High-Energy Proton-Beam-Induced Polymerization/Oxygenation of Hydroxynaphthalenes on Meteorites and Nitrogen Transfer from Urea: Modeling Insoluble Organic Matter?

Formation and structural modification of oxygenated polycyclic aromatic hydrocarbons (oxyPAHs) by UV irradiation on minerals have recently been proposed as a possible channel of PAH transformation in astrochemical and prebiotic scenarios of possible relevance for the origin of life. Herein, it is demonstrated that high-energy proton-beam irradiation in the presence of various meteorites, including stony iron, achondrite, and chondrite types, promotes the conversion of two representative oxyPAH compounds, 1-naphthol and 1,8-dihydroxynaphthalene, to complex mixtures of oxygenated and oligomeric derivatives. The main identified products include polyhydroxy derivatives, isomeric dimers encompassing benzofuran and benzopyran scaffolds, and, notably, a range of quinones and perylene derivatives. Addition of urea, a prebiotically relevant chemical precursor, expanded the range of identified species to include, among others, quinone diimines. Proton-beam irradiation of oxyPAH modulated by nitrogen-containing compounds such as urea is proposed as a possible contributory mechanism for the formation and processing of insoluble organic matter in meteorites and in prebiotic processes.     

Inhibitory Effect of Lithospermic Acid on the HIV-1 Nucleocapsid Protein

The HIV-1 nucleocapsid protein (NC) is a desirable target in antiretroviral therapy due to its high conservation among HIV-1 strains, and to its multiple and crucial roles in the HIV-1 replication cycle. Natural products represent a valuable source of NC inhibitors, with the catechol group being a privileged scaffold in NC inhibition. By coupling molecular modeling with NMR spectroscopy and fluorescence-based assays, we disclosed lithospermic acid, a catechol derivative extracted from Salvia miltiorrhizza, as a potent and chemically stable non-covalent inhibitor of the NC. Being different from other catechol derivative reported so far, lithospermic acid does not undergo spontaneous oxidation in physiological conditions, thus becoming a profitable starting point for the development of efficient NC inhibitors.     

Controlling the Functional Properties of Oligothiophene Crystalline Nano/Microfibers via Tailoring of the Self‐Assembling Molecular Precursors

Oligothiophenes are π‐conjugated semiconducting and fluorescent molecules whose self‐assembly properties are widely investigated for application in organic electronics, optoelectronics, biophotonics, and sensing. Here an approach to the preparation of crystalline oligothiophene nano/microfibers is reported based on the use of a “sulfur overrich” quaterthiophene building block, ? T4S4 ? , containing in its covalent network all the information needed to promote the directional, π–π stacking‐driven, self‐assembly of Y‐T4S4‐Y oligomers into fibers with hierarchical supramolecular arrangement from nano‐ to microscale. It is shown that when Y varies from unsubstituted thiophene to thiophene substituted with electron‐withdrawing groups, a wide redistribution of the molecular electronic charge takes place without substantially affecting the aggregation modalities of the oligomer. In this way, a structurally comparable series of fibers is obtained having progressively varying optical properties, redox potentials, photoconductivity, and type of prevailing charge carriers (from p‐ to n‐type). With the aid of density functional theory (DFT) calculations, combined with powder X‐ray diffraction data, a model accounting for the growth of the fibers from molecular to nano‐ and microscale is proposed.     

Relative stereochemistry of a diterpene from Salvia cinnabarina

The relative stereochemistry of 3,4-secoisopimara-4(18),7,15-triene-3-oic acid, a diterpenoid with antispasmodic, hypotensive and antibacterial activities isolated from Salvia cinnabarina, was determined by an X-ray diffraction analysis of a single crystal of a suitable crystalline derivative.     

Adherence to the Mediterranean diet in a Sicilian student population

Since the last decades, socio-economic changes have a key role on eating habits affecting the nutritional status and health of people, in particular children and adolescents. The aim of this study was to compare the diet of student population both normal weight and overweight and obese in order to understand their eating habits by comparing the different diets of the student referring to the Mediterranean diet. The study comprised 337 Sicilian students aged 9 to 13 years, 96 in primary schools and 241 in secondary schools, respectively, in three Sicilian cities namely, Messina, San Piero Patti and Ragusa. The variables studied were height, weight, body mass index (BMI) and adherence to the Mediterranean Adequacy Index (MAI) diet quality indicator. Interestingly, the results highlighted 2.67 MAI mean value for normal weight students while 1.27 MAI mean value indicating a decreased adherence to the Mediterranean diet in overweight students.     

On a class of hyperbolic 3-orbifolds of small volume and small heegaard genus associated to 2-bridge links

We consider a class of hyperbolic 3-orbifoldsO(α/β); the underlying topological space of such an orbifold is the 3-sphere and the singular set is obtained by adding the two standard (upper and lower) unknotting tunnels to a 2-bridge linkL(α/β) (and associating branching order two to both unknotting tunnels). These 3-orbifolds are extremal with respect to the notion of Heegaard genus or Heegaard number of 3-orbifolds; it is to be expected that they are also extremal with respect to the volume, that is the smallest volume hyperbolic 3-orbifolds should belong to this or some closely related class. We show that an orbifoldO(α/β) has a uniqueD ₂-covering by an orbifold? _n(α/β) wose space is the 3-sphere and whose singular set is the same 2-bridge linkL(α/β) used for the construction ofO(α/β); moreoverO(α/β) is hyperbolic if and only if? _n(α/β) is hyperbolic. As the volumes of the orbifolds? _n(α/β) are known resp. can be computed, this allows to compute the volumes of the orbifoldsO(α/β). The problem of computation of volumes remains open for some closely related classes of 3-orbifolds which are also extremal with respect to the Heegaard genus (for example associating a branching order bigger than two to one or both unknotting tunnels).     

Molecular dynamics simulation of Matrix Metalloproteinase 2: fluctuations and time evolution of recognition pockets

We report a molecular dynamics simulation study of a zinc-protease--gelatinase A or MMP2--which is a major target for drug design, being involved in tumor metastasis and other degenerative diseases. Two structures have been employed as starting conditions, one based on the crystal of multi-domain proMMP2, the other consisting of the catalytic domain only. The overall fold of the two models is maintained over the 1260 ps trajectory, enabling us to analyze correlations of fluctuations among domains, and to observe the presence of correlations within the catalytic domain in the multi-domain enzyme only, hence due to the presence of hemopexin and fibronectin domains. In the multi-domain protein, two cavities are conserved over the trajectory, one of them pointing to a key region, a crevice surrounding the catalytic zinc. The other one is localized across the three domains of the MMP2 metalloproteinase. These areas are partially covered by the propeptide in the crystal structure of proMMP2. We propose a model of MMP2-collagen interaction that involves both identified cavities and takes into account the inter/intra domain cross-correlations.     

On the antioxidant activity of eumelanin biopigments: a quantitative comparison between free radical scavenging and redox properties

Abstract

The antioxidant activity of eumelanin, a ubiquitous pigment in flora and fauna, constitutes one of its most fascinating physicochemical properties. To shed light on free radical scavenging vs redox facets of such activity, we applied hydrogen atom transfer- and electron transfer-based assays to pristine Sepia ink, eumelanin from Sepia ink, chemically controlled eumelanins and their precursor building blocks. Our work contributes to the rational use of the antioxidant properties of eumelanin for health, cosmetics and environmental applications.