Analytical method for biomonitoring of endocrine-disrupting compounds (bisphenol A,parabens, perfluoroalkyl compounds and a brominated flame retardant) in human hair by liquid chromatography-tandem mass spectrometry

In this paper, a method for the determination of four groups of endocrine-disrupting compounds in human hair is proposed. Target compounds were a plastic monomer (bisphenol A), three parabens commonly used as preservatives (methylparaben, ethylparaben and propylparaben), six perfluoroalkyl compounds commonly used as water, oil and dirt repellents (perfluorooctane sulfonic acid and five perfluoroalkyl carboxylic acids, with alkyl chains from four to eight carbon atoms) and a brominated flame retardant (hexabromocyclododecane). All of them are of especial concern to human health because they are utilized in many everyday products. The method is based on hair incubation with methanol/acetic acid solution (85:15, v/v), extraction with acetone for 15 min in an ultrasonic bath and analysis by liquid chromatography-electrospray-tandem mass spectrometry in negative ionization mode. Limits of quantification in hair samples ranged from 0.6 ng g⁻¹ to 6.1 ng g⁻¹, except for hexabromocyclododecane (36 ng g⁻¹). Recoveries were higher than 69%. Intra-day and inter-day precision, expressed as relative standard deviation, were lower than 15% and 10%, respectively. The applicability of the method was proven by analyzing the target compounds in hair samples from six volunteers. High frequencies of detection and concentrations were obtained for bisphenol A (83% of samples; concentrations up to 158 ng g⁻¹) and parabens (100% of samples; concentrations up to 624 ng g⁻¹). Lower concentrations were detected for the perfluoroalkyl compounds (up to 13 ng g⁻¹). Hexabromocyclododecane was not detected.     

Melanopsin and the Non‐visual Photochemistry in the Inner Retina of Vertebrates

Melanopsin (Opn4), a member of the G‐protein‐coupled receptor family, is a vitamin A‐based opsin in the vertebrate retina that has been shown to be involved in the synchronization of circadian rhythms, pupillary light reflexes, melatonin suppression and other light‐regulated tasks. In nonmammalian vertebrates there are two Opn4 genes, Opn4m and Opn4x, the mammalian and Xenopus orthologs respectively. Opn4x is only expressed in nonmammalian vertebrates including reptiles, fish and birds, while Opn4m is found in a subset of retinal ganglion cells (RGCs), the intrinsically photosensitive (ip) RGCs of the inner retina of both mammals and nonmammalian vertebrates. All opsins described utilize retinaldehyde as chromophore, photoisomerized from 11‐cis‐ to all‐trans‐retinal upon light exposure. Visual retinal photoreceptor cones and rods, responsible for day and night vision respectively, recycle retinoids through a process called the visual cycle that involves the retinal pigment epithelium or glial Müller cells. Although Opn4 has been characterized as a bistable photopigment, little is known about the mechanism/s involved in its chromophore regeneration. In this review, we will attempt to shed light on the visual cycle taking place in the inner retina and discuss the state of the art in the nonvisual photochemistry of vertebrates.     

Synthesis and characterization of polyesters derived from sebacic acid,hexanediol, and hydroquinone

Oils and fats derived from animals and plants provide a good renewable source for polymer precursors. In this investigation, fatty acids derived from plant oils and diols were used as monomers to produce polyesters by melt polycondensation. Sebacic acid, hexanediol, and hydroquinone were used as precursors in the polymer synthesis. The polymers were characterized by gel permeation chromatography, Fourier transform infrared spectroscopy, three-bending point flexural test, X-ray diffraction, tensile testing, and contact angle. The resulting polyesters were blended with epoxies to create materials with an increased elongation at break without affecting other mechanical properties.     

Sequential Voltammetric Determination of Uranium,Cadmium and Lead by Using the ex situ Bismuth Film Electrode: Application to Phosphate Fertilizers

A sequential voltammetric procedure for the determination of uranium, cadmium and lead was investigated at an ex situ bismuth film electrode (BiFE). First, the adsorptive stripping voltammetry was applied to assay the U(VI)‐cupferron complex in the differential pulse mode (detection limit of 1.0 µg L^?1, 200 s accumulation time). Through the manipulation of the same aliquot of the sample, efforts were made to quantify cadmium and lead by square wave anodic stripping voltammetry. Detection limits of 2.03 µg L^?1 for Cd (II) and 2.43 µg L^?1 for Pb (II) were calculated (100 s accumulation time). The methodology was successfully applied to phosphate fertilizer samples after open vessel wet decomposition (HNO₃/H₂O₂). The following value ranges were evaluated: U (VI) 37.2–150 mg kg^?1, Pb (II) 78.3–204 mg kg^?1 and Cd (II) 44.1–71.6 mg kg^?1. Validation was performed by using the standard reference materials SRM‐695 – phosphate fertilizer – and SRM‐1643e – water.     

Benign‐by‐Design Solventless Mechanochemical Synthesis of Three‐, Two‐, and One‐Dimensional Hybrid Perovskites

Organic–inorganic hybrid perovskites have attracted significant attention owing to their extraordinary optoelectronic properties with applications in the fields of solar energy, lighting, photodetectors, and lasers. The rational design of these hybrid materials is a key factor in the optimization of their performance in perovskite‐based devices. Herein, a mechanochemical approach is proposed as a highly efficient, simple, and reproducible method for the preparation of four types of hybrid perovskites, which were obtained in large amounts as polycrystalline powders with high purity and excellent optoelectronics properties. Two archetypal three‐dimensional (3D) perovskites (MAPbI₃ and FAPbI₃) were synthesized, together with a bidimensional (2D) perovskite (Gua₂PbI₄) and a “double‐chain” one‐dimensional (1D) perovskite (GuaPbI₃), whose structure was elucidated by X‐ray diffraction.     

Uniqueness of Radial Solutions for the Fractional Laplacian

We prove general uniqueness results for radial solutions of linear and nonlinear equations involving the fractional Laplacian (?Δ)^s with s ? (0,1) for any space dimensions N ≥ 1. By extending a monotonicity formula found by Cabré and Sire , we show that the linear equation has at most one radial and bounded solution vanishing at infinity, provided that the potential V is radial and nondecreasing. In particular, this result implies that all radial eigenvalues of the corresponding fractional Schrödinger operator H = (?Δ)^s + V are simple. Furthermore, by combining these findings on linear equations with topological bounds for a related problem on the upper half‐space , we show uniqueness and nondegeneracy of ground state solutions for the nonlinear equation for arbitrary space dimensions N ≥ 1 and all admissible exponents α > 0. This generalizes the nondegeneracy and uniqueness result for dimension N = 1 recently obtained by the first two authors and, in particular, the uniqueness result for solitary waves of the Benjamin‐Ono equation found by Amick and Toland .© 2016 Wiley Periodicals, Inc.     

Asymptotic behavior of the p-torsion functions as p goes to 1

Let \({\Omega}\) be a Lipschitz bounded domain of \({\mathbb{R}^N}\), \({N\geq2}\), and let \({u_p\in W_0^{1,p}(\Omega)}\) denote the p-torsion function of \({\Omega}\), p > 1. It is observed that the value 1 for the Cheeger constant \({h(\Omega)}\) is threshold with respect to the asymptotic behavior of u_p, as \({p\rightarrow 1^+}\), in the following sense: when \({h(\Omega) > 1}\), one has \({\lim_{p\rightarrow 1^+}\left\|u_{p}\right\| _{L^\infty(\Omega)}=0}\), and when \({h(\Omega) < 1}\), one has \({\lim_{p\rightarrow 1^+}\left\|u_p\right\| _{L^\infty(\Omega)}=\infty}\). In the case \({h(\Omega)=1}\), it is proved that \({\limsup_{p\rightarrow1^+}\left\|u_p\right\|_{L^\infty(\Omega)}<\infty}\). For a radial annulus \({\Omega_{a,b}}\), with inner radius a and outer radius b, it is proved that \({\lim_{p\rightarrow 1^+}\left\|u_p\right\| _{L^\infty(\Omega_{a,b})}=0}\) when \({h(\Omega_{a,b})=1}\).     

Oxidative degradations of the side chain of unsaturated ent-labdanes. Part II

A route for the degradation of the side chain of ent-labdane derivatives has been devised, giving the useful synthon 2beta,12-dihydroxy-13,14,15,16,17-pentanor-ent-labdane-8-one (8). The use of this compound in the preparation of terpenylquinone derivatives shall be reported elsewhere. In addition we have synthesized the compound 2beta,12-diacetoxy-8beta,17-epoxy-13,14,15,16-tetranor-ent-labdane (10), which upon catalytic epoxide ring opening in alkaline or acid media gave rise in all cases to the formation of tricyclicc ompounds.