Al/Cu-PILC as a Photo-Fenton Catalyst: Paracetamol Mineralization.

Pillared clays have shown to effectively catalyze the photo-Fenton process without the necessity of acidic conditions, which is a very attractive feature from the perspective of environmentally friendly processes, especially when high natural abundance of chemical elements are incorporated. In this work, the catalytic activity of Al/Cu interlayered pillared clays for the degradation and mineralization of paracetamol through a photo-Fenton-like process was investigated. Al/Cu-pillared clays were prepared by adding ane Al/Cu pillaring solution to a bentonite suspension. X-ray diffraction (XRD) confirmed the enlargement of the interlayer space of the clay provoked by the pillaring process and Al and Cu species in the prepared samples were verified by atomic absorption spectroscopy (AAS). The specific surface area of pure bentonite was 2-fold increased after the Al/Cu pillaring process. A synthetic paracetamol solution with an initial concentration of 100 ppm was prepared for the assessment of the activity of the prepared materials. Different catalyst concentrations were tested (0.2, 0.5, 0.75, and 1 g L-1) and the complete removal of paracetamol was achieved in all cases, but the highest mineralization rate (69.8 mg total organic carbon (TOC) gcat -1 h-1) corresponds to the catalyst loading of 0.5 g L-1. An ultraviolet-C (UVC) light source was employed, and no adjustment of the pH to acidic conditions was needed to achieve these results. Liquid chromatography coupled to mass spectroscopy (LC-MS) was employed to identify the reaction intermediates of paracetamol degradation. A proposed pathway for the oxidation of paracetamol molecule is presented. The effect of Cu content in the pillared clay and the stability and reusability of the catalyst were also assessed. The kinetic constants of paracetamol removal were 0.2318 and 0.0698 min-1, under photo-Fenton and UV + H2O2 processes, respectively.

An improved method for the determination of cannabidiol in topical products using ultrasound-assisted extraction and gas chromatography-mass spectrometry.

The recent surge in the sale of cannabidiol (CBD)-based topicals has risen rapidly in recent years, as it can be used to treat a multitude of skin disorders. However, there is minimal regulation concerning actual CBD content in these products. Topicals on the market may contain various concentrations of CBD and may be combined with a range of other compounds. The concentration of CBD has to be determined before the products enter the market. For this reason, a selective analytical method was developed using a 23 factorial design; and validated to determine CBD content in various topicals based on ultrasound-assisted extraction (UAE) followed by gas chromatography coupled to mass spectrometry (GC-MS). The method showed good precision (relative standard deviation ≤ 7.7%), accuracy at three concentration levels (recovery > 97.9%) for three different matrices, acceptable linearity (R2 > 0.99), and limit of detection (0.05 µg/mg). The method was successfully applied to the analysis of five commercial topicals. The proposed method is rapid, sensitive, precise, and accurate. In addition, it does not require derivatization and it is suitable for the determination of CBD in topicals for quality control purposes.

Recent advances in analysis of bisphenols and their derivatives in biological matrices.

Biomonitoring is a very useful tool to evaluate human exposure to endocrine-disrupting compounds (EDCs), like bisphenols (BPs), which are widely used in the manufacture of plastics. The development of reliable analytical methods is key in the field of public health surveillance to obtain biomonitoring data to determine what BPs are reaching people's bodies. This review discusses recent methods for the quantitative measurement of bisphenols and their derivatives in biological samples like urine, blood, breast milk, saliva, and hair, among others. We also discuss the different procedures commonly used for sample treatment, which includes extraction and clean-up, and instrumental techniques currently used to determine these compounds. Sample preparation techniques continue to play an important role in the analysis of complex matrices, for liquid matrices the most commonly employed is solid-phase extraction, although microextraction techniques are gaining importance in this field, and for solid samples ultrasound-assisted extraction. The main instrumental techniques used are liquid and gas chromatography coupled with mass spectrometry. Finally, we present data on the main parameters obtained in the validation of the revised methods. This review focuses on various methods developed and applied for trace analysis of bisphenols, their conjugates, halogenated derivatives, and diglycidyl ethers in biological samples to enable the required selectivity and sensitivity. For this purpose, a review is carried out of the most recent relevant publications from 2016 up to present.

A targeted review on fate, occurrence, risk and health implications of bisphenol analogues.

Due to its widespread applications and its ubiquitous occurrence in the environment, bisphenol A (BPA) and its alternatives have gained increasing attention, especially in terms of human safety. Like BPA, alternatives such as bisphenol S (BPS), bisphenol F (BPF), and bisphenol AF (BPAF) have also been identified to be endocrine-disrupting chemicals (EDCs). Hence, in this study, we reviewed the literature of BPA and its alternatives mainly published between the period 2018-2020, including their occurrences in the environment, human exposure, and adverse health effects. The review shows that bisphenols are prevalent in the environment with BPA, BPS, and BPF being the most ubiquitous in the environment worldwide, though BPA remains the most abundant bisphenol. However, the levels of BPS and BPF in different environmental media have been constantly increasing and their fates and health risks are being evaluated. The studies show that humans and animals are exposed to bisphenols in many different ways through inhalation and ingestion and the exposure can have serious health effects. Urinary bisphenols (BPs) levels were frequently reported to be positively associated with different health problems such as cancer, infertility, cardiovascular diseases, diabetes and neurodegenerative diseases. Our literature study also shows that BPs generate reactive oxygen species and disrupt various signalling pathways, which could lead to the development of chronic diseases. Activated carbon-based and chitosan-based sorbents have been widely utilized in the removal of BPA in aqueous solutions. In addition, enzymes and microorganisms have also been getting much attention due to their high removal efficiencies.

Conditions on the Mexican moulting grounds influence feather colour and carotenoids in Bullock's orioles (Icterus bullockii).

Carotenoid-based plumage coloration plays a critical role for both inter- and intrasexual communication. Habitat and diet during molt can have important consequences for the development of the ornamental signals used in these contexts. When molt occurs away from the breeding grounds (e.g., pre-alternate molt on the wintering grounds, or stopover molt), discerning the influence of habitat and diet can be particularly important, as these effects may result in important carryover effects that influence territory acquisition or mate choice in subsequent seasons. Several species of songbirds in western North America, including the Bullock's oriole (Icterus bullockii), migrate from the breeding grounds to undergo a complete prebasic (post-breeding) molt at a stopover site in the region affected by the Mexican monsoon climate pattern. This strategy appears to have evolved several times independently in response to the harsh, food-limited late-summer conditions in the arid West, which contrast strongly with the high productivity driven by heavy rains that is characteristic of the Mexican monsoon region. Within this region, individuals may be able to optimize plumage coloration by molting in favourable areas characterized by high resource abundance. We used stable isotope analysis (δ13C, δ15N) to ask whether the diet and molt habitat/location of Bullock's orioles influenced their expression of carotenoid-based plumage coloration as well as plumage carotenoid content and composition. Bullock's orioles with lower feather δ15N values acquired more colorful plumage (orange-shifted hue) but had feathers with lower total carotenoid concentration, lower zeaxanthin concentration, and marginally lower canthaxanthin and lutein concentration. Examining factors occurring throughout the annual cycle are critical for understanding evolutionary and ecological processes. Here, we demonstrate that conditions experienced during a stopover molt, occurring hundreds to thousands of kilometers from the breeding grounds, influence the production of ornamental plumage coloration, which may carryover to influence inter- and intrasexual signaling in subsequent seasons.

Micellar electrokinetic chromatography method development for simultaneous determination of thiabendazole, carbendazim, and fuberidazole.

Thiabendazole (TBz), carbendazim (CBz), and fuberidazole (FBz) are systemic benzimidazole-type fungicides used for pre- and post-harvest treatment to control various types of fungal diseases on a variety of crops. Significant levels of these fungicides could alter the composition or flavour of crops, and being possible carcinogens, they could also pose risks for humans and the environment. A mode of capillary electrophoresis called micellar electrokinetic chromatography (MEKC) was investigated for the determination of these three benzimidazole fungicides. The study involved two kinds of surfactants in which several experimental conditions were optimized, i.e., buffer concentration, pH, micelle concentration, and percent organic modifier (methanol). Using the optimum experimental conditions, the fungicides were successfully separated by MEKC. The limits of detection and quantification were in the range of 0.6-0.7 and 2.1-2.5 mg L(-1), respectively, and the calibration curves were linear over the range of 5-60 mg L(-1) for the three fungicides. The potential of the proposed MEKC method was demonstrated by analyzing water samples which were fortified with the fungicides. The proposed method enabled simultaneous determination of the three benzimidazole fungicides and method validation with spiked water samples yielded satisfactory quantitative recoveries for all the three fungicides.

Rapid determination of total conjugated linoleic acid content in select Canadian cheeses by (1)h NMR spectroscopy.

The application of (1)H nuclear magnetic resonance (NMR) spectroscopy to the measurement of conjugated linoleic acid (CLA) content in the lipid fraction of dairy products is both a novel and inviting alternative to traditional methods such as gas chromatography (GC), which can require time-consuming sample derivatization. In this work, a newly developed, rapid, and reliable lipid extraction protocol was combined with simple, nondestructive (1)H NMR spectroscopic analysis to measure the total CLA content in CLA standards and in various Canadian cheeses from conventional, organic, and grass-fed dairy sources. The total CLA concentrations (mg/g cheese) obtained using these new extraction and analysis methods were consistent with amounts found using the modified Folch extraction and GC analysis (correlation coefficient of 0.948). Results showed that cheeses from exclusively grass-fed dairy cows were significantly higher in total CLA content than either conventional or organic cheese.

Separation of dietary omega-3 and omega-6 fatty acids in food by capillary electrophoresis.

A lower dietary omega-6/omega-3 (n-6/n-3) fatty acid ratio (<4) has been shown to be beneficial in preventing a number of chronic illnesses. Interest exists in developing more rapid and sensitive analytical methods for profiling fatty acid levels in foods. An aqueous CE method was developed for the simultaneous determination of 15 n-3 and n-6 relevant fatty acids. The effect of pH and concentration of buffer, type and concentration of organic modifier, and additive on the separation was investigated in order to determine the best conditions for the analysis. Baseline separations of the 15 fatty acids were achieved using 40 mM borate buffer at pH 9.50 containing 50 mM SDS, 10 mM ß-cyclodextrin, and 10% acetonitrile. The developed CE method has LODs of <5 mg/L and good linearity (R(2) > 0.980) for all fatty acids studied. The proposed method was successfully applied to the determination of n-3 and n-6 fatty acids in flax seed, Udo® oils and a selection of grass-fed and grain-fed beef muscle samples.

The design and synthesis of alanine-based indolicidin derivatives with identical physicochemical properties and their separation using capillary electrophoresis.

Four novel alanine-based indolicidin peptide derivatives were designed containing one WPW motif and two alanine residues, resulting in peptides of similar sequence. The separation of these peptides with identical physicochemical properties including molar mass, charge, and secondary structure as characterized by circular dichroism spectroscopy is very difficult; and the separation of peptides with differing physicochemical properties has only previously been reported. Capillary electrophoresis parameters such as separation buffer concentration, separation buffer pH, capillary length, and separation voltage were investigated to optimize the analysis. Using optimized conditions of a background electrolyte containing 5 mM formic acid of pH 2.0, total capillary length of 51 cm and a voltage of 10 kV enabled a baseline separation of the four peptides. The relative standard deviation of the peak areas and migration times for method repeatability (n = 3) were found to be lower than 8% and 3%, respectively. In addition, reasoning for the separation of these peptides is proposed based on the acidity of the formic acid buffer and the hydrophobic grouping of the tryptophan residues in the peptide primary sequence.

Separation and determination of closely related lantibiotics by micellar electrokinetic chromatography.

A sensitive micellar electrokinetic chromatography (MEKC) method was developed for the separation and determination of four closely related lantibiotics: gallidermin, cinnamycin, duramycin and nisin. Factors affecting the separation of the lantibiotics such as pH, phosphate buffer concentration, SDS concentration and wavelength for UV detection were investigated. By optimizing these experimental conditions, successful separation was achieved between class 1A lantibiotics (nisin and gallidermin) and class 1B lantibiotics (duramycin and cinnamycin). The four lantibiotics were separated within 12 min in 50 mM phosphate buffer at pH 3.95 +/- 0.1 containing 80 mM SDS with UV detection of 214 nm. The LOD (S/N = 3) were 61 ng/mL for gallidermin, 57 ng/mL for cinnamycin, 55 ng/mL for duramycin and 58 ng/mL for nisin. The method was successfully applied to real samples such as fermentation broth, bovine colostrum and predrop beer. This method yielded satisfactory results, with quantitative recoveries of spiked lantibiotics in the three samples ranging from 86.1 to 99.6%.

Determination of thermodynamic pKa values of benzimidazole and benzimidazole derivatives by capillary electrophoresis.

Thermodynamic pK(a) values for benzimidazole and several substituted benzimidazoles were determined by CE. Electrophoretic mobilities of benzimidazoles were determined by CE at different pH levels and ionic strengths. The dependence of electrophoretic mobilities on pH was used to obtain pK(a) values at different ionic strengths. Extrapolations to zero ionic strength were used to determine the thermodynamic pK(a) values. Using this method the thermodynamic pK(a) values of 15 benzimidazoles were determined and found to range from 4.48 to 7.38. Results from the CE measurements were compared with spectrophotometric measurements which were evaluated at wavelengths where the highest absorbance difference for varying pH was recorded. The two analytical techniques were in good agreement.