Search

The present study deals with the assessment of different physicochemical parameters (pH, electrical conductivity (E.C.), turbidity, total dissolved solids (TDS), and dissolved oxygen) in different surface water such as pond, river, and canal water in four different seasons, viz. March, June, September, and December 2023. The research endeavors to assess the impact of a cationic polyelectrolyte, specifically poly(diallyl dimethyl ammonium chloride) (PDADMAC), utilized as a coagulation aid in conjunction with lime for water treatment. Employing a conventional jar test apparatus, turbidity removal from diverse water samples is examined. Furthermore, the samples undergo characterization utilizing X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The study also conducts correlation analyses on various parameters such as electrical conductivity (EC), pH, total dissolved solids (TDS), turbidity of raw water, polyelectrolyte dosage, and percentage of turbidity removal across different water sources. Utilizing the Statistical Package for Social Science (SPSS) software, these analyses aim to establish robust relationships among initial turbidity, temperature, percentage of turbidity removal, dosage of coagulant aid, electrical conductivity, and total dissolved solids (TDS) in pond water, river water, and canal water. A strong positive correlation could be found between the percentage of turbidity removal and the value of initial turbidity of all surface water. However, a negative correlation could be observed between the polyelectrolyte dosage and raw water's turbidity. By elucidating these correlations, the study contributes to a deeper understanding of the effectiveness of PDADMAC and lime in water treatment processes across diverse environmental conditions. This research enhances our comprehension of surface water treatment methodologies and provides valuable insights for optimizing water treatment strategies to address the challenges posed by varying water sources and seasonal fluctuations., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Quaternary ammonium salt bactericides are broad-spectrum bactericides often used in oral care products because of their high antibacterial efficacy, strong penetration, and low toxicity. However, the excessive use of quaternary ammonium salt bactericides may cause contact dermatitis, scalding poisoning, and even death. Existing methods to determine quaternary ammonium salt bactericides are unable to meet current requirements owing to the lack of determination components. Therefore, establishing a simple and accurate method for the simultaneous detection of more quaternary ammonium salt bactericides is necessary. In this study, a method that couples sample pretreatment with high performance liquid chromatography-evaporative light-scattering detection (HPLC-ELSD) was developed for the simultaneous determination of quaternary ammonium salt bactericides in oral care products, including dodecyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, benzethonium chloride, tetradecyl trimethyl ammonium chloride, tetradecyldimethylbenzylammonium chloride, N -hexadecyltrimethylammonium chloride, benzyldimethylhexadecylammonium chloride, trimethylstearylammonium chloride, stearyldimethylbenzylammonium chloride, and docosyltrimethylammonium chloride. Some of these bactericides do not absorb ultraviolet light, so a universal evaporative light-scattering detector was used owing to testing cost and stability concerns. The paste samples contained thickening agents, which are highly soluble in water but insoluble in organic solvents; these agents can seriously affect the results of sample pretreatment and damage the chromatographic column. Hence, sample dehydration was necessary. In this study, four dehydration methods were compared. Anhydrous sodium sulfate (Na 2 SO 4 ) was selected, and the amount of Na 2 SO 4 was optimized. Based on the solubility of the 10 target compounds and extraction efficiency, three extraction solvents were compared, and ethanol was selected. Ultrasonic extraction was the primary extraction process used in this study. The effects of different ultrasonication times, temperatures, and powers on the extraction recoveries were also investigated. Ultimately, the optimized conditions were as follows: extraction of the dehydrated paste and powder samples using ethanol at room temperature (25 ℃) for 20 min under 100 W ultrasound power, and dilution of the liquid sample with ethanol. After extraction, the samples were separated on an Acclaim Surfactant column (150 mm×4.6 mm, 5 μm) with 50 mmol/L ammonium acetate aqueous solution (pH=5.5) (A) and acetonitrile (B) as mobile phases. The gradient elution program were as follows: 0-5.0 min, 75%A-35%A, 5.0-15.0 min, 35%A-20%A, 15.0-20.0 min, 20%A, 20.0-21.0 min, 20%A-75%A, 21.0-25.0 min, 75%A. An external standard method was used for quantitative determination. The 10 compounds were analyzed within 25 min. Linear equations, correlation coefficients, and linear ranges were obtained by analyzing a series of mixed standard working solutions. The limits of detection (LODs, S/N =3) and quantification (LOQs, S/N =10) of the 10 components were determined. Stearyldimethylbenzylammonium chloride and docosyltrimethylammonium chloride showed good linear relationships in the range of 10-200 mg/L, while the other compounds demonstrated good linear relationships in the range of 5-100 mg/L. In all cases, correlation coefficients ( R 2 ) of no less than 0.9992 were obtained. The LODs and LOQs were in the range of 1.42-3.31 mg/L and 4.25-9.94 mg/L, respectively. Ten analytes were spiked in blank matrices, such as toothpaste (paste), mouthwash (liquid), and dentifrice powder (powder) at three levels, and the recoveries and precisions were calculated. The average recoveries were 87.9%-103.1%, and the corresponding relative standard deviations (RSDs) did not exceed 5.5% ( n =6). The developed method was used to detect 109 oral care products. Benzyldimethylhexadecylammonium chloride and stearyldimethylbenzylammonium chloride revealed high detection rates. Moreover, the amount of stearyldimethylbenzylammonium chloride in one toothpaste sample exceeded regulatory requirements. Given its advantages of good precision and accuracy, the developed method is suitable for the quantitative analysis of the 10 aforementioned compounds in typical oral care products. The study findings can serve as a reference for the quality and safety monitoring of oral care products.

Didecyldimethylammonium chloride (DDAC), a toxic quaternary ammonium compound (QAC) linked to multidrug resistance, is used widely in households and hospitals and on swine farms to prevent disease transmission. However, little is known about its occurrence in watersheds receiving livestock wastewaters or manure. We monitored DDAC and tracers (veterinary and human drugs) once a season over a year at 14 sites in a Japanese watershed where swine outnumbered humans 1.2 to 1 and where both swine and human wastewaters were largely treated on site. DDAC concentrations in sewage-treatment-plant effluent (33-52 ng/L) were close to, whereas those in river waters (3.6-16,672 ng/L) far exceeded, those reported worldwide. DDAC mass flows at the catchment outlet (1692-3816 μg/s) were higher than those of any of the drugs. DDAC concentrations were significantly correlated with total concentrations of veterinary drugs (Spearman's correlation coefficient, 0.95, P < 0.01), indicating that the major pathway of DDAC entry to surface waters was via effluent discharge from swine farms. Comparison of observed and predicted mass flows implied that a substantial percentage of DDAC was washed from the barn floor into swine excrement. To our knowledge, this is the first study to demonstrate QAC hotspots attributable to animal husbandry., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Purpose: The purpose of the study was to determine the fluoride (F) and silver (Ag) ions levels in the saliva and urine of healthy children after silver diamine fluoride (SDF) application on dental carious lesions., Methods: Sixty children (4-6 years with ≥ 3 caries lesions) were recruited from the outpatient department of Pediatric Dentistry. From each child, 3 ml unstimulated saliva samples were collected at baseline, one hour, and 24 h after SDF application. Similarly, 3 ml urine samples were collected prior to and after 24 h of SDF application. F and Ag ion concentrations were determined by fluoride ion-selective electrode (ISE) and inductively coupled plasma mass spectrometry (ICPMS), respectively., Results: The mean ± standard deviation (SD) baseline, 1-h, and 24-h salivary F concentrations (ppm) were 0.07 ± 0.07, 0.93 ± 0.48, and 0.19 ± 0.19, respectively, while the mean baseline and 24-h urinary F concentrations (ppm) were 0.33 ± 0.20 ppm and 0.43 ± 0.25 ppm, respectively. The mean baseline, 1-h, and 24-h salivary Ag concentrations (ppb) were 4.22 ± 3.15, 4198 ± 350, and 56.93 ± 37, respectively. The mean baseline and 24-h urinary Ag concentrations (ppb) were 2.80 ± 2.93 ppb and 4.72 ± 4.0 ppb, respectively. There were statistically elevated F and Ag ion concentrations at 1 h and 24 h after SDF application as compared to the baseline., Conclusion: Salivary and urinary F and Ag ions concentrations elevated significantly at 24 h following SDF applications in children. A significant high recovery of these ions in urine indicates minimal systemic absorption, thus intermittent topical application of 38% SDF has a minimal risk of toxicity., (© 2024. The Author(s), under exclusive licence to European Academy of Paediatric Dentistry.)

The COVID-19 pandemic has led to significantly increased human exposure to the widely used disinfectants quaternary ammonium compounds (QACs). Xenobiotic metabolism serves a critical role in the clearance of environmental molecules, yet limited data are available on the routes of QAC metabolism or metabolite levels in humans. To address this gap and to advance QAC biomonitoring capabilities, we analyzed 19 commonly used QACs and their phase I metabolites by liquid chromatography-ion mobility-tandem mass spectrometry (LC-IM-MS/MS). In vitro generation of QAC metabolites by human liver microsomes produced a series of oxidized metabolites, with metabolism generally occurring on the alkyl chain group, as supported by MS/MS fragmentation. Discernible trends were observed in the gas-phase IM behavior of QAC metabolites, which, despite their increased mass, displayed smaller collision cross-section (CCS) values than those of their respective parent compounds. We then constructed a multidimensional reference SQLite database consisting of m / z , CCS, retention time ( rt ), and MS/MS spectra for 19 parent QACs and 81 QAC metabolites. Using this database, we confidently identified 13 parent QACs and 35 metabolites in de-identified human fecal samples. This is the first study to integrate in vitro metabolite biosynthesis with LC-IM-MS/MS for the simultaneous monitoring of parent QACs and their metabolites in humans.

Benzylalkyldimethylammonium (BACs), dialkyldimethylammonium (DDACs), and alkyltrimethylammonium compounds (ATMACs) are quaternary ammonium compounds (QACs) used widely as biocides, disinfectants, and sanitizers. Owing to their toxicity, human exposure to this class of chemicals is a concern. Pet animals are sentinels of human exposure to several indoor environmental chemicals. For the first time, we measured 7 BACs, 6 DDACs, 6 ATMACs, and 8 metabolites of BACs in urine and feces of pet dogs and cats from New York State, USA. We found widespread occurrence of QACs in feces, with median concentration of ∑All (sum concentration of all 27 QAC analytes) at 9680 and 1260 ng/g dry weight (dw) in dog and cat feces, respectively. BACs were the most abundant compounds among the four types of QACs, accounting for 64 % and 57 % of ∑All in dog and cat feces, respectively, followed by DDACs (33 % and 34 %, respectively), ATMACs (4 % and 9 %, respectively), and BAC metabolites (0.2 % and 0.3 %, respectively). However, in urine, only ω-carboxylic acid metabolites of BACs were found at median concentrations at 2.08 and 0.28 ng/mL in dogs and cats, respectively. Samples collected from animal shelters contained elevated levels of QACs than those from homes of pet owners. A significant positive correlation was found among the four types of QACs analyzed, which suggested usage of these chemicals in combination as mixtures. Based on the concentrations measured in feces, and through a reverse dosimetry approach, the median cumulative daily intakes (CDIs) of QACs were estimated to be 49.4 and 4.75 µg/kg body weight (BW)/day for dogs and cats, respectively. This study provides first evidence that pet dogs and cats are exposed to QACs at significant levels that warrant further attention., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

In this study water and sediment samples, collected from the River Nene (Northamptonshire) at several sites in the vicinity of the Great Billing sewage treatment plant (STP), were analysed for triethanolamine quaternary compounds (TEAQ, ester quats). A method was developed using liquid chromatography tandem mass spectrometry (LC/MS/MS) with a electrospray ionisation source (ESI). Ten components were determined using a characterised commercial sample of Tallow TEAQ as a standard. To our knowledge this is the first time environmental concentrations of a wide spectrum of individual homologues of TEAQ have been reliably quantified covering a broad range of environmental matrices (STP influent, STP effluent, surface waters and sediments), due to the challenging nature of the analytical method. The method featured novel solutions for the determination of long and multiple chain length alkyl quats, controlling loss processes, background contamination and chromatographic performance. TEAQ compounds were found to be highly removed in the sewage treatment plant resulting in low effluent concentrations. Low concentrations in both river water and sediment samples were found also. In many cases levels were below the Method Detection Limit (MDL). In river water samples, mean values of TEAQ compounds found were 210-398 ng/L for C 16:0 /C 18:0 TEAQ diester and 126-287 ng/L for C 18:0 /C 18:0 TEAQ diester. River sediment was found to contain mean TEAQ levels of 7.07-12.5, 19.7 to 40.3 and 7.04-35.1 μg/kg dry weight for C 16:0 /C 16:0 , C 16:0 /C 18:0, and C 18:0 /C 18:0 TEAQ, respectively. At Great Billing STP monoesters and diesters of TEAQ were shown to be efficiently removed (>97 and 99 %, respectively), although limited samples were taken on this occasion., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Survival of foodborne Gram-negative bacteria during osmotic stress often leads to multidrug resistance development. However, despite the concern, how osmoadaptation alters drug penetration across the Gram-negative bacterial cell envelope has remained inconclusive for years. Here, we have investigated drug permeation and accumulation inside hypo-osmotically shocked Escherichia coli . Three different quaternary ammonium compounds (QACs) are used as cationic amine-containing drug representatives; they also serve as envelope permeability indicators in different assays. Propidium iodide fluorescence reveals cytoplasmic accumulation and overall envelope permeability, while crystal violet sorption and second harmonic generation (SHG) spectroscopy reveal periplasmic accumulation and outer membrane permeability. Malachite green sorption and SHG results reveal transport across both the outer and inner membranes and accumulation in the periplasm as well as cytoplasm. The findings are found to be complementary to one another, collectively revealing enhanced permeabilities of both membranes and the periplasmic space in response to hypo-osmotic stress in E. coli . Enhanced permeability leads to faster QACs transport and higher accumulation in subcellular compartments, whereas transport and accumulation both are negligible under isosmotic conditions. The QACs' transport rates are found to be highly influenced by the osmolytes used, where phosphate ion emerges as a key facilitator of transport across the periplasm into the cytoplasm. E. coli is found viable, with morphology unchanged under extreme hypo-osmotic stress; i.e., it adapts to the situation. The outcome shows that the hypo-osmotic shock to E. coli , specifically using phosphate as an osmolyte, can be beneficial for drug delivery.

Quaternary ammonium compounds (QACs) are used in consumer and industrial products, including disinfectants. Due to the COVID-19 pandemic, disinfectant use has increased, purportedly increasing loads to wastewater treatment plants and the environment. To understand how the increased usage has affected QAC loadings to treatment plants and to determine how effectively plants remove QACs from liquid effluent that is discharged to surface and groundwaters, influent and effluent wastewater samples were collected from four treatment plants (treatment capacities < 5 MGD to > 100 MGD) for 21 months beginning in May 2020. Influent QAC concentrations were hundreds of μg/L and effluent QAC concentrations were < 1 μg/L, corresponding to an average removal of 98% from all four plants. The most prevalent QACs in influent were those used most commonly in disinfectants, specifically benzylalkyldimethylammonium compounds (BACs) and short-chain dialkyldimethylammonium compounds (DADMACs), and influent levels of these compounds were correlated with QAC sales. Prior to this study, ethylbenzylalkyldimethylammonium compounds (EtBACs) had not been studied, and they comprised 13 ± 6% of QACs in influent. While removal was high at all plants, low μg/L concentrations were still continuously discharged into the environment. For QACs with equivalent alkyl chain lengths, those with aromatic substituents (BACs and EtBACs) appear to be removed more effectively than those with only alkyl chains (DADMACs).

With the pandemic of COVID-19, the application of quaternary ammonium compounds (QACs), which can be used in SARS-CoV-2 disinfection products, has increased substantially. QACs cumulated in sewer system are ultimately deposited and enriched in sludge. QACs in the environment can adversely affect human health and the environment. In this study, a liquid chromatography-mass spectrometry method was established for the simultaneous determination of 25 QACs in sludge samples. Ultrasonic extraction and filtration of the samples was performed using a 50 mM hydrochloric acid-methanol solution. The samples were separated by liquid chromatography and detected in multiple reaction monitoring mode. The matrix effects of the sludge on the 25 QACs ranged from - 25.5% to 7.2%. All substances showed good linearity in the range of 0.5-100 ng/mL, with all determination coefficients (R 2 ) greater than 0.999. The method detection limits (MDLs) were 9.0 ng/g for alkyltrimethylammonium chloride (ATMAC), 3.0 ng/g for benzylalkyldimethylammonium chloride (BAC), and 3.0 ng/g for dialkyldimethylammonium chloride (DADMAC). The spiked recovery rates were in the range of 74-107%, while the relative standard deviations were in the range of 0.8-20.6%. Considering its sensitivity, accuracy, and easy operation, the proposed method in this study was used to determine 22 sludge samples collected from a comprehensive wastewater treatment plant. The results showed that the concentrations of ΣATMACs, ΣBACs, and ΣDADMACs were 19.684, 3.199, and 8.344 μg/g, respectively. The main components included ATMAC-C16, ATMAC-C18, ATMAC-C20, ATMAC-C22, BAC-C12, and DADMAC-C18:C18, with concentrations exceeding 1.0 μg/g. The concentration relationships of different components in the congeners showed that some components were of similar origin., (© 2023. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

Quaternary ammonium compounds (QACs) are a class of surfactants commonly used in disinfecting and cleaning products. Their use has substantially increased during the COVID-19 pandemic leading to increasing human exposure. QACs have been associated with hypersensitivity reactions and an increased risk of asthma. This study introduces the first identification, characterization and semi-quantification of QACs in European indoor dust using ion-mobility high-resolution mass spectrometry (IM-HRMS), including the acquisition of collision cross section values ( DT CCS N2 ) for targeted and suspect QACs. A total of 46 indoor dust samples collected in Belgium were analyzed using target and suspect screening. Targeted QACs (n = 21) were detected with detection frequencies ranging between 4.2 and 100 %, while 15 QACs showed detection frequencies > 90 %. Semi-quantified concentrations of individual QACs showed a maximum of 32.23 µg/g with a median ∑QAC concentration of 13.05 µg/g and allowed the calculation of Estimated Daily Intakes for adults and toddlers. Most abundant QACs matched the patterns reported in indoor dust collected in the United States. Suspect screening allowed the identification of 17 additional QACs. A dialkyl dimethyl ammonium compound with mixed chain lengths (C16:C18) was characterized as a major QAC homologue with a maximum semi-quantified concentration of 24.90 µg/g. The high detection frequencies and structural variabilities observed call for more European studies on potential human exposure to these compounds. For all targeted QACs, drift tube IM-HRMS derived collision cross section values ( DT CCS N2 ) are reported. Reference DT CCS N2 values allowed the characterization of CCS-m/z trendlines for each of the targeted QAC classes. Experimental CCS-m/z ratios of suspect QACs were compared with the CCS-m/z trendlines. The alignment between the two datasets served as an additional confirmation of the assigned suspect QACs. The use of the 4bit multiplexing acquisition mode with consecutive high-resolution demultiplexing confirmed the presence of isomers for two of the suspect QACs., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Environmental pollution has strong links to adverse human health outcomes with risks of pollution through production, use, ineffective wastewater (WW) remediation, and/or leachate from landfill. 'Fit-for-purpose' monitoring approaches are critical for better pollution control and mitigation of harm, with current sample preparation methods for complex environmental matrices typically time-consuming and labour intensive, unsuitable for high-throughput screening. This study has shown that a modified 'Quick Easy Cheap Effective Rugged and Safe' (QuEChERS) sample preparation is a viable alternative for selected environmental matrices required for pollution monitoring (e.g. WW effluent, treated sludge cake and homogenised biota tissue). As a manual approach, reduced extraction times (hours to ∼20 min/sample) with largely reproducible (albeit lower) recoveries of a range of pharmaceuticals and biocidal surfactants have been reported. Its application has shown clear differentiation of matrices via chemometrics, and the measurement of pollutants of interest to the UK WW industry at concentrations significantly above suggested instrument detection limits (IDL) for sludge, indicating insufficient removal and/or bioaccumulation during WW treatment. Furthermore, new pollutant candidates of emerging concern were identified - these included detergents, polymers and pharmaceuticals, with quaternary ammonium compound (QAC) biocides observed at 2.3-70.4 mg/kg, and above levels associated with priority substances for environmental quality regulation (EQSD). Finally, the QuEChERS protocol was adapted to function as a fully automated workflow, further reducing the resource to complete both the preparation and analysis to <40 min. This operated with improved recovery for soil and biota (>62%), and when applied to a largely un-investigated clay matrix, acceptable recovery (88.0-131.1%) and precision (≤10.3% RSD) for the tested pharmaceuticals and biocides was maintained. Therefore, this preliminary study has shown the successful application of a high-throughput QuEChERS protocol across a range of environmental solids for potential deployment in a regulated laboratory., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The present work aims to describe and review the available technologies and the recent advancements in treating industrial wastewater containing tetramethylammonium hydroxide (TMAH). It is a quaternary ammonium salt and widely used in the microelectronics industry; this kind of company produces large quantities of wastewater containing TMAH. The exhausted solutions must be treated appropriately since TMAH is corrosive, toxic to human health, and ecotoxic. Regarding the concentration at discharge, currently there are no European regulations. Still, it has been indicated that the substance has a negative influence on the oxygen balance and cause eutrophication, and fall into the relevant categories. In the first part of the work, the available technologies and the recent advancements for the treatment of TMAH contained in industrial wastewater are reviewed. Separation methods as such adsorption, ion exchange, membrane processes, and destruction technologies classified as advanced oxidation processes and biological processes have been considered. In the second part of the manuscript, industrial patented wastewater treatments have been described. Biological processes are those more used, being more economically feasible, require very long times not always sustainable., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Background: Quaternary ammonium compounds (QACs), commonly used in cleaning, disinfecting, and personal care products, have recently gained worldwide attention due to the massive use of disinfectants during the COVID-19 pandemic. However, despite extensive use of these chemicals, no studies have focused on the analysis of QACs in human milk, a major route of exposure for infants., Objective: Our objectives were to identify and measure QACs in breast milk and evaluate early-life exposure to this group of compounds for nursing infants., Methods: Eighteen QACs, including 6 benzylalkyldimethyl ammonium compounds (BACs, with alkyl chain lengths of C8-C18), 6 dialkyldimethyl ammonium compounds (DDACs, C8-C18), and 6 alkyltrimethyl ammonium compounds (ATMACs, C8-C18), were measured in breast milk samples collected from U.S. mothers. Daily lactational intake was estimated based on the determined concentrations for 0-12 month old nursing infants., Results: Thirteen of the 18 QACs were detected in breast milk and 7 of them were found in more than half of the samples. The total QAC concentrations (ΣQAC) ranged from 0.33 to 7.4 ng/mL (median 1.5 ng/mL). The most abundant QAC was C14-BAC with a median concentration of 0.45 ng/mL. The highest median ΣQAC estimated daily intake (EDI) was determined for <1-month old infants based on the average (using the median concentration) and high (using the 95 th percentile concentration) exposure scenarios (230 and 750 ng/kg body weight/day, respectively)., Significance: Our findings provide the first evidence of the detection of several QACs in breast milk and identify breastfeeding as an exposure pathway to QACs for nursing infants., Impact Statement: Our findings provide the first evidence of QAC occurrence in breast milk and identify breastfeeding as one of the exposure pathways to QACs for nursing infants., (© 2022. The Author(s), under exclusive licence to Springer Nature America, Inc.)

The frequency of surface disinfectant use has increased over the last several years in public settings such as schools, especially during the COVID-19 pandemic. Although these products are important for infection control and prevention, their increased use may intensify the exposure to both persons applying the disinfection product as well as bystanders. Safety assessments have demonstrated that these products, when used as intended, are considered safe for use and effective; however, point-of-contact effects (such as respiratory or dermal irritation) may still occur. Additionally, relative exposures may vary significantly due to the wide variation in disinfectant formulation and application methods. Quantitative estimations of exposures to two commonly used active ingredients, quaternary ammonium compounds (QACs) and ethanol, are not well characterized during product use and application scenarios. To assess the potential for health risks attributable to increased use in classroom settings, as well as to quantitatively evaluate the potential exposure to both ethanol and QACs, student and adult bystander surface and air measurements were collected in a K-8 school setting in Ohio, United States, over a three-day period. Direct-reading instruments were utilized to collect real-time air samples that characterized mass fraction concentrations following the use of the QAC- and ethanol-based disinfectants. Furthermore, surface and air sampling of microbial species were conducted to establish the overall bioburden and effectiveness of each disinfectant to inform the comparative risk and health effect impacts from the tested products use scenario. Both tested products were approximately equally effective at reducing bioburdens on desk surfaces. In some classrooms, concentrations of QAC congeners were significantly increased on desk surfaces following the application of the disinfectant spray; however, the magnitude of the change in concentration was small. Ethanol was not measured on surfaces due to its volatility. Airborne concentrations increased immediately following spray of each disinfectant product but rapidly returned to baseline. Each of the QAC congeners listed in the product safety data sheets were detected and measurable on desk surfaces; however, air concentrations were generally below the limit of detection. The 15-min time-weighted averages (TWAs) of both QACs and ethanol in the air were below respective health effects benchmarks, and therefore, the negative impact on health outcomes is considered to be minimal from short-term, repeated use of ethanol- or QAC-based spray products in a school setting when the products are used as directed., (© 2022 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

A qualitative and quantitative liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for the sensitive and exhaustive analysis of residues from triarylmethane dyes, triarylmethane-derivative dyes, phenothiazines, phenoxazines and xanthenes in aquaculture samples. For a wider and more robust detection of dye misuse on farms, other residue markers were also included the leuco forms of brilliant green, crystal violet and malachite green; one direct metabolite of Victoria pure blue BO and methylene blue and three bile acids, which are endogenous markers of the effects of dye contamination in fish. We optimised the extraction method by comparing several extraction solvents and sample solvents reported in the literature to have the best extraction efficiency. The residues were determined using a positive electrospray ionisation source. We assessed the parameters of this LC-MS/MS method by evaluating the matrix effects, identification and quantitative parameters according to the criteria stipulated in the European Commission Decision No. 2002/657/EC. A study on the applicability of the method was conducted on various aquaculture species and on a positive catfish.

Controlling and monitoring the residual activity of quaternary ammonium compounds (QACs) are critical for maintaining safe yet effective levels of these agents in the environment. This study investigates the utility of bromophenol blue (BPB) as a safe, rapid and user-friendly indicator to detect in situ residual QACs dried on hard, non-porous surfaces, as well a means to assess their antimicrobial efficacy. At pH 7, BPB has a purple colour which turns blue upon its complexation with QACs such as didecyldimethylammonium chloride (DDAC). BPB itself has no antimicrobial properties up to 400 ppm. Within the range of 0-400 ppm, BPB colour change was tied to specific DDAC antimicrobial performances with a detection threshold of 100 ppm. BPB concentration and application volume could be adjusted such that a colour shift from purple to blue correlated with a set percent reduction (>99·9%) in test bacteria (Staphylococcus aureus and Klebsiella aerogenes). The BPB solutions developed in this study yielded similar colour shifts on polycarbonate and stainless steel surfaces and did not cross-react with chemical ingredients commonly found in sanitizers and disinfectant products. Overall, this study suggests that BPB provides a simple solution to safely monitor the post-application level and biocidal activity of residual dried QACs on surfaces., (© 2020 The Society for Applied Microbiology.)

A microfluidic, label-free optical sensor for water pollutants, which is based on a packed micro-column of microspheres with refractive index similar to that of water, is presented. The perfluoropolyether microspheres are synthetized by membrane emulsification followed by UV irradiation. The microfluidic channel hosting the packed column is transparent when filled with pure water as a consequence of refractive index matching, whereas it scatters light in presence of compounds with lipophilic moieties that spontaneously adsorb on the fluorinated microspheres. The device is characterized by investigating the response to cationic and anionic surfactants. Both the signal growth rate and the recovery rate measured during washing with water depend on the type and concentration of the compounds. The cationic surfactants tested display a larger signal increase, linearly scaling with concentration. A limit of detection of 1 μM is obtained in the current configuration. The water index-matched microspheres enable to access an additional analytical parameter, that is the propagation velocity of the scattering signal along the column. This parameter is also found to scale linearly with concentration, hence providing a complementary analytical tool sensitive to the adhesion kinetics.

A novel magnetic solid-phase extraction (MSPE) material (Fe 3 O 4 @SiO 2 -NH 2 -G2) had been prepared and employed for adsorption and analysis of seven quaternary ammonium compounds (QACs) in infant fruit and vegetable products coupled with high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). In this paper, Fe 3 O 4 @SiO 2 -NH 2 -G2 was synthesized based on Fe 3 O 4 @SiO 2 -NH 2 and dendrimer (G2) consisting of cyanuric chloride and imidazole. The morphology, configuration and magnetic behavior of the magnetic material were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectrometry (FT-IR), X-ray diffraction (XRD), and vibrating sample magnetometer (VSM). Critical parameters affecting extraction efficiency, such as the adsorbent amount, sample pH, extraction time, the type of eluent, and desorption time, were optimized. The proposed method provided good linearity with the correlation coefficients (R 2 ) of 0.9992-0.9999, low limits of detection (LODs) (0.05-0.50 μg kg -1 ) and limits of quantitation (LOQs) (0.20-2.00 μg kg -1 ). The satisfactory method recoveries in three spiked infant fruit and vegetable products samples were between 80.12% and 101.35% with the relative standard deviations (RSDs) less than 12.04%. In summary, the established method was an effective sample preparation method and showed good prospect for the analysis of QACs in complex matrices., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

In this study, a lab-scale upflow anaerobic sludge blanket (UASB) reactor was applied to the treatment of artificial electronics industry wastewater containing tetramethylammonium-hydroxide (TMAH), monoethanolamine (MEA), and isopropyl-alcohol (IPA) in order to evaluate process performance and degradation properties. During 800 days of operation, 96% efficiency of chemical oxygen demand (COD) removal was stably achieved at an organic loading rate of 8.5 kgCOD/m 3 /day at 18-19 °C. MEA degradation, carried out by acid-forming eubacteria, was confirmed within a week. The physical properties of the retained granular sludge were degraded by feeding with TMAH wastewater, but maintained by feeding with MEA wastewater due to an accumulation of species from the genus Methanosaeta and family Geobacteraceae . Analysis of the microbial community structure via SEM and 16S rRNA genes showed a proliferation of Methanomethylovorans -like cells and Methanosaeta -like cells at the surface and in the core of the granular sludge with TMAH, MEA and IPA acclimation. Furthermore, a batch degradation experiment confirmed that process inhibition due to increasing chemical concentration was relatively stronger for TMAH than for MEA or IPA. Thus, controlling the TMAH concentration of the influent to below 1 gCOD/L will be important for the stable treatment of electronics industry wastewater by UASB technology.

For simultaneous analysis of four fat-soluble tocopherols (α-, β-, γ-, and δ-) in edible oils, an efficient and green method using deep eutectic solvent-based liquid-phase microextraction (DES-LPME) coupled with reversed-phase high-performance liquid chromatography (RP-HPLC) was developed. The DESs formed by different quaternary ammonium salts and ethanol were used as the extractants. Tetrabutylammonium chloride (TBAC)-ethanol DES at a molar ratio of 1:2 achieved the best extraction efficiency. Under the optimized conditions, the detection limits were in the range of 2.1-3.0 ng mL -1 . The intra-day and inter-day repeatability were in the ranges of 3.9-5.3% and 4.8-7.1%, respectively, and the recoveries for the real samples varied from 80.7% to 105.4%. The developed method was successfully employed for the determination of all four tocopherol homologues with an RP-HPLC system containing a COSMOSIL π-NAP column in five edible oils collected locally. Graphical abstract.

Purpose: P-glycoprotein (P-gp) at the blood-brain barrier (BBB) precludes the brain penetration of many xenobiotics and mediates brain-to-blood clearance of β-amyloid, which accumulates in the Alzheimer's disease (AD) brain. Zinc and copper are reported to modulate BBB expression and function of P-gp; however, the impact of exogenous iron, which accumulates in AD, on P-gp dynamics remains unknown., Methods: P-gp protein and MDR1 transcript levels were assessed in immortalised human cerebral microvascular endothelial (hCMEC/D3) cells treated with ferric ammonium citrate (FAC; 250 μM, 72 h), by Western blotting and RT-qPCR, respectively. P-gp function was assessed using rhodamine-123 and [ 3 H]-digoxin accumulation. Intracellular reactive oxygen species (ROS) levels were determined using 2',7'-dichlorofluorescin diacetate and intracellular iron levels quantified using a ferrozine assay., Results: FAC treatment significantly reduced P-gp protein (36%) and MDR1 mRNA (16%) levels, with no significant change in rhodamine-123 or [ 3 H]-digoxin accumulation. While P-gp/MDR1 downregulation was associated with elevated ROS and intracellular iron, MDR1 downregulation was not attenuated with the antioxidant N-acetylcysteine nor the iron chelators desferrioxamine and deferiprone, suggesting the involvement of a ROS-independent mechanism or incomplete iron chelation., Conclusions: These studies demonstrate that iron negatively regulates P-gp expression at the BBB, potentially impacting CNS drug delivery and brain β-amyloid clearance.

Alkyltrimethylammonium compounds (ATMACs), dialkyldimethylammonium compounds (DADMACs) and benzylalkyldimethylethylammonium compounds (BACs) are quaternary alkylammonium compounds (QAAC), which are released into the environment in large quantities after their use in cleaning agents and disinfectants. Despite their potential role as selective agents promoting resistance against QAACs as well as antibiotics, there is a lack of data for QAACs in soil due to the lack of sensitive analytical methods. Therefore, we present a robust and fast method for the extraction and quantification of concentrations of these compounds in soil and sewage sludge. The method is based on ultrasonic extraction (USE) with a mixture of acetonitrile and HCl followed by a solid phase extraction (SPE) cleaning step and a subsequent quantification of concentrations with high performance liquid chromatography with mass spectrometry (HPLC-MS/MS) in multi mass reaction mode (MRM). The proposed method is suitable for the quantification of ATMACs (chain length C-8 to C-16), BACs (C-8 to C-18) and DADMACs (C-8 to C-16). The achieved limits of quantification (LOQ) range from 0.1 μg kg-1 to 2.1 μg kg-1. The recovery rates of spiked soil samples for non-deuterated homologues were between 47% and 57%. The analysis of sewage sludge samples and soil samples revealed that BAC-C12 was the most abundant QAAC with concentrations up to 38600 μg kg-1 in sewage sludge and up to 81 μg kg-1 in a Mexican soil that was irrigated with wastewater. Overall, the presented methods open perspectives for effectively studying fate and effects of QAACs in soils., Competing Interests: The authors have declared that no competing interests exist.

Gemini surfactants are a class of lipid molecules that have been successfully used in vitro and in vivo as nonviral gene delivery vectors. However, the biological fate of gemini surfactants has not been well investigated. In particular, the metabolism of gemini surfactants after they enter cells as gene delivery vehicles is unknown. In this work, we used a high-resolution quadrupole-Orbitrap mass spectrometry (Q-Exactive) instrument to detect the metabolites of three model gemini surfactants, namely, (a) unsubstituted (16-3-16), (b) with pyridinium head groups (16(Py)-S-2-S-16(Py)), and (c) substituted with a glycyl-lysine di-peptide (16-7N(GK)-16). The metabolites were characterized, and structures were proposed, based on accurate masses and characteristic product ions. The metabolism of the three gemini surfactants was very different as 16-3-16 was not metabolized in PAM 212 cells, whereas 16(Py)-S-2-S-16(Py) was metabolized primarily via phase I reactions, including oxidation and dealkylation, producing metabolites that could be linked to its observed high toxicity. The third gemini surfactant 16-7N(GK)-16 was metabolized mainly via phase II reactions, including methylation, acetylation, glucose conjugation, palmityl conjugation, and stearyl conjugation. The metabolism of gemini surfactants provides insight for future directions in the design and development of more effective gemini surfactants with lower toxicity. The reported approach can also be applied to study the metabolism of other structurally related gemini surfactants.

Chemical characterization of PM 2.5 and PM 10 is important to identify potential compounds that induce biological responses that translate into cardio-respiratory health problems. This study shows the reliability of the use of crystalline phases, identified in samples from receptor sites, as source markers, helping researchers to infer the main sources of air pollution, even without the use of receptor models. PM 2.5 and PM 10 samples were collected at two sites in an urban industrialized region located at southeast of Brazil and analyzed by Synchrotron X-ray Diffraction to identify crystalline compounds. Results show 5 PM 10 and PM 2.5 species not previously reported in the literature. We propose reaction mechanisms for these species and identify specific sources for each crystalline phase found: BaTiO 3 was found in PM 10 receptor samples and proved to be a vehicular marker formed during brake action; maghemite (γ-Fe 2 O 3 ), pyracmonite [(NH 4 ) 3 Fe(SO 4 ) 3 ], ammonium perchlorate (NH 3 OHClO 4 ) and potassium ferrate (K 2 Fe 2 O 4 ) were found in PM 2.5 proved to be markers of industrial activities. The crystalline phases found in PM samples from receptor sites and the mechanisms of reactions showed the reliability of the use of crystalline phases as source markers in the identification of potential sources of air pollution without misinterpretation of the likely source., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In this paper, a process combining biodegradation and Fenton oxidation was proposed for the removal of polydiallyldimethylammonium chloride-acrylic-acrylamide-hydroxyethyl acrylate (PDM) in aqueous phase. Biodegradation of PDM was investigated in activated sludge systems, and the effects of the solution pH, mixed liquid suspended solids (MLSS), salinity, co-substrate, and initial substrate concentration, were studied. The biodegradation process was well-described with the Monod model and the values of the kinetics parameters v max , k s were 0.05 h -1 and 333 mg/L. The optimal biodegradation conditions in the experimental range were determined to be: pH = 7.0, 0%-0.01% (w/v) NaCl, 4000 mg/L of MLSS, and 500 mg/L of glucose as co-substrate. FT-IR analysis indicated that PDM molecules biodegradation partly. The microbial community structures and dehydrogenase activity analysis revealed that PDM showed some toxicity to microorganisms in activated sludge. The effects of several parameters, including the pH and chemical doses, were investigated for removing PDM in Fenton oxidation process. The optimal Fenton oxidation process conditions in the experimental range were pH = 2.0, Fe 2+ concentration of 40 mg/L, and H 2 O 2 dosage of 23 mL/L. PDM was treated by biodegradation and subsequent Fenton oxidation under the optimal operating conditions. The removal efficiency was 44.5% after the biodegradation process and further increased to 85.5% after Fenton oxidation. The combined process was revealed to be a promising solution for achieving effective and economical removal of PDM., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Poly(sodium-p-styrenesulfonate)-enhanced and D-penicillamine stabilized Ag nanoclusters (PSS-DPA-AgNCs) were prepared using one-step ultraviolet irradiation combined with microwave heating method, and the effects of the AgNCs photo-luminescence performance based on different types of polyelectrolytes and energy suppliers were studied detailedly. The as-prepared AgNCs can be used as a viable fluorescent probe for monitoring indirectly iron(II) lactate hydrate (ILH) and ammonium ferric citrate (AFC), respectively. The fluorescence (FL) quenching of PSS-DPA-AgNCs by Fe 3+ (it is obtained from oxidized ILH/ionized AFC) mainly derives from a dynamic quenching process. Excellent linear relationships exist between the FL quenching degree of the AgNCs and the concentrations of ILH/AFC in the range of 0.17-6.00/0.067-3.33 μmol·L -1 , and corresponding limit of detection (at 3σ/slope) is 12.4/6.04 nmol·L -1 . Moreover, the AgNCs probe was extended to the assays of ILH in tablets, solid beverage or ILH additive and AFC in two kinds of edible salts or syrup with satisfactory results compared with the standard 1, 10-phenanthroline method. In addition, the AgNCs probe reveals a good temperature sensing capability., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Standard ready biodegradability tests are conducted at unrealistically high test concentration and therefore cannot properly evaluate toxic substances to microorganisms. The present study evaluated the effects of four adsorbent carriers in modified ready biodegradability tests of four quaternary ammonium salts (QASs) demonstrating microbial toxicity according to the Organization for Economic Co-operation and Development Test Guideline 301F and cautions for using carriers were found. In the tests with silica gel, the concentration of all QASs in the test solutions decreased due to adsorption. The percentages of biodegradation of octadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and benzyldimethyloctadecylammonium chloride, which have a linear alkyl chain, were 89.9%, 80.6%, and 70.1% on day 28, respectively; benzethonium chloride, with a branched alkyl chain, did not undergo biodegradation. In the tests with activated carbon, although the concentrations of QASs greatly decreased, no QASs underwent biodegradation. In the tests with sea sand or quartz sand, QASs were not adsorbed on the carriers and were not biodegraded. Using an adsorbent carrier for toxic substances will increase biodegradation, but it has no effect on highly persistent substances with specific chemical structures, e.g., branched carbons, which is very important because ready biodegradability is not overestimated. Carriers having moderate adsorbability should be selected.

The application of membrane and cell wall selective fluorescent dyes for live-cell imaging analyses of organelle dynamics in fungal cells started two decades ago and since then continues to contribute greatly to our understanding of the filamentous fungal lifestyle. This paper provides a practical guide for the utilization of the two membrane dyes FM 1-43 and FM 4-64 and the four cell wall stains Calcofluor White M2R, Solophenyl Flavine 7GFE 500, Pontamine Fast Scarlet 48 and Congo Red. The focus is on their low-dose application to ascertain artefact-free staining, their co-imaging properties, and their quantitative evaluation. The presented methods are applicable to all filamentous fungal samples that can be prepared in the described ways. The fundamental staining approaches can serve as starting points for adaptations to species that might require different cultivation conditions. First, biophysical and biochemical properties are reviewed as their understanding is essential for using these dyes as truly vital fluorescent stains. Secondly, step-by-step protocols are presented that detail the preparation of various fungal sample types for fluorescent live-cell imaging. Finally, example experiments illustrate different approaches to: (1) identify defects in the spatio-temporal organization of endocytosis in genetic mutants, (2) comparatively characterize shared and distinct co-localization of GFP-labeled target proteins in the endocytic pathway, (3) identify morphogenetic cell wall defects in a genetic mutant, and (4) monitor cell wall biogenesis in real time.

In this study, we developed a novel bioelectronic taste sensor for the detection of specific bitter substances. A human bitter taste receptor, hT2R4, was efficiently expressed in Escherichia coli (E. coli), which was used as the primary recognition element. A simple and low-cost electrochemical device based on ITO-based electrolyte-semiconductor (ES) structure was innovatively employed as the transducer to assess bacterial metabolic consequences of receptor activation in real time. An apparent increase in extracellular acidification rate was observed, which was resulted from the triggering of hT2R4 receptors by their target ligand of denatonium. The sensor showed dose-dependent responses to denatonuim ranging from 50 nM to 500 nM, while non-bioengineered bacteria without hT2R4 receptors exhibited negligible responses to the same stimulus. In addition, the specificity of the proposed taste biosensor was verified using other typical bitter substances such as quinine and alpha-naphthylthiourea (ANTU). This research provides a simple and inexpensive approach for the construction of bioelectronic taste sensors., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The aim of the study was to initiate an exhaustive strategy of control by implementing both targeted and non-targeted metabolomics approaches. A LC-MS/MS method including an oxidative step for most of dyes was developed and validated to target the analysis of 14 residues belonging to different families of dyes. The method was suitable for the quantitative confirmation of 13 dyes at low ppb levels. The metabolomics approach objective was to compare fingerprints between farmed fish treated with malachite green and farmed fish treated with victoria pure blue bo. Analytical information on modifications in the metabolome of muscle, liver and plasma was exploited by HRMS following by multivariate statistics and revealed some direct or endogenous metabolites among relevant mass features contributing to the constructed models. These two approaches, either appropriate biomarkers either enlarged targeted dyes are explored concomitantly to help improving the strategy for tracking new illegal practices in aquaculture., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Precise and efficient endocytosis is critical for sustained neurotransmission during continuous neuronal activity. Endocytosis is a prerequisite for maintaining the auditory function. However, the differences between the patterns of endocytosis in cochlear inner hair cells (IHCs) and outer hair cells (OHCs) remain unclear. Both IHCs and OHCs were obtained from adult C57 mice. Patterns of endocytosis in cells were estimated by analyzing the uptake of FM1-43, a fluorescent. The observations were made using live confocal imaging, fluorescence intensities were calculated statistically. Results revealed the details about following phenomenon, i) sites of entry: the FM1-43 dye was found to enter IHC at the apical area initially, the additional sites of entry were then found at basolateral membrane of the cells, The entry of the dye into OHCs initially appeared to be occurring around whole apical membranes area, which then diffused towards the other membrane surface of the cells, ii) capacity of endocytosis: fluorescence intensity in IHCs showed significantly higher than that of OHCs (P<0.01). We have found different patterns of endocytosis between IHCs and OHCs, this indicated functional distinctions between them. Moreover, FM1-43 dye can be potentially used as an indicator of the functional loss or repair of cochlear hair cells.

In this work, ion mobility spectrometry (IMS) function as a detector and another dimension of separation was coupled with CE to achieve two-dimensional separation. To improve the performance of hyphenated CE-IMS instrument, electrospray ionization correlation ion mobility spectrometry is evaluated and compared with traditional signal averaging data acquisition method using tetraalkylammonium bromide compounds. The effect of various parameters on the separation including sample introduction, sheath fluid of CE and drift gas, data acquisition method of IMS were investigated. The experimental result shows that the optimal conditions are as follows: hydrodynamic sample injection method, the electrophoresis voltage is 10 kilo volts, 5 mmol/L ammonium acetate buffer solution containing 80% acetonitrile as both the background electrolyte and the electrospray ionization sheath fluid, the ESI liquid flow rate is 4.5 μL/min, the drift voltage is 10.5 kilo volts, the drift gas temperature is 383 K and the drift gas flow rate is 300 mL/min. Under the above conditions, the mixture standards of seven tetraalkylammoniums can be completely separated within 10 min both by CE and IMS. The linear range was 5-250 μg/mL, with LOD of 0.152, 0.204, 0.277, 0.382, 0.466, 0.623 and 0.892 μg/mL, respectively. Compared with traditional capillary electrophoresis detection methods, the developed CE-ESI-IMS method not only provide two sets of qualitative parameters including electrophoresis migration time and ion drift time, ion mobility spectrometer can also provide an additional dimension of separation and could apply to the detection ultra-violet transparent compounds or none fluorescent compounds., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this study, a modified Quick Polar Pesticides (QuPPe) method, optimized by a central composite design, was developed to determine quaternary ammonium pesticides (QUATs) residues in barley and wheat by ultra-high-performance liquid chromatographic tandem mass spectrometry (UHPLC-MS/MS) using a hydrophilic interaction chromatography (HILIC) column. Considering the high polarity of these compounds, special conditions of sample preparation and analysis are required. Different mobile phases, extraction procedure and clean-up were evaluated. An isocratic elution with aqueous solution of ammonium formate 60 mmol L -1 (pH 3.7) and acetonitrile, 40:60 (v/v), was selected. Water and acidified methanol as extraction solvent, without heating, and a clean-up with dichloromethane, chitosan and acetonitrile presented good results. The validated method presented satisfactory selectivity, linearity, matrix effect, trueness and precision, providing recoveries from 93 to 110% with RSD < 13% for barley, and 70 to 115% with RSD < 18% for wheat. The complexity of these matrices requires the calibration in matrix and the diluted standard addition calibration (DSAC) procedure has been shown to be an excellent option to compensate for the matrix effect and the losses of the analytes in the extraction. Real samples of barley and wheat were analyzed and 60% presented concentrations of paraquat above the maximum limits allowed by the European Union. The modified QuPPe method combined with DSAC and HILIC-UHPLC-MS/MS demonstrated to be an effective approach to determine QUATs in barley and wheat, and is a good alternative for routine analysis. The use of the biosorbent chitosan is effective, low cost and more ecological when compared to others conventional sorbents., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Capparis spinosa L. is a perennial plant typical of the Mediterranean flora and a multipurpose plant used for curing various human ailments. Quaternary ammonium compounds (QACs), as constituents of Capparaceae, play important roles in protecting against abiotic stress. Aim of this work was to determine QACs in root and leaves of caper from two proveniences. The presence of stachydrine, choline, glycine betaine and homo-stachydrine has been confirmed by high resolution MS, while 1 H NMR was applied to quantify the main QACs in the aqueous extracts. Stachydrine was quantified at 20.2 mg/g and 32.3 mg/g on dry leaves from South of Italy and Saudi Arabia, respectively, while a minor content was in dry roots (from 10.4 to 12.5 mg/g). Choline was considerably lower both in leaves and roots (from 0.3 to 1.2 mg/g). To our knowledge, this is the first report on the determination of QACs both in root and leaves of C. spinosa.

The cycling of synaptic vesicles ensures that neurons can communicate adequately through their synapses on repeated occasions when activity is sustained, and several steps in this cycle are modulated by actin. The effects of pharmacological stabilization of actin with jasplakinolide or its depolymerization with latrunculin A was assessed on the synaptic vesicle cycle at individual boutons of cerebellar granule cells, using FM1-43 imaging to track vesicle recycling and its photoconversion to specifically label recycled organelles. Remarkable differences in the recycling capacity of individual boutons are evident, and their dependence on the actin cytoskeleton for recycling is clear. Disrupting actin dynamics causes a loss of functional boutons, and while this indicates that exo/endocytotic cycling in boutons is fully dependent on such events, this dependence is only partial in other boutons. Indeed, exocytosis and vesicle trafficking are impaired significantly by stabilizing or depolymerizing actin, whereas repositioning recycled vesicles at the active zone seems to be dependent on actin polymerization alone. These findings support the hypothesis that different steps of synaptic vesicle cycling depend on actin dynamics and that such dependence varies among individual boutons.

The increasing finding of pathogens and antibiotic resistance genes (ARGs) in drinking water has become one of the most challenging global health threats worldwide. However, conventional disinfection strategies in drinking water treatment plants (DWTPs) require further optimization in combating the antibiotic resistome. Here, we show that antimicrobial resins with quaternary ammonium salts (AMRs-QAS) exhibit great potentials in diminishing specific potential pathogens that relatively resist chlorine or UV disinfection in DWTPs, and comprehensive analyses using microscopy and fluorescence techniques revealed that the antimicrobial capacity of AMRs-QAS mainly proceed via the bacterial adsorption and cell membrane dissociation. Moreover, a total of 15 among 30 selected ARGs, as well as 4 selected potential pathogens including Pseudomonas aeruginosa, Bacillus subtilis, Escherichia coli and Staphylococcus aureus were all detected in the source water. Coupling the AMRs-QAS with 0.2 mg/L chlorine resulted in higher removal efficiencies than chlorination (2 mg/L) or UV disinfection (400 mJ cm -2 ) for all the detected pathogens and ARGs in drinking water and significantly decreased the relative abundances of Pseudomonas aeruginosa, Bacillus subtilis, Escherichia coli, as well as all the detected ARGs (p < 0.05). Co-occurrences of pathogens and ARGs were revealed by a correlation network and possibly accounts for the ARGs removal. This coupled disinfection strategy overcomes the limitations of individual disinfection methods, i.e. the enrichment of specific pathogens and ARGs among bacterial populations, and provides an alternative for minimizing health risks induced by the antibiotic resistome in DWTPs., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The scientific multistep approach described herein is a result of two years of research into a control method against microbial fouling and biodeterioration of historic building materials by phototrophs. A series of tests were conducted to select the best antifouling agent for eliminating 'green' coatings and protecting surfaces against biofouling. Of the seven active compounds, two with the best penetration abilities were subjected to a photosynthetic activity inhibition test using confocal microscopy. Of the two, a quaternary ammonium salt (QAC) - didecyldimethylammonium chloride (DDAC) - was found to be the most effective. Ten biocides containing QACs at different concentrations were then tested against 'green' coatings on wood, brick and plaster, with the best four being selected for further research in model conditions. As a result, biocides containing >14% (v v -1 ) DDAC were found to be successful antifouling agents for protecting historical materials against biodeterioration by phototrophs.

This study investigated the feasibility of the methanogenic treatment of electronic industry wastewater containing tetramethylammonium hydroxide (TMAH), monoethanolamine (MEA) and sulfate in a lab-scale mesophilic up-flow anaerobic sludge blanket reactor. Feeding a mixture of electronic industry wastewater and co-substrate organics to the reactor for smooth acclimatization of sludge gave complete degradation of each organics within five days. When the reactor was fed only electronic industry wastewater, total COD removal, TMAH removal and MEA removal were achieved over 80, 99 and 99%, respectively, at an organic loading rate of 11.5 kg-COD m -3  day -1 . 173 mg-S L -1 of influent sulfate was almost reduced simultaneously with the COD removal. In order to evaluate performance stability, the TMAH shock load event was performed under the conditions of 11,000 mg-COD L -1 for 24 h. Inflow of high TMAH concentration inhibited TMAH degradation and sulfate reduction for more than one month, however, not MEA. The batch feeding experiment and specific activity measurement revealed degradation pathways of each organics. TMAH was degraded via methanogenic pathway without sulfate reduction, MEA was degraded via methanogenic pathway with sulfate reduction. The results indicated that methanogenic treatment was applicable to electronic industry wastewater by appropriate reactor handling.

The cationic polyelectrolyte pDADMAC is widely used in biopharmaceutical industry as a flocculating agent to enhance clarification throughput and downstream filtration operations. Due to the possible toxicity, pDADMAC should be assessed for an acceptable residual level to ascertain the safety of the product to patients. The strong protein-polyelectrolyte interaction, however, can negatively affect sensitivity and accuracy of measurements. This paper reports on the application of size exclusion (SE) chromatography coupled to evaporative light scattering detector (ELSD) to the quantitative determination of pDADMAC in monoclonal antibody formulations and in process intermediates during downstream purification. The SE chromatography was performed under isocratic condition with a mobile phase consisting of 0.1% TFA in water (90%) and acetonitrile (10%) at a flow rate of 0.4 ml/min. A quantification limit (S/N = 10) of 0.85 ppm was achieved in sample matrix, which is sufficiently low for the trace analysis of this compound in protein-containing samples., (Copyright © 2018 International Alliance for Biological Standardization. Published by Elsevier Ltd. All rights reserved.)

Quaternary ammonium compounds (QACs) are surface-active organic compounds common in industrial cleaner formulations widely used in various sanitation applications. While acting as effective pathogenic biocides, QACs lack selective toxicity and often have poor target specificity. As a result, adverse effects on biological processes and thus the performance of biological nutrient removal (BNR) systems may be encountered when QACs enter wastewater treatment plants (WWTPs). Because of these impacts, there is motivation to screen wastewater influents for QACs and for process engineers to consider the inhibition effects of QACs on process evaluation and design of BNR plants. This paper introduces a mathematical model to describe the fate of QACs in a WWTP via biodegradation and bio-adsorption, and the inhibitory effect of QACs on nitrifiers and ordinary heterotrophic organisms. The model was incorporated as an add-on model in BioWin 5.3 and simulations of experimental systems were used for comparison of model results to measured data reported in the literature. The model was found to accurately predict the bulk phase concentration of QAC and the inhibition of nitrification with QAC concentrations ≥2 mg/L. This work provides a preliminary framework for simulation of BNR plants receiving inhibitory substances in the influent.

In this work, the distribution of quaternary ammonium compounds (QACs) in two dated sediment cores, collected from the Pearl River Estuary (PRE) and Tokyo Bay (TB), were investigated to understand the historical input of QACs and their diagenetic behavior in urban estuarine environments. The vertical variation profiles of QAC concentrations showed that benzylalkyldimethyl ammonium compounds (BACs) and dialkyldimethyl ammonium compounds (DADMACs) were widely used during 1970s and 1980s both in China and Japan. The declining environmental concentrations of QACs suggested a compositional change of commodities and the effectiveness of emission control strategies. For the individual QAC homologues, BAC homologues decreased significantly over time, while DADMAC compositions remained relatively stable. The differences in concentration and composition profiles of BACs and DADMACs in the sediment cores provided useful information on the patterns of use of QACs in China and Japan, as well as their diagenetic behaviors in the sediments., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Background: A flow-injection MS (FI/MS) method was evaluated for the quantitation of quaternary ammonium cations (QACs) in simple food simulants. Methods: The calibration standard was dimethyldioctadecyl ammonium ion (C18-C18), and the internal standard was benzyldimethylhexadecyl (BDMHD) ammonium ion. Calibration standards based on the C18-C18 ion were prepared in ethanol with a range of 5 to 500 ppb and contained 100 ppb BDMHD. The mobile phase was 90 + 10 (v/v) acetonitrile-5 mM aqueous ammonium acetate and flowed directly into an electrospray source of the mass spectrometer. Detection was accomplished by single ion recording (SIR) in positive mode. Results: Calibration curves were linear with coefficients of determination above 0.995, and the LOQ was 5 ppb. Recoveries of four QACs derived from Arquad 2HT-75, a commercially available surfactant, were measured in common food simulants: ethanol, water, 10% (v/v) ethanol in water, and 3% (v/v) aqueous acetic acid. A solvent exchange procedure was employed for the three aqueous solvents, which included complete evaporation of the sample followed by reconstitution in ethanol prior to injection. The solvent exchange method minimized losses because of QAC adsorption on glass surfaces. Recoveries ranged from 74.4 ± 4.0 to 106.7 ± 6.6% for the two most abundant Arquad 2HT-75 component cations, dimethyldioctadecyl ammonium and dimethyloctadecyl-hexadecyl ammonium. Conclusions: This method is suitable to quantify trace levels of QACs in food simulants as part of exposure evaluations related to their use in emerging food contact materials.

Voltammetric DNA sensor has been proposed on the platform of glassy carbon electrode covered with carbon black with adsorbed pillar[5]arene molecules. Electropolymerization of Neutral Red performed in the presence of native or oxidatively damaged DNA resulted in formation of hybrid material which activity depended on the DNA conditions. The assembling of the surface layer was confirmed by scanning electron microscopy and electrochemical impedance spectroscopy. The influence of DNA and pillar[5]arene on redox activity of polymeric dye was investigated and a significant increase of the peak currents was found for DNA damaged by reactive oxygen species generated by Cu 2+ /H₂O₂ mixture. Pillar[5]arene improves the electron exchange conditions and increases the response and its reproducibility. The applicability of the DNA sensor developed was shown on the example of ascorbic acid as antioxidant. It decreases the current in the concentration range from 1.0 μM to 1.0 mM. The possibility to detect antioxidant activity was qualitatively confirmed by testing tera infusion. The DNA sensor developed can find application in testing of carcinogenic species and searching for new antitumor drugs.

Nowadays, parabens have been replaced by domiphen bromide, which is widely used in pharmaceutical and cosmetic products. The main aim of this study was to investigate stressed degradation products of domiphen bromide by mean of a rapid, specific and reliable LC-ESI MS/MS since phenyl bromination may occur due to the oxidation of bromide counter ion under oxidative conditions. LC-ESI-MS/MS have characterized a new compound, p-bromodomiphen, as the only degradation product and structure elucidation was also confirmed by the synthesis of the standard. Notably, the resulting p-bromodomiphen bromide is more stable then domiphen bromide in oxidizing conditions since no di-bromoderivatives were detected by MS studies; both domiphen and its p-bromo derivative were tested for antibacterial activity and were more effective on Gram positive (Staphylococcus aureus ATCC25923 and Bacillus cereus DSM31) compared to Gram negative bacteria (Escherichia coli ATCC25922 and Pseudomonas aeruginosa DSM22644). In conclusion, stressed degradation studies by LC-ESI-MS/MS have characterized a new compound that comprises an alternative to domiphen bromide since its antimicrobial activity is comparable to, if not better than, the parental compound., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In this study, dispersive liquid-liquid micro-extraction using ionic liquid (IL-DLLME) combined with zero crossing first derivative spectrophotometric method was applied to quantitative determination of triphenylmethane dyes in binary mixtures. The 1-methyl-3-octylimidazolium hexafluorophosphate [OMIM][PF 6 ] ionic liquid was used to extract Brilliant Green (BG) and Crystal Violet(CV) dyes from aqueous solutions. The amplitude of the zero crossing first derivative spectra at 670 nm and 532 nm were selected for the determination of BG and CV, respectively. Significant factors influencing the extraction of BG and CV such as sample pH, kind of extraction solvent, amount of extractant, extraction and centrifuging times and ionic strength were investigated. Under the optimal conditions, the calibration curves for the simultaneous determination of both dyes were found to be linear in the range of 10-500 μg L -1 with detection limits (LODs) of 2.7 μg L -1 and 1.4 μg L -1 for BG and CV, respectively. The relative standard deviation (RSD%) for five replicate simultaneous determinations of BG and CV were 4.7% and 1.7%, respectively. Extraction efficiencies of the BG and CV dyes in the presence of interfering ions were also investigated. Sample preparation based on the quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction combined with the IL-DLLME method and zero crossing first derivative spectrophotometric detection was applied for the simultaneous analysis of BG and CV in fish and water samples with quantitative recoveries., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Chemical compounds are useful to perturb biological functions in the same way as classical genetic approaches take advantage of mutations at the DNA level to perturb gene function. The use of bioactive chemicals currently called chemical genetic is especially valuable for cell biology. Chemical genetic approaches allow perturbations of cellular processes post-germination in a given time window controlling the severity of the effect by modifying or modulating the dose and/or the period of the treatment. Additionally, compounds can be applied directly to different mutants and translational fluorescent reporters/marker lines, expanding the repertoire of experimental setups addressing cell biology research. In this chapter, we describe standard protocols to visualize vacuole morphology and trafficking to the vacuole and the use of bioactive compounds as a proxy to study these biological processes.

The isolation of vacuoles is an essential step to unravel the important and complex functions of this organelle in plant physiology. Here, we describe a method for the isolation of vacuoles from Catharanthus roseus leaves involving a simple procedure for the isolation of protoplasts, and the application of a controlled osmotic/thermal shock to the naked cells, leading to the release of intact vacuoles, which are subsequently purified by density gradient centrifugation. The purity of the isolated intact vacuoles is assayed by microscopy, western blotting, and measurement of vacuolar (V)-H + -ATPase hydrolytic activity. Finally, membrane functionality and integrity is evaluated by measuring the generation of a transtonoplast pH gradient by the V-H + -ATPase and the V-H + -pyrophosphatase, also producing further information on vacuole purity.

In plant cells, vacuoles are extremely important for growth and development, and influence important cellular functions as photosynthesis, respiration, and transpiration. Plant cells contain lytic and storage vacuoles, whose size can be different depending on cell type and tissue developmental stage. One of the main roles of vacuoles is to regulate the cell turgor in response to different stimuli. Thus, studying the morphology, dynamics, and physiology of vacuole is fundamentally important to advance knowledge in plant cell biology at large. The availability of fluorescent probes allows marking vacuoles in multiple ways. These may be fast, when using commercially available chemical dyes, or relatively slow, in the case of specific genetically encoded markers based on proteins directed either to the membrane of the vacuole (tonoplast) or to the vacuole lumen. Any of these approaches provides useful information about the morphology and physiology of the vacuole.

A series of optimized protocols to isolate vacuoles from both yeast and plant cells, and to characterize the purified organelles at a functional and structural level, are described. For this purpose, we took advantage of the combined use of cell fractionation techniques with different fluorescence-based approaches namely flow cytometry, fluorescence microscopy and spectrofluorimetry. These protocols altogether constitute valuable tools for the study of vacuole structure and function, as well as for the high-throughput screening of drug libraries to identify new molecules that target the vacuole.