Programmable Polymer‐Based Supramolecular Temperature Sensor with a Memory Function

A new class of polymeric thermometers with a memory function is reported that is based on the supramolecular host–guest interactions of poly(N‐isopropylacrylamide) (PNIPAM) with side‐chain naphthalene guest moieties and the tetracationic macrocycle cyclobis(paraquat‐p‐phenylene) (CBPQT⁴⁺) as the host. This supramolecular thermometer exhibits a memory function for the thermal history of the solution, which arises from the large hysteresis of the thermoresponsive LCST phase transition (LCST=lower critical solution temperature). This hysteresis is based on the formation of a metastable soluble state that consists of the PNIPAM–CBPQT⁴⁺ host–guest complex. When heated above the transition temperature, the polymer collapses, and the host–guest interactions are disrupted, making the polymer more hydrophobic and less soluble in water. Aside from providing fundamental insights into the kinetic control of supramolecular assemblies, the developed thermometer with a memory function might find use in applications spanning the physical and biological sciences.     

Coordination and Redox Isomerization in the Reduction of a Uranium(III) Monoarene Complex

Synthetic studies on the redox chemistry of trivalent uranium monoarene complexes were undertaken with a complex derived from the chelating tris(aryloxide)arene ligand (^Ad,MeArO)₃mes^3?. Cyclic voltammetry of [{(^Ad,MeArO)₃mes}U^III] ( 1 ) revealed a nearly reversible and chemically accessible reduction at ?2.495 V vs. Fc/Fc⁺—the first electrochemical evidence for a formally divalent uranium complex. Chemical reduction of 1 indicates that reduction induces coordination and redox isomerization to form a uranium(IV) hydride, and addition of a crown ether results in hydride insertion into the coordinated arene to afford uranium(IV) complexes. This stoichiometric reaction sequence provides structural insight into the mechanism of arene functionalization at diuranium inverted sandwich complexes.     

Semiconductor Quantum Dots as Components of Photoactive Supramolecular Architectures

Luminescent quantum dots (QDs) are colloidal semiconductor nanocrystals consisting of an inorganic core covered by a molecular layer of organic surfactants. Although QDs have been known for more than thirty years, they are still attracting the interest of researchers because of their unique size-tunable optical and electrical properties arising from quantum confinement. Moreover, the controlled decoration of the QD surface with suitable molecular species enables the rational design of inorganic-organic multicomponent architectures that can show a vast array of functionalities. This minireview highlights the recent progress in the use of surface-modified QDs – in particular, those based on cadmium chalcogenides – as supramolecular platforms for light-related applications such as optical sensing, triplet photosensitization, photocatalysis and phototherapy.     

Involvement of Proton Transfer for Carbon Dioxide Reduction Coupled with Extracellular Electron Uptake in Shewanella oneidensis MR‐1

Microbial biosynthesis of hydrocarbon from CO₂ reduction driven by electron uptake process from the cathodic electrode has gained intensive attention in terms of potential industrial application. However, a lack of a model system for detailed studies on the mechanism of the CO₂ reduction hinders the improvement in efficiency for microbial electrosynthesis. Here, we examined the mechanism of microbial CO₂ reduction at the cathode by a well‐described microbe for extracellular electron uptake, Shewanella oneidensis MR‐1, capable of reducing gaseous CO₂ to produce formic acid. Using whole‐cell electrochemical assay, we observed stable cathodic current production at ?0.65 V vs Ag/AgCl KCl sat. associated with the introduction of CO₂. The observed cathodic current was enhanced by the addition of 4 μM riboflavin, which specifically accelerates the electron uptake process of MR‐1 by the interaction to its outer‐membrane c‐type cytochromes. The significant impact of an uncoupler agent and a mutant strain of MR‐1 lacking sole F‐type ATPase suggested the importance of proton import to the cytoplasm for the cathodic CO₂ reduction. The present data suggest that MR‐1 potentially serves as a model system for microbial electrosynthesis from CO₂.     

Natural Products Extracted from Fungal Species as New Potential Anti-Cancer Drugs: A Structure-Based Drug Repurposing Approach Targeting HDAC7

Mushrooms can be considered a valuable source of natural bioactive compounds with potential polypharmacological effects due to their proven antimicrobial, antiviral, antitumor, and antioxidant activities. In order to identify new potential anticancer compounds, an in-house chemical database of molecules extracted from both edible and non-edible fungal species was employed in a virtual screening against the isoform 7 of the Histone deacetylase (HDAC). This target is known to be implicated in different cancer processes, and in particular in both breast and ovarian tumors. In this work, we proposed the ibotenic acid as lead compound for the development of novel HDAC7 inhibitors, due to its antiproliferative activity in human breast cancer cells (MCF-7). These promising results represent the starting point for the discovery and the optimization of new HDAC7 inhibitors and highlight the interesting opportunity to apply the “drug repositioning” paradigm also to natural compounds deriving from mushrooms.     

The Elusive Ketene (H2CCO) Channel in the Infrared Multiphoton Dissociation of Solid 1,3,5-Trinitro-1,3,5-Triazinane (RDX)

Understanding of the fundamental mechanisms involved in the decomposition of 1,3,5-trinitro-1,3,5-triazinane (RDX) still represents a major challenge for the energetic materials and physical (organic) chemistry communities mainly because multiple competing dissociation channels are likely involved and previous detection methods of the products are not isomer selective. In this study we exploited a microsecond pulsed infrared laser to decompose thin RDX films at 5 K under mild conditions to limit the fragmentation channels. The subliming decomposition products during the temperature programed desorption phase are detected using isomer selective single photoionization time-of-flight mass spectrometry (PI-ReTOF-MS). This technique enables us to assign a product signal at m/z=42 to ketene (H₂CCO), but not to diazomethane (H₂CNN; 42 amu) as speculated previously. Electronic structure calculations support our experimental observations and unravel the decomposition mechanisms of RDX leading eventually to the elusive ketene (H₂CCO) via an exotic, four-membered ring intermediate. This study highlights the necessity to exploit isomer-selective detection schemes to probe the true decomposition products of nitramine-based energetic materials.     

Aurones: A Golden Resource for Active Compounds

Deemed as poorly represented in nature, aurones have been often overlooked by researchers compared to other members of the flavonoid superfamily. However, over the past two decades, they have been reassessed by the scientific community, who are increasingly appreciating their ability to modulate several biological pathways. This review summarizes the recent literature on this class of compounds, which has been analyzed from both a chemical and a functional point of view. Original articles, reviews and editorials featured in Pubmed and Scifinder over the last twenty years have been taken into account to provide the readers with a view of the chemical strategies to obtain them, their functional properties, and their potential of technological use. The resulting comprehensive picture aims at raising the awareness of these natural derivatives as effective drug candidates, fostering the development of novel synthetic analogues.     

Single and double electron capture associated with target K-shell ionization for F7 + ,8 + ,9++Ar

Ratios for target Ar K-shell ionization associated with single and double electron capture, as well as the ratios corresponding to total capture and the projectile K x rays, were determined for 1.8- to 2.2-MeV/u F^{7 + ,8 + ,9+} projectiles. This work was performed at Western Michigan University with the tandem Van de Graaff accelerator. Coincidences between emitted K-shell X-rays (both target and projectile) and the corresponding charge-changed particles were observed. The F⁹⁺ Ar K X-ray coincidence ratios for double to single capture are found to well exceed unity over the limited energy range of the measurements. Possible explanations for this anomalous behavior are discussed.     

The blossoming of quantum mechanics in Italy: the roots,the context and the first spreading in Italian universities (1900–1947)

The European Physical Journal H - The widespread positivist approach of physics research in Italy at the turn of the XIX and XX centuries did not provide a fertile ground for the scientific debate...