A rapid method for the quantification of urinary phthalate monoesters: A new strategy for the assessment of the exposure to phthalate ester by solid‐phase microextraction with gas chromatography and tandem mass spectrometry

In the following work, a new method for the analysis of the phthalate monoesters in human urine was reported. Phthalate monoesters are metabolites generated as a result of phthalate exposure. In compliance with the dictates of Green Analytical Chemistry, a rapid and simple protocol was developed and optimized for the quantification of phthalate monoesters (i.e., monoethyl phthalate, monoisobutyl phthalate, mono‐n‐butyl phthalate, mono‐(2‐ethylhexyl) phthalate, mono‐n‐octyl phthalate, monocyclohexyl phthalate, mono‐isononyl phthalate) in human urine, which entails preceding derivatization with methyl chloroformate combined with the use of commercial solid phase microextraction and the analysis by gas chromatography‐triple quadrupole mass spectrometry. The affinity of the derivatized analytes toward five commercial coatings was evaluated, and in terms of analyte extraction, the best results were reached with the use of the divinylbenzene/carboxen/polydimethylsiloxane fiber. The multivariate approach of experimental design was used to seek for the best working conditions of the derivatization reaction and the solid phase microextraction, thus obtaining the optimum response values. The proposed method was validated according to the guidelines issued by the Food and Drug Administration achieving satisfactory values in terms of linearity, sensitivity, matrix effect, intra‐ and inter‐day accuracy, and precision.     

Bioinspired benzoxanthene lignans as a new class of antimycotic agents: synthesis and Candida spp. growth inhibition

Abstract

In this work we synthetized the bioinspired benzoxanthene lignans (BXLs) 3, 14–22, and the phenazine derivative 23 as potential antimycotic agents. MICs and MFCs against Candida strains were determined. In a preliminary screening, compounds 3, 15, 20, 21, 22 were substantially inactive. Compounds 14 and 17 showed antifungal activity, being able to inhibit the growth of the majority of Candida strains with MIC values in the range 4.6–19.2?µM (14) and 26.0–104.3?µM (17); for three strains, the MICs were lower than those obtained using the antimycotic drug fluconazole. The three BXLs 18, 19 and 23 showed some MIC values lower than that of fluconazole; 18 was also active against two non-albicans Candida strains resistant to fluconazole. Phenazine 23, although active only against one strain (MIC?=?1.3?µM), was one order of magnitude more potent than fluconazole. All the BXLs were fungicidal.     

The Maximal Operator Associated to a Nonsymmetric Ornstein–Uhlenbeck Semigroup

Let (ℋ _t ) _t≥0 be the Ornstein–Uhlenbeck semigroup on ℝ ^d with covariance matrix I and drift matrix λ(R−I), where λ>0 and R is a skew-adjoint matrix, and denote by γ _∞ the invariant measure for (ℋ _t ) _t≥0. Semigroups of this form are the basic building blocks of Ornstein–Uhlenbeck semigroups which are normal on L ²(γ _∞). We prove that if the matrix R generates a one-parameter group of periodic rotations, then the maximal operator ℋ_* f(x)=sup  _t≥o |ℋ _t f(x)| is of weak type 1 with respect to the invariant measure γ _∞. We also prove that the maximal operator associated to an arbitrary normal Ornstein–Uhlenbeck semigroup is bounded on L ^p (γ _∞) if and only if 1<p≤∞.      

A chiral electrophilic selenium reagent to promote the kinetic resolution of racemic allylic alcohols

[reaction: see text] The first example of a kinetic resolution process promoted by electrophilic selenium reagents is reported. Racemic allylic alcohols react with half equivalents of a selenenylating agent in methanol leading to the regiospecific formation of the corresponding addition products with a very high level of facial selectivity (from 95:5 to 98:2 dr). The unreacted alcohols can be recovered in an optically enriched form (from 90 to 94% ee).     

Development of Electrochemical Platform Based on Molecularly Imprinted Poly(methacrylic acid) Grafted on Iniferter-modified Carbon Nanotubes for 17β-Estradiol Determination in Water Samples

This paper describes the development of a new electrochemical sensor for 17β-estradiol (E2) determination based on glassy carbon electrode (GCE) modified with molecularly imprinted polymer grafted onto iniferter-multiwall carbon nanotubes surface (MIP-MWCNT) and dihexadecyl-hydrogen-phosphate (DHP). The electrochemical method was based on closed-circuit preconcentration of E2 in 0.1 mol L⁻¹ phosphate buffer (pH 7.0) during 500 s. Upon preconcentration, E2 was determined by differential pulse voltammetry (DPV) exhibiting a limit of detection of 0.01 μmol L⁻¹. The sensor exhibited higher selectivity toward E2 and it was applied for E2 determination in natural water samples, with accuracy attested by HPLC-DAD.     

Structural Characterisation of Complex Layered Double Hydroxides and TGA‐GC‐MS Study on Thermal Response and Carbonate Contamination in Nitrate‐ and Organic‐Exchanged Hydrotalcites

Layered double hydroxides (LDHs) are versatile materials used for intercalating bioactive molecules in the fields of pharmaceuticals, nutraceuticals and cosmetics, with the purpose of protecting them from degradation, enhancing their water solubility to increase bioavailability and improving their pharmacokinetic properties and formulation stability. Moreover, LDHs are used in various technological applications to improve stability and processability. The crystal chemistry of hydrotalcite‐like compounds was investigated by X‐ray powder diffraction (XRPD), automated electron diffraction tomography (ADT) and thermogravimetric analysis (TGA)‐GC‐MS to shed light on the mechanisms involved in ion exchange and absorption of contaminants, mainly carbonate anions. For the first time, ADT allowed a structural model of LDH_NO₃ to be obtained from experiment, shedding light on the conformation of nitrate inside LDH and on the loss of crystallinity due to the layer morphology. The ADT analysis of a hybrid LDH sample (LDH_EUS) clearly revealed an increase in defectivity in this material. XRPD demonstrated that the presence of carbonate can influence the intercalation of organic molecules into LDH, since CO₃‐contaminated samples tend to adopt d spacings that are approximate multiples of the d spacing of LDH_CO₃. TGA‐GC‐MS allowed intercalated and surface‐ adsorbed organic molecules to be distinguished and quantified, the presence and amount of carbonate to be confirmed, especially at low concentrations (<2 wt %), and the different types and strengths of adsorption to be classified with respect to the temperature of elimination.     

New Halogen-Containing Drugs Approved by FDA in 2021: An Overview on Their Syntheses and Pharmaceutical Use

This review describes the recent Food and Drug Administration (FDA)-approved drugs (in the year 2021) containing at least one halogen atom (covalently bound). The structures proposed throughout this work are grouped according to their therapeutical use. Their synthesis is presented as well. The number of halogenated molecules that are reaching the market is regularly preserved, and 14 of the 50 molecules approved by the FDA in the last year contain halogens. This underlines the emergent role of halogens and, in particular, of fluorine and chlorine in the preparation of drugs for the treatment of several diseases such as viral infections, several types of cancer, cardiovascular disease, multiple sclerosis, migraine and inflammatory diseases such as vasculitis.     

Polydimethylsiloxane amino functionalized sponge for adsorption of copper in water

Journal of Sol-Gel Science and Technology - This work describes the preparation and use of a polydimethylsiloxane sponge amino functionalized for the adsorption of copper in water. The sponge was...