Organic Conjugated Trimers with Donor–Acceptor–Donor Structures for Photocatalytic Hydrogen Generation Application

Organic donor–acceptor–donor (D–A–D) polymers or small molecules are widely investigated in organic solar cells due to their broad light absorption, narrow band gap, excellent charge mobility, and exciton seperation at the interface. However, studies of conjugated small molecules with D–A–D molecule structures as photocatalytically active materials are still rare. In this study, an unprecedented demonstration that photocatalytic activity can in fact be affected by tuning the D and A is given. Especially, the EBE trimer, comprising 3,4-ethylenedioxythiophene (E) and benzothiadiazole (B) units, exhibits the best photophysical, chemical, and photocatalytic properties compared to other D–A–D combinations of D and A. Detailed kinetic studies show that all trimers in organic solution present relatively long-lived and highly emissive photogenerated singlet excitons (τ = 4–13 ns; ϕ_em = 0.5–0.9) as judged by photoluminescence and transient absorption measurements, while in specific cases formation of long-lived triplet states can be identified. Organic microparticles of the trimers are efficiently formed in aqueous solution by nanoprecipitation, and rapid photoinduced electron release/injection to the solvent is evidenced spectroscopically. The results indicate that organic small molecule structures with D–A–D structures pave a new pathway for photocatalytic solar-to-chemical energy conversion of novel small organic molecules.     

Near-infrared spectroscopy: A possible routine analysis to detect the use of frozen curds in the production of Buffalo Mozzarella cheese

Mozzarella di Bufala Campana is a pasta filata cheese with a Protected Designation of Origin whose specifications require the use of fresh milk, forbidding the use of frozen curds. The goal is to develop a routine analysis to identify frozen curd presence. The Buffalo Mozzarella samples were analysed by the near-infrared analytical technique, and the spectral data were processed through an artificial neural network. The results make it possible to identify the use of frozen curd in samples of Buffalo Mozzarella for up to 9 days of storage. The model reported very high accuracy either in training (0.5% of bad prediction) or in tests (6.8% of bad prediction).     

Synthesis of Aminoethyl-Substituted Piperidine Derivatives as σ1 Receptor Ligands with Antiproliferative Properties

A series of novel σ₁ receptor ligands with a 4-(2-aminoethyl)piperidine scaffold was prepared and biologically evaluated. The underlying concept of our project was the improvement of the lipophilic ligand efficiency of previously synthesized potent σ₁ ligands. The key steps of the synthesis comprise the conjugate addition of phenylboronic acid at dihydropyridin-4(1H)-ones 7 , homologation of the ketones 8 and introduction of diverse amino moieties and piperidine N-substituents. 1-Methylpiperidines showed particular high σ₁ receptor affinity and selectivity over the σ₂ subtype, whilst piperidines with a proton, a tosyl moiety or an ethyl moiety exhibited considerably lower σ₁ affinity. Molecular dynamics simulations with per-residue binding free energy deconvolution demonstrated that different interactions of the basic piperidine-N-atom and its substituents (or the cyclohexane ring) with the lipophilic binding pocket consisting of Leu105, Thr181, Leu182, Ala185, Leu186, Thr202 and Tyr206 are responsible for the different σ₁ receptor affinities. Recorded logD_7.4 and calculated clogP values of 4a and 18a indicate low lipophilicity and thus high lipophilic ligand efficiency. Piperidine 4a inhibited the growth of human non-small cell lung cancer cells A427 to a similar extent as the σ₁ antagonist haloperidol. 1-Methylpiperidines 20a , 21a and 22a showed stronger antiproliferative effects on androgen negative human prostate cancer cells DU145 than the σ₁ ligands NE100 and S1RA.     

A Modular System for the Rapid Comparison of Different Membrane Anchors for Surface Display on Escherichia coli

Comparison of different membrane anchor motifs for the surface display of a protein of interest (passenger) is crucial for achieving the best possible performance. However, generating genetic fusions of the passenger to various membrane anchors is time-consuming. We herein employ a recently developed modular display system, in which the membrane anchor and the passenger are expressed separately and assembled in situ via SpyCatcher and SpyTag interaction, to readily combine a model passenger cytochrome P450 BM3 (BM3) with four different membrane anchors (Lpp-OmpA, PgsA, INP and AIDA-I). This approach has the significant advantage that passengers and membrane anchors can be freely combined in a modular fashion without the need to generate direct genetic fusion constructs in each case. We demonstrate that the membrane anchors impact not only cell growth and membrane integrity, but also the BM3 surface display capacity and whole-cell biocatalytic activity. The previously used Lpp-OmpA as well as PgsA were found to be efficient for the display of BM3 via SpyCatcher/SpyTag interaction. Our strategy can be transferred to other user-defined anchor and passenger combinations and could thus be used for acceleration and improvement of various applications involving cell surface display.     

Experimental tests and FE simulations to compute the mechanical and fracture properties of the shot-earth 772

The present paper is dedicated to the mechanical and fracture characterization of a specific earthen material, that is, the shot-earth 772. Although such a material has been recently characterized from a microstructural, chemical and physical point of view, the knowledge of its mechanical and fracture properties (essential for extending its use in construction industry) is still lacking. Such characterizations are here performed both experimentally, through laboratory tests, and numerically, through a FE model. The experimental tests (i.e., flexural, compression, and fracture tests) are carried out on shot-earth specimens according to recommendations available for concrete and a method proposed by the present authors, named Modified Two-Parameter Model. The numerical analyses are performed by employing a micromechanical model (implemented in a nonlinear 2D FE homemade code), which allows to simulate both flexural and fracture behavior of the shot-earth examined. Finally, the obtained numerical results are compared with the experimental ones.     

Tools for monitoring toxicological and genotoxicological changes in a drinking water treatment plant in Northeast Italy

Drinking water quality can be compromised at different stages, from raw water to treated one. This research aimed to evaluate the toxicity and genotoxicity of groundwater contaminated by fluorinated compounds treated in a drinking water treatment plant, through several bioassays. Water samples underwent chemical analyses and were assayed on Daphnia magna, Pseudokirchneriella subcapitata, Allium cepa, human leukocytes and Salmonella typhimurium. Physical–chemical parameters were always within the Italian legislation limits. Water after filtration and disinfection caused slight toxicity in D. magna; the sample after filtration inhibited the proliferation of P. subcapitata. None of the water samples exerted toxicity in A. cepa. All the analysed samples had genotoxic effects on A. cepa and human leucocytes, while only disinfected water caused mutations in S. typhimurium. A battery composed of tests on D. magna, P. subcapitata, S. typhimurium and A. cepa could represent a useful tool to verify the toxicity/genotoxicity through the water treatment stages and to improve drinking water quality management.