Zinc (II) and AIEgens: The “Clip Approach” for a Novel Fluorophore Family. A Review

Aggregation-induced emission (AIE) compounds display a photophysical phenomenon in which the aggregate state exhibits stronger emission than the isolated units. The common term of “AIEgens” was coined to describe compounds undergoing the AIE effect. Due to the recent interest in AIEgens, the search for novel hybrid organic–inorganic compounds with unique luminescence properties in the aggregate phase is a relevant goal. In this perspective, the abundant, inexpensive, and nontoxic d¹⁰ zinc cation offers unique opportunities for building AIE active fluorophores, sensing probes, and bioimaging tools. Considering the novelty of the topic, relevant examples collected in the last 5 years (2016–2021) through scientific production can be considered fully representative of the state-of-the-art. Starting from the simple phenomenological approach and considering different typological and chemical units and structures, we focused on zinc-based AIEgens offering synthetic novelty, research completeness, and relevant applications. A special section was devoted to Zn(II)-based AIEgens for living cell imaging as the novel technological frontier in biology and medicine.     

New furoquinoline alkaloid and flavanone glycoside derivatives from the leaves of Oricia suaveolens and Oricia renieri (Rutaceae)

Fractionation of the methanol extract of the leaves of Oricia renieri and Oricia suaveolens (Rutaceae) led to the isolation of 13 compounds including the hitherto unknown furoquinoline alkaloid named 6,7-methylenedioxy-5-hydroxy-8-methoxy-dictamnine (1) and a flavanone glycoside named 5-hydroxy-4′-methoxy-7-O-[α-l-rhamnopyranosyl(1?→5″)-β-d-apiofuranosyl]-flavanoside (2), together with 11 known compounds (3–13). The structures of the compounds were determined by comprehensive analyses of their 1D and 2D NMR, mass spectral data and comparison. All compounds isolated were examined for their activity against human carcinoma cell lines. The alkaloids 1, 5, 12, 13 and the phenolic 2, 8, 11 tested compounds exhibited non-selective moderate cytotoxic activity with IC₅₀ 8.7–15.9 μM whereas compounds 3, 4, 6, 7, 9 and 10 showed low activity.     

Rapid genotyping of CYP2D6, CYP2C19 and TPMT polymorphisms by primer extension reaction in a dipstick format

In recent years an increasing amount of interest has been directed at the study and routine testing of polymorphisms responsible for variations in drug metabolism. Most of the current methods involve either time-consuming electrophoresis steps or specialized and expensive equipment. In this context, we have developed a rapid, simple and robust method for genotyping of CYP2D6*3, CYP2D6*4, CYP2C19*2, CYP2C19*3 and TPMT*2 single nucleotide polymorphisms (SNP). Genomic DNA is isolated from whole blood and the segments that span the SNP of interest are amplified by PCR. The products are subjected directly (without purification) to two primer extension (PEXT) reactions (three cycles each) using normal and mutant primers in the presence of biotin-dUTP. The PEXT primers contain a (dA)₃₀ segment at the 5′ end. The PEXT products are detected visually by a dry-reagent dipstick-type assay in which the biotinylated extension products are captured from immobilized streptavidin on the test zone of the strip and detected by hybridization with oligo(dT)-functionalized gold nanoparticles. Patient samples (76 variants in total) were genotyped and the results were fully concordant with those obtained by direct DNA sequencing.     

Synthesis, multiphase characterization, and helicity control in chiral DACH-linked oligothiophenes

A new class of chiral oligothiophenes is described. Mono-, bi-, ter-, and quarterthiophenes have been linked to enantiopure trans-1,2-cyclohexanediamine (DACH) via diamino or diimino moieties. The stereochemistry of DACH, the type of linker, and oligothiophene size determine the conformational flexibility of these molecules and consequently their molecular and supramolecular helicity in solution and in the solid state. The case of diaminobis(bithiophene), which inverts helicity and shows chiral amplification in the transition from solution to film, is described in detail. Based on the combined use of circular dichroism in solution and in the solid state, single-crystal/thin-film X-ray diffraction, and polarized optical microscopy, a working mechanism has been proposed to explain this unexpected behavior.     

A perturbation method for evaluating nonlinear normal modes of a piecewise linear two-degrees-of-freedom system

The classical Lindstedt–Poincaré method is adapted to analyze the nonlinear normal modes of a piecewise linear system. A simple two degrees-of-freedom, representing a beam with a breathing crack is considered. The fundamental branches of the two modes and their stability are drawn by varying the severity of the crack, i.e., the level of nonlinearity. Results furnished by the asymptotic method give insight into the mechanical behavior of the system and agree well with numerical results; the existence of superabundant modes is proven. The unstable regions and the bifurcated branches are followed by a numerical procedure based on the Poincarè map.     

Insights into Two Novel Orthopalladated Chromophores with Antimicrobial Activity against Escherichia coli

Advanced chromophoric tools, besides being biologically active, need to meet the expectations of the technological demands including stability, colour retention, and proper solubility for their target. Many coordination compounds of conjugated ligands are antibacterial dyes, able to combine a strong dyeing performance with a useful biological activity. Specifically, palladium (II) complexes of Schiff base ligands are known for their relevant activity against common bacteria. In this article, we report the synthesis and comprehensive experimental and theoretical characterization of two novel Pd(II) chromophore complexes obtained from a cyclopalladated Schiff base as two different chelating azo dyes. The antibacterial response of these two novel complexes was tested against the ubiquitous Escherichia coli bacterium in an aqueous medium and revealed a noteworthy antimicrobial activity, higher than when compared with their uncoordinated biologically active ligands.     

Postcritical Behavior of Cables Undergoing Two Simultaneous Galloping Modes

Abstract. A nonlinear two degree-of-freedom model, describing a flexible elastic suspended cable undergoing galloping oscillations, is analyzed. By using a perturbative approach, the critical conditions occuring for different values of the aerodynamic coefficients are described. Two different type of critical conditions, corresponding to simple or double Hopf bifurcations are found. The nonlinear postcritical behavior of single taut strings in 1:1 primary internal resonance is studied through the multiple scale perturbation method. In the double Hopf bifurcation case the influence of the detuning between the critical eigenvalues on the postcritical behavior is illustrated. It is found that quasi-periodic motions, which are likely to occur in the linear field when the two critical frequencies are incommensurable, are really unstable in the nonlinear range. Therefore, the postcritical behavior of the string consists of stable periodic motions for any detuning values.Sommario. Viene analizzato un modello non lineare a due gradi di libertrappresentativo di un cavo elastico flessibile sospeso alle estremite soggetto ad oscillazioni galoppanti. Utilizzando un approccio perturbativo, vengono descritte le condizioni critiche per differenti valori dei coefficienti aerodinamici. Sono presenti due diversi tipi di condizioni critiche, corrispondenti a biforcazioni di Hopf semplici e doppie. Attraverso il metodo perturbativo delle scale multiple viene studiato il comportamento post-critico non lineare di singole stringhe tese in risonanza interna primaria 1:1. Nel caso di biforcazione doppia di Hopf viene illustrata l'influenza del detuning tra gli autovalori critici sul comportamento post-critico. Si trova che i moti quasi-periodici, presenti in campo lineare quando le due frequenze critiche sono incommensurabili, sono in realtinstabili in campo non lineare. Quindi, il comportamento post-critico della stringa risulta composto da moti periodici stabili per un qualsiasi valore del detuning.     

Monotonely Cauchy locally-solid topologies

The lattice of monotonely Cauchy (=pre-Lebesgue) locally solid topologies on a given lattice-ordered group is studied. Indentifying topologies agreeing on order bounded sets this lattice becomes a complete Boolean algebra isomorphic to the subalgebra of the lattice's complemented members and realizable as a Boolean algebra of order projections. Some consequences of these results are indicated.Work done while Tim Traynor was visiting professor at University of Napoli sponsored by CNR-Italia.