Response surface methodology approach for the preparation of a molecularly imprinted polymer for solid‐phase extraction of fenoxycarb pesticide in mussels

The aim of this work was to develop an efficient method for the selective extraction and analysis of fenoxycarb, a carbamate pesticide, in mussel samples using a molecularly imprinted solid‐phase extraction device. The optimization of molecularly imprinted polymer synthesis was performed using the experimental design under the response surface methodology approach. A fast rebinding study and Freundlich isotherm adsorption were carried out to calculate binding capacity B, site number n, and affinity constant K_f. The optimum molecularly imprinted polymer was successfully used as sorbent of a solid‐phase extraction cartridge for the determination of fenoxycarb in real mussel samples. The range of linearity was 0.3–30 mg/L with a correlation coefficient of 0.991. The limit of detection was 0.247 mg/kg. The recovery of fenoxycarb extracted from mussel samples of Mediterranean sea was 97% (n = 3) with relative standard deviation between 6 and 7% proving the reliability of the developed method.     

Stress concentration factor due to a functionally graded ring around a hole in an isotropic plate

The aim of this work is to present an analytical solution to reduce the stress concentration factor (SCF) around a circular hole in an isotropic homogeneous plate subjected to far-field uniaxial loading. In this paper the elastic response of an inhomogeneous annular ring made of functionally graded material (FGM), inserted around a hole of a homogeneous plate, is studied. By assuming that Young’s modulus varies in the radial direction with power law and that Poisson’s ratio is constant, the governing differential equations for plane stress conditions are obtained. Using stress function a general solution in explicit closed form is presented and the SCF investigated to highlight the inhomogeneity effects. Furthermore, the explicit solution for an inner homogeneous ring, with different properties with respect to those of the plate, is explicitly obtained and numerical results are compared between homogeneous ring and FGM ring.     

A rheological phase diagram of additives for cement formulations

A detailed rheological study of aqueous solutions of methylhydroxyethylcellulose has been carried out in the presence of different acrylate-based graft polymer used as additive contents. Both polymer components are used in cement formulations to improve the flow performances of the concretes, but no physicochemical studies can be easily found in the literature. The content of the graft polymer has been varied between 0.1 and 2.7 wt% in an aqueous solution with a fixed content of 6.5 wt% of methylhydroxyethylcellulose. Creep curves were performed at different stresses in order to build up the flow curves for the various solutions. We found that the addition of the graft polymer triggers a phase transition, which is made more dramatic by the presence of an external flow. A “flow-phase diagram” has been obtained, which could be used as a guide for determining the critical conditions for the onset of the flow-induced instability.     

Synergistic Effects of Metals in a Promising RuII−PtII Assembly for a Combined Anticancer Approach: Theoretical Exploration of the Photophysical Properties

Ru^II?Pt^II complexes are a class of bioactive molecules of interest as anticancer agents that combine a light‐absorbing chromophore with a cisplatin‐like unit. The results of a DFT and TDDFT investigation of a Ru^II complex and its conjugate with a cis‐PtCl₂ moiety reveal that a synergistic effect of the metals makes the assembly a promising multitarget anticancer drug. Inspection of type I and type II photoreactions and spin–orbit coupling computations reveals that the cis‐PtCl₂ moiety improves the photophysical properties of the Ru^II chromophore, ensuring efficient singlet oxygen generation and making the assembly suitable for photodynamic therapy. At the same time, the Ru^II chromophore promotes a new alternative activation mechanism of the Pt^II ligand via a triplet metal‐to‐ligand charge transfer (³M LCT) state, before reaching the biological target. The importance of the supramolecular architecture is accurately derived, opening interesting new perspectives on the use of bimetallic Ru^II?Pt^II assemblies in a combined anticancer approach.     

Triptycene‐Roofed Quinoxaline Cavitands for the Supramolecular Detection of BTEX in Air

Two novel triptycene quinoxaline cavitands ( DiTriptyQxCav and MonoTriptyQxCav ) have been designed, synthesized, and applied in the supramolecular detection of benzene, toluene, ethylbenzene, and xylenes (BTEX) in air. The complexation properties of the two cavitands towards aromatics in the solid state are strengthened by the presence of the triptycene moieties at the upper rim of the tetraquinoxaline walls, promoting the confinement of the aromatic hydrocarbons within the cavity. The two cavitands were used as fiber coatings for solid‐phase microextraction (SPME) BTEX monitoring in air. The best performances in terms of enrichment factors, selectivity, and LOD (limit of detection) values were obtained by using the DiTriptyQxCav coating. The corresponding SPME fiber was successfully tested under real urban monitoring conditions, outperforming the commercial divinylbenzene–Carboxen–polydimethylsiloxane (DVB–CAR–PDMS) fiber in BTEX adsorption.