimental conditions, acesulfame-K in soy sauce was well separated and sensitively detected. The limit of detection and limit of quantification were 0.15 mg/kg and 0.48 mg/kg, respectively. The accuracy was tested by spiking acesulfame-K into soy sauce samples, and the recoveries ranged from 92.3% to 108.1%. The relative standard deviations were below 8.0%. The proposed method can meet the requirements for the fast screening and sensitive detection of acesulfame-K in soy sauce samples.

Sucralose and acesulfame as an indicator of domestic wastewater contamination in Wuhan surface water.

Artificial sweeteners (ASs) are applied widely as sucrose substitutes in food, pharmaceuticals, and personal-care products, which results in their release into surface water. The occurrence of ASs in aquatic environments in China has rarely been reported. In this study, we determined the concentration of seven ASs in surface water and sediment samples from 16 lakes in Wuhan. The sum of the ASs concentration ranged from 0.89 to 20.6 µg/L in the surface water, with a mean value of 4.96 ± 5.16 µg/L. The most abundant AS was sucralose (SUC), with a concentration from 0.33 to 18.0 µg/L, followed by acesulfame (ACE) (0.40-2.78 µg/L), saccharin (SAC) (

FTIR spectroscopy coupled with machine learning approaches as a rapid tool for identification and quantification of artificial sweeteners.

Fourier transform infrared (FTIR) spectroscopy calibrations were developed to simultaneously determine the multianalytes of five artificial sweeteners, including sodium cyclamate, sucralose, sodium saccharin, acesulfame-K and aspartame. By combining the pretreatment of the spectrum and principal component analysis, 131 feature wavenumbers were extracted from the full spectral range for modelling to qualitative and quantitative analysis. Compared to random forest, k nearest neighbour and linear discriminant analysis, support vector machine model had better predictivity, indicating the most effective identification performance. Furthermore, multivariate calibration models based on partial least squares regression were constructed for quantifying any combinations of the five artificial sweeteners, and validated by prediction data sets. As shown by the good agreement between the proposed method and the reference HPLC for the determination of the sweeteners in beverage samples, a promising and rapid tool based on FTIR spectroscopy, coupled with chemometrics, has been performed to identify and objectively quantify artificial sweeteners.

Nanoantenna enhanced terahertz interaction of biomolecules.

Terahertz time-domain spectroscopy (THz-TDS) is a non-invasive, non-contact and label-free technique for biological and chemical sensing as THz-spectra are less energetic and lie in the characteristic vibration frequency regime of proteins and DNA molecules. However, THz-TDS is less sensitive for the detection of micro-organisms of size equal to or less than λ/100 (where, λ is the wavelength of the incident THz wave), and molecules in extremely low concentration solutions (like, a few femtomolar). After successful high-throughput fabrication of nanostructures, nanoantennas were found to be indispensable in enhancing the sensitivity of conventional THz-TDS. These nanostructures lead to strong THz field enhancement when in resonance with the absorption spectrum of absorptive molecules, causing significant changes in the magnitude of the transmission spectrum, therefore, enhancing the sensitivity and allowing the detection of molecules and biomaterials in extremely low concentration solutions. Herein, we review the recent developments in ultra-sensitive and selective nanogap biosensors. We have also provided an in-depth review of various high-throughput nanofabrication techniques. We also discussed the physics behind the field enhancements in the sub-skin depth as well as sub-nanometer sized nanogaps. We introduce finite-difference time-domain (FDTD) and molecular dynamics (MD) simulation tools to study THz biomolecular interactions. Finally, we provide a comprehensive account of nanoantenna enhanced sensing of viruses (like, H1N1) and biomolecules such as artificial sweeteners which are addictive and carcinogenic.

Competitive immunoassay for simultaneous detection of imidacloprid and thiacloprid by upconversion nanoparticles and magnetic nanoparticles.

A rapid and sensitive immunoassay for the simultaneous detection of imidacloprid and thiacloprid was developed by using magnetic nanoparticles (MNPs) and upconversion nanoparticles (UCNPs). The UCNPs of NaYF4:Yb, Er and NaYF4:Yb, Tm were synthesized and conjugated with anti-imidacloprid monoclonal antibody (mAb) and anti-thiacloprid mAb as signal labels, while the MNPs were conjugated with antigens of thiacloprid and imidacloprid as separation elements. The fluorescence intensities of Yb/Er- and Yb/Tm-doped UCNPs were detected simultaneously in 544 nm and 477 nm under the excitation of NIR light (980 nm). The amounts of mAb-conjugated UCNPs that were separated by antigen-conjugated MNPs were determined based on competitive immunoassays. Under the optimal conditions, the 50% inhibiting concentration (IC50) and limit of detection (LOD, IC10) were 5.80 and 0.32 ng/mL for imidacloprid and 6.45 and 0.61 ng/mL for thiacloprid, respectively. The immunoassay exhibited negligible cross-reactivity with analogs of imidacloprid and thiacloprid except imidaclothiz (86.2%). The average recoveries of imidacloprid and thiacloprid in environmental and agricultural samples, including paddy water, soil, pears, oranges, cucumbers, and wheat, ranged from 78.4 to 105.9% with relative standard deviations (RSDs) of 2.1-11.9% for imidacloprid and ranged from 82.5 to 102.3% with RSDs of 1.0-16.5% for thiacloprid. In addition, the results of the immunoassay correlated well with high-performance liquid chromatography for the detection of the authentic samples.

Occurrence and distribution of neonicotinoid insecticides in surface water and sediment of the Guangzhou section of the Pearl River, South China.

Little information is available about the occurrence of neonicotinoid insecticides in surface water and sediment of the metropolitan regions around the rivers in China. Here we investigate the residual level of neonicotinoids in the Guangzhou section of the Pearl River. At least one or two neonicotinoids was detected in each surface water and sediment, and the total amount of neonicotinoids (∑5neonics) in surface water ranged from 92.6 to 321 ng/L with a geometric mean (GM) of 174 ng/L. Imidacloprid, thiamethoxam and acetamiprid were three frequently detected neonicotinoids (100%) from surface water. As for the sediment, total concentration was varied between 0.40 and 2.59 ng/g dw with a GM of 1.12 ng/g dw, and acetamiprid and thiacloprid were the common sediment neonicotinoids. Western and Front river-route of the Guangzhou section of the Pearl River suffered a higher neonicotinoids contamination than the Rear river-route, resulting from more effluents of WWTPs receiving, and intensive commercial and human activities. Level of residual neonicotinoids in surface water was significantly correlated with the water quality (p < 0.01), especially items of pH, DO and ORP, and nitrogen and phosphorus contaminants. Compared with reports about residual neonicotinoids in water and sediment previously, the metropolitan regions of the Guangzhou could be confronted with a moderate contamination and showed serious ecological threats (even heavier than the Pearl Rivers). Our results will provide valuable data for understanding of neonicotinoids contamination in the Pearl River Delta and be helpful for further assessing environmental risk of neonicotinoids.

Rapid removal of acesulfame potassium by acid-activated ferrate(VI) under mild alkaline conditions.

Acesulfame potassium (ACE) is a widely used artificial sweetener that has consistently been detected in wastewater and surface waters. The high-valent iron-based green oxidant known as ferrate(VI) (potassium ferrate(VI); Fe(VI)) had low reactivity with ACE (i.e. 4 h (or 240 min) contact time removed only ∼ 67% ACE) at a molar ratio of 6.0 ([Fe(VI)]:[ACE]). Comparatively, it took 60 s (or 1 min) to remove ∼94% ACE when HCl (786 µM) was added to a mixture of Fe(VI)-ACE at the same molar ratio of 6.0 (or acid-activated Fe(VI)). Significantly, the final pH (i.e. 7.6-8.1) was similar for Fe(VI) and acid-activated Fe(VI). An empirical model using response surface methodology was developed that could describe reasonably well the removal efficiency of ACE. Inorganic constituents of wastewater (Cl-, Na+, Ca2+, and Mg2+) had no significant effect on the oxidation of ACE by acid-activated Fe(VI). The degradation efficiency of ACE decreased in the presence of 10 mg/L of natural organic matter (NOM) but remained unchanged at 5 mg NOM/L. Sulfamic acid as the oxidized product of ACE was identified by liquid chromatography high resolution mass spectrometry method. Reaction pathways include ring opening of ACE through hydrolytic transformation. Acid-activated Fe(VI) has advantage of rapid removal of ACE under mild alkaline conditions of wastewater treatment plants compared to other oxidation processes such as chlorination, ozonation, and light-based processes.

Environmentally Evaluated New HPLC/UV Method for the Simultaneous Determination of Acesulfame-K, Butylated Hydroxytoluene, and Aspartame and Its Degradant in Chewing Gum.

Background: Acesulfame-K (ACE), butylated hydroxytoluene (BHT), and aspartame (ASP) are a common combination of food additives added to chewing gums. The abuse of these additives results in severe adverse health effects; however, they are still extensively used owing to their high performance and low cost. Objective: The development and optimization of a simple, cheap, sensitive, and eco-friendly HPLC/UV method for the simultaneous determination of ASP, ACE, and BHT along with aspartame degradation product phenylalanine (PHEN) in chewing gum. Methods: The method was optimized using a 5 µm C18 column and an eluent consisting of methanol and 0.1 M phosphate buffer (pH 5.0) according to a suitable gradient elution program. Simple sample preparation, consisting of dilution, homogenization, and sonication followed by centrifugation and filtration, was optimized and used for the extraction of chewing gum. The greenness of the method was evaluated. Results: The proposed method exhibited excellent linearity (R² > 0.9996), low LOQ (0.08-0.95 µg/mL), and recoveries between 85.3 and 98.83% with relative SD (RSD) ≤ 2.7%. High resolution was obtained with <25 min run times with excellent precision (RSD: 0.28-1.33%). This method was successfully applied for the simultaneous determination of ACE, ASP, and BHT in commercial chewing gum; PHEN was not detected. Furthermore, our method is considered to be environmentally acceptable. Conclusions: The results demonstrate that the developed method can be used to detect ACE, BHT, ASP, and PHEN in chewing gum. Highlights: A new sensitive, green HPLC/UV method is developed to be used as a minimal-cost routine analysis procedure for commercial chewing gum.

A versatile HPLC method with an isocratic single mobile phase system for simultaneous determination of anti-glaucoma formulations containing timolol.

Timolol is a non-cardioselective beta blocker and has different combined ophthalmic dosage forms for treatment of glaucoma. This research introduce an HPLC method for the separation of three drugs used in combination with timolol simultaneously by applying isocratic mobile phase system in a single run and the same detection wavelength with short time. The drugs included in the separation procedures are; dorzolamide, brinzolamide, and brimonidine. The HPLC method was carried out through a single mobile phase system, which contains acetonitrile: 0.05M phosphate buffer at the ratio of 30:70, respectively at pH 3.5 and wavelength of 220nm. The method, regarding its simplicity allows determination of the studied drugs simultaneously using single run in about 8minutes. The method was rectilinear in the ranges of concentration: 1.25-25µg/mL for timolol, 4-80µg/mL for dorzolamide, 5-50µg/mL for brinzolamide and 2-20µg/mL for brimonidine. Different factors affecting the separation are thoroughly studied. The developed method was validated based on the official guidelines and the results were compared statistically with previously published methods and showed non-significant difference.