Simultaneous Quantification of 16 Bisphenol Analogues in Food Matrices.

Exposure to bisphenol analogues can occur in several ways throughout the food production chain, with their presence at higher concentrations representing a risk to human health. This study aimed to develop effective analytical methods to simultaneously quantify BPA and fifteen bisphenol analogues (i.e., bisphenol AF, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol P, bisphenol PH, bisphenol S, bisphenol Z, bisphenol TMC, and tetramethyl bisphenol F) present in canned foods and beverages. Samples of foods and beverages available in the Swiss and EU markets (n = 22), including canned pineapples, ravioli, and beer, were prepared and analyzed using QuEChERS GC-MS. The quantification method was compared to a QuEChERS LC-MS/MS analysis. This allowed for the selective and efficient simultaneous quantitative analysis of bisphenol analogues. Quantities of these analogues were present in 20 of the 22 samples tested, with the most frequent analytes at higher concentrations: BPA and BPS were discovered in 78% and 48% of cases, respectively. The study demonstrates the robustness of QuEChERS GC-MS for determining low quantities of bisphenol analogues in canned foods. However, further studies are necessary to achieve full knowledge of the extent of bisphenol contamination in the food production chain and its associated toxicity.

Electro- and photochemical H2 generation by Co(ii) polypyridyl-based catalysts bearing ortho-substituted pyridines.

Cobalt(ii) complexes featuring hexadentate amino-pyridyl ligands have been recently discovered as highly active catalysts for the Hydrogen Evolution Reaction (HER), whose high performance arises from the possibility of assisting proton transfer processes via intramolecular routes involving detached pyridine units. With the aim of gaining insights into such catalytic routes, three new proton reduction catalysts based on amino-polypyridyl ligands are reported, focusing on substitution of the pyridine ortho-position. Specifically, a carboxylate (C2) and two hydroxyl substituted pyridyl moieties (C3, C4) are introduced with the aim of promoting intramolecular proton transfer which possibly enhances the efficiency of the catalysts. Foot-of-the-wave and catalytic Tafel plot analyses have been utilized to benchmark the catalytic performances under electrochemical conditions in acetonitrile using trifluoroacetic acid as the proton source. In this respect, the cobalt complex C3 turns out to be the fastest catalyst in the series, with a maximum turnover frequency (TOF) of 1.6 (±0.5) × 105 s-1, but at the expense of large overpotentials. Mechanistic investigations by means of Density Functional Theory (DFT) suggest a typical ECEC mechanism (i.e. a sequence of reduction - E - and protonation - C - events) for all the catalysts, as previously envisioned for the parent unsubstituted complex C1. Interestingly, in the case of complex C2, the catalytic route is triggered by initial protonation of the carboxylate group resulting in a less common (C)ECEC mechanism. The pivotal role of the hexadentate chelating ligand in providing internal proton relays to assist hydrogen elimination is further confirmed within this novel class of molecular catalysts, thus highlighting the relevance of a flexible polypyridine ligand in the design of efficient cobalt complexes for the HER. Photochemical studies in aqueous solution using [Ru(bpy)3]2+ (where bpy = 2,2'-bipyridine) as the sensitizer and ascorbate as the sacrificial electron donor support the superior performance of C3.

Rethinking Electronic Effects in Photochemical Hydrogen Evolution Using CuInS2@ZnS Quantum Dots Sensitizers.

Molecular catalysts based on coordination complexes for the generation of hydrogen via photochemical water splitting exhibit a large versatility and tunability of the catalytic properties through chemical functionalization. In the present work, we report on light-driven hydrogen production in an aqueous solution using a series of cobalt polypyridine complexes as hydrogen evolving catalysts (HECs) in combination with CuInS2@ZnS quantum dots (QDs) as sensitizers, and ascorbate as the electron donor. A peculiar trend in activity has been observed depending on the substituents present on the polypyridine ligand. This trend markedly differs from that previously recorded using [Ru(bpy)3]2+ (where bpy = 2,2'-bipyridine) as the sensitizer and can be ascribed to different kinetically limiting pathways in the photochemical reaction (viz. protonation kinetics with the ruthenium chromophore, catalyst activation via electron transfer from the QDs in the present system). Hence, this work shows how the electronic effects on light-triggered molecular catalysis are not exclusive features of the catalyst unit but depend on the whole photochemical system.

Recent findings and future directions in photosynthetic hydrogen evolution using polypyridine cobalt complexes.

The production of hydrogen gas using water as the molecular substrate currently represents one of the most challenging and appealing reaction schemes in the field of artificial photosynthesis (AP), i.e., the conversion of solar energy into fuels. In order to be efficient, this process requires a suitable combination of a light-harvesting sensitizer, an electron donor, and a hydrogen-evolving catalyst (HEC). In the last few years, cobalt polypyridine complexes have been discovered to be competent molecular catalysts for the hydrogen evolution reaction (HER), showing enhanced efficiency and stability with respect to previously reported molecular species. This perspective collects information about all relevant cobalt polypyridine complexes employed for the HER in aqueous solution under light-driven conditions in the presence of Ru(bpy)32+ (where bpy = 2,2'-bipyridine) as the photosensitizer and ascorbate as the electron donor, trying to highlight promising chemical motifs and aiming towards efficient catalytic activity in order to stimulate further efforts to design molecular catalysts for hydrogen generation and allow their profitable implementation in devices. As a final step, a few suggestions for the benchmarking of HECs employed under light-driven conditions are introduced.

Concentrations of Seven Phthalate Monoesters in Infants and Toddlers Quantified in Urine Extracted from Diapers.

Carrying out exposure studies on children who are not toilet trained is challenging because of the difficulty of urine sampling. In this study, we optimized a protocol for urine collection from disposable diapers for the analysis of phthalate metabolites. The exposure of Swiss children (n = 113) between 6 months and 3 years of life to seven phthalates was assessed by gas chromatography-mass spectrometry measurements. The study showed limited exposures to phthalates, with only 22% of the samples containing some of the metabolites investigated. The three most frequently detected metabolites were monoethyl phthalate, mono-cyclohexyl phthalate, and mono-benzyl phthalate. We also detected mono-n-octyl phthalate and mono(3,5,5-trimethylhexyl) phthalate, which have rarely been observed in urine from infants and toddlers; therefore, di-n-octyl phthalate and bis(3,5,5-trimethylhexyl) phthalate can be considered as potentially new emerging phthalates. This study presents an initial snapshot of the Swiss children's exposure to phthalates and provides a promising approach for further phthalate biomonitoring studies on young children using disposable diapers as urine sampling technique.

Rationalizing Photo-Triggered Hydrogen Evolution Using Polypyridine Cobalt Complexes: Substituent Effects on Hexadentate Chelating Ligands.

Four novel polypyridine cobalt(II) complexes were developed based on a hexadentate ligand scaffold bearing either electron-withdrawing (-CF3 ) or electron-donating (-OCH3 ) groups in different positions of the ligand. Experiments and theoretical calculations were combined to perform a systematic investigation of the effect of the ligand modification on the hydrogen evolution reaction. The results indicated that the position, rather than the type of substituent, was the dominating factor in promoting catalysis. The best performances were observed upon introduction of substituents on the pyridine moiety of the hexadentate ligand, which promoted the formation of the Co(II)H intermediate via intramolecular proton transfer reactions with low activation energy. Quantum yields of 11.3 and 10.1 %, maximum turnover frequencies of 86.1 and 76.6 min-1 , and maximum turnover numbers of 5520 and 4043 were obtained, respectively, with a -OCH3 and a -CF3 substituent.

Multiorder Nonlinear Mixing in Metal Oxide Nanoparticles.

Whereas most of the reports on the nonlinear properties of micro- and nanostructures address the generation of distinct signals, such as second or third harmonic, here we demonstrate that the novel generation of dual output lasers recently developed for microscopy can readily increase the accessible parameter space and enable the simultaneous excitation and detection of multiple emission orders such as several harmonics and signals stemming from various sum and difference frequency mixing processes. This rich response, which in our case features 10 distinct emissions and encompasses the whole spectral range from the deep ultraviolet to the short-wave infrared region, is demonstrated using various nonlinear oxide nanomaterials while being characterized and simulated temporally and spectrally. Notably, we show that the response is conserved when the particles are embedded in biological media opening the way to novel biolabeling and phototriggering strategies.

Exposure to New Emerging Bisphenols Among Young Children in Switzerland.

Restrictions on the use of bisphenol A (BPA) in consumer products led to its replacement by various bisphenol (BP) analogues, yet young children's exposure to these analogues has been poorly characterized so far. This study aimed to characterize infants' and toddlers' exposure to BPA and 14 emerging BP analogues (i.e., bisphenol AF, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C (BPC), bisphenol E, bisphenol F (BPF), bisphenol G, bisphenol M (BPM), bisphenol P, bisphenol PH, bisphenol S (BPS), bisphenol TMC, and bisphenol Z). We extracted infants' and toddlers' urine from diapers (n = 109) collected in Swiss daycare centers as a practical and noninvasive alternative approach to urinary biomonitoring. Bisphenols were present in 47% of the samples, with BPC and BPM being the most frequently detected (23% and 25% of all samples, respectively). The mean concentrations of urinary BPS and BPF were greater than that of BPA. This contrasts with data reported previously. Furthermore, statistical analysis revealed a significant and negative correlation between urinary BPM concentration and the population's age. Our results provide a first characterization of infants' and toddlers' exposure to bisphenols in Switzerland. This knowledge can be used to support ongoing biomonitoring studies and to prioritize exposure reduction and prevention strategies.

Heptacoordinate Co(II) Catalyst for Light-driven Hydrogen Production in Fully Aqueous Medium.

Photocatalytic hydrogen production is an appealing way to store solar energy as chemical fuel. The most studied molecular catalysts for H2 production are based on earth-abundant metals such as Ni, Co and Fe. Efforts have been recently focused on the design of Co complexes with distorted octahedral geometries induced by tetra- or pentapyridyl ligands. We synthesized a new Co(II) complex based on a hexapyridyl ligand that leads to the formation of an unusual heptacoordinate structure. In this paper, we review the characterization of the new catalyst and the optimization of the conditions for hydrogen evolution. The high activity reached after two hours of irradiation under visible light (475 nm) suggests that heptacoordinate cobalt complexes, not used so far in the field of light-driven hydrogen evolution, represent a promising alternative platform for the development of highly active and stable photocatalysts.

Functional Metathesis Catalyst Through Ring Closing Enyne Metathesis: One Pot Protocol for Living Heterotelechelic Polymers.

Enyne ring closing metathesis has been used to synthesize functional group carrying metathesis catalysts from a commercial (Ru-benzylidene) Grubbs' catalysts. The new Grubbs-type ruthenium carbene was used to synthesize living heterotelechelic ROMP polymers without any intermediate purification. Olefin metathesis with a mono substituted alkyne followed by ring closing metathesis with an allylic ether provided efficient access to new functional group carrying metathesis catalysts. Different functional benzylidene and alkylidene derivatives have been investigated in the synthesis of heterotelechelic polymers in one pot.

Hydrogen Atom Transfer (HAT) Processes Promoted by the Quinolinimide-N-oxyl Radical. A Kinetic and Theoretical Study.

A kinetic study of the hydrogen atom transfer (HAT) reactions from a series of organic compounds to the quinolinimide-N-oxyl radical (QINO) was performed in CH3CN. The HAT rate constants are significantly higher than those observed with the phthalimide-N-oxyl radical (PINO) as a result of enthalpic and polar effects due to the presence of the N-heteroaromatic ring in QINO. The relevance of polar effects is supported by theoretical calculations conducted for the reactions of the two N-oxyl radicals with toluene, which indicate that the HAT process is characterized by a significant degree of charge transfer permitted by the π-stacking that occurs between the toluene and the N-oxyl aromatic rings in the transition state structures. An increase in the HAT reactivity of QINO was observed in the presence of 0.15 M HClO4 and 0.15 M Mg(ClO4)2 due to the protonation or complexation with the Lewis acid of the pyridine nitrogen that leads to a further decrease in the electron density in the N-oxyl radical. These results fully support the use of N-hydroxyquinolinimide as a convenient substitute for N-hydroxyphthalimide in the catalytic aerobic oxidations of aliphatic hydrocarbons characterized by relatively high C-H bond dissociation energies.

Heptacoordinate CoII Complex: A New Architecture for Photochemical Hydrogen Production.

The first heptacoordinate cobalt catalyst for light-driven hydrogen production in water has been synthesized and characterized. Photochemical experiments using [Ru(bpy)3 ]2+ as photosensitizer gave a turnover number (TON) of 16300 mol H2 (mol cat.)-1 achieved in 2 hours of irradiation with visible (475 nm) light. This promising result provides a path forward in the development of new structures to improve the efficiency of the catalysis.