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For their great structural versatility, thiophene-based π-conjugated systems have been widely exploited in the preparation of low band gap materials. Here, we report the synthesis of a highly conjugated tetrathiophene system, namely 1,4-di([2,2′-bithiophen]-3-yl)buta-1,3-diyne (1), that presents two bithiophene units connected at position 3 by a butadiynylene spacer. Single-crystal X-ray diffraction (SC-XRD) analysis elucidated the structure of 1, confirming the planarity of the molecule. The molecule was then electropolymerized onto the surface of a gold-coated piezoelectric quartz crystal, showing a high reactivity that is ascribable to the extended conjugation. The frontier molecular orbital energies of 1 were obtained via DFT optimization performed on the crystal structure-derived molecular geometry. Finally, DFT was also used to estimate the polymer band gap. [ABSTRACT FROM AUTHOR]

The potential of a voltametric E-tongue coupled with a custom data pre-processing stage to improve the performance of machine learning techniques for rapid discrimination of tomato purées between cultivars of different economic value has been investigated. To this aim, a sensor array with screen-printed carbon electrodes modified with gold nanoparticles (GNP), copper nanoparticles (CNP) and bulk gold subsequently modified with poly(3,4-ethylenedioxythiophene) (PEDOT), was developed to acquire data to be transformed by a custom pre-processing pipeline and then processed by a set of commonly used classifiers. The GNP and CNP-modified electrodes, selected based on their sensitivity to soluble monosaccharides, demonstrated good ability in discriminating samples of different cultivars. Among the different data analysis methods tested, Linear Discriminant Analysis (LDA) proved to be particularly suitable, obtaining an average F1 score of 99.26%. The pre-processing stage was beneficial in reducing the number of input features, decreasing the computational cost, i.e., the number of computing operations to be performed, of the entire method and aiding future cost-efficient hardware implementation. These findings proved that coupling the multi-sensing platform featuring properly modified sensors with the custom pre-processing method developed and LDA provided an optimal tradeoff between analytical problem solving and reliable chemical information, as well as accuracy and computational complexity. These results can be preliminary to the design of hardware solutions that could be embedded into low-cost portable devices. [ABSTRACT FROM AUTHOR]

Given the widespread use of esters and polyesters in products like cosmetics, fishing nets, lubricants and adhesives, whose specific application(s) may cause their dispersion in open environments, there is a critical need for stringent eco-design criteria based on biodegradability and ecotoxicity evidence. Our approach integrates experimental and computational methods based on short oligomers, offering a screening tool for the rapid identification of sustainable monomers and oligomers, with a special focus on bio-based alternates. We provide insights into the relationships between the chemical structure and properties of bio-based oligomers in terms of biodegradability in marine environments and toxicity in benchmark organisms. The experimental results reveal that the considered aromatic monomers (terephthalic acid and 2,5-furandicarboxylic acid) accumulate under the tested conditions (OECD 306), although some slight biodegradation is observable when the inoculum derives from sites affected by industrial and urban pollution, which suggests that ecosystems adapt to non-natural chemical pollutants. While clean seas are more susceptible to toxic chemical buildup, biotic catalytic activities offer promise for plastic pollution mitigation. Without prejudice to the fact that biodegradability inherently signifies a desirable trait in plastic products, nor that it automatically grants them a sustainable "license", this study is intended to facilitate the rational design of new polymers and materials on the basis of specific uses and applications. [ABSTRACT FROM AUTHOR]

Point‐of‐care technologies need particularly stringent requirements, including portability, rapidity, affordability, and ease of use, enabling healthcare practitioners to perform reliable analyses in decentralized settings. Such diagnostic tests are usually based on bioassays that allow for the detection of clinically relevant biomarkers, namely proteins, antibodies and nucleic acids. In the context of electrochemical biosensors, the implementation of magnetic beads offers unique advantages stemming from their high surface‐to‐volume ratio, easy manipulation through magnetic fields and versatility in surface chemistries for bio‐conjugation. The present concept article highlights the advantages achieved through the implementation of magnetic beads in electrochemical binding assays, immunosensors and genosensors. These methods mostly exploit magnetic beads for immobilization purposes, allowing for the assembly of bio‐complexes in liquid suspensions under precise temperature and shaking control, as well as simplifying the manipulation steps to enable untrained personnel to perform analyses. In addition, magnetic beads can also take part in the detection mechanism, leading to innovative sensing strategies with great potential for point‐of‐care diagnostic applications. [ABSTRACT FROM AUTHOR]

Dinuclear Cu(I) complexes with bifunctionalized homoscorpionate ligands, hydrotris(thioxotriazolyl)borato [Li(Tr(super Me,o-Py), and Li(Tr(super Mes,Me), and the heteroscorpionate ligand hydro[bis(thioxotriazolyl)-3-(2-pyridyl)pyrazolyl]borato[K(Br(super Mes)pz(super o-Py)] were synthesized and crystallographically characterized. The complexes [Cu(Tr(super Mes,Me) and [Cu(Tr(super Me,o-Py)] exhibit a similiar coordination geometry where every metal is surrounded by three thioxo groups in a trigonal arrangement.

Penta-O-alkylated p-tert-butylcalix[5]arenes 1-5 (R = benzyl, isohexyl, isopropoxyethyl, isopropoxycarbonylmethyl, and tert-butoxycarbonylmethyl, respectively) in a fixed [C.sub.5e] cone conformation have been studied as ionophores in liquid membrane ion-selective electrodes (ISEs) for n-butylammonium against the other branched butylammonium isomers, alkali metals, and ammonium ions, in terms of detection limits, sensitivity, and selectivity. The highest levels of potentiometric selectivity and detection limits up to 3 x [10.sup.-6] M are observed with ISEs based on ionophore 2, where selectivity follows the order n-BuN[H.sub.-] [much greater than] i-BuN[H.sub.3] [greater than] s-BuN[H.sub.3] [greater than] t-Bu[NH.sub.3] The lower potentiometric selectivity displayed by ISEs based on ionophores 3-5 is ascribed to their affinity for the [Na.sup.+] ion of the lipophilic salt present in the membrane, as evidenced by appropriate 1H NMR competition experiments with [Na.sup.-] and n-Bu[NH.sub.3-] ions. Further investigation on the selectivity mechanism of ionophore 2 by means of frequency response analysis shows that the interaction of the linear butylammonium ion with membranes containing 2 involves a lower resistance process than that occurring with the other branched isomers, thus suggesting the presence of a favorable kinetic-controlled mechanism.