Biomimetic sulfide oxidation by the means of immobilized Fe(III)-5,10,15,20-tetrakis(pentafluorophenyl)porphin under mild experimental conditions

This paper describes the oxidation of inorganic sulfide to sulfate, minimizing the formation of elemental sulfur. The described catalytic reaction uses dilute hydrogen peroxide at nearly neutral pH values in the presence of a bioinspired, heterogenized, and commercial ferriporphin. A substantial increase of the percentage of sulfide converted to sulfate is obtained in comparison with the yields obtained when working with hydrogen peroxide alone. The biomimetic catalyst also proved to be a much more efficient catalyst than horseradish peroxidase. Accordingly, it could be suitable for large-scale applications. Further studies are in progress to drive sulfate yields up to nearly quantitative

The Role of the Coagulation System in Peripheral Arterial Disease: Interactions with the Arterial Wall and Its Vascular Microenvironment and Implications for Rational Therapies

Peripheral artery disease (PAD) is a clinical manifestation of atherosclerotic disease with a large-scale impact on the economy and global health. Despite the role played by platelets in the process of atherogenesis being well recognized, evidence has been increasing on the contribution of the coagulation system to the atherosclerosis formation and PAD development, with important repercussions for the therapeutic approach. Histopathological analysis and some clinical studies conducted on atherosclerotic plaques testify to the existence of different types of plaques. Likely, the role of coagulation in each specific type of plaque can be an important determinant in the histopathological composition of atherosclerosis and in its future stability. In this review, we analyze the molecular contribution of inflammation and the coagulation system on PAD pathogenesis, focusing on molecular similarities and differences between atherogenesis in PAD and coronary artery disease (CAD) and discussing the possible implications for current therapeutic strategies and future perspectives accounting for molecular inflammatory and coagulation targets. Understanding the role of cross-talking between coagulation and inflammation in atherosclerosis genesis and progression could help in choosing the right patients for future dual pathway inhibition strategies, where an antiplatelet agent is combined with an anticoagulant, whose role, despite pathophysiological premises and trials' results, is still under debate

A structural spproach to the strength evaluation of linear chalcogen bonds

The experimental structural features of chalcogen bonding (ChB) interactions in over 34,000 linear fragments R–Ch⋯A (Ch = S, Se, Te; R = C, N, O, S, Se, Te; A = N, O, S, Se, Te, F, Cl, Br, I) were analyzed. The bond distances dR–Ch and the interaction distances dCh⋯A were investigated, and the functions δR–Ch and δCh⋯A were introduced to compare the structural data of R–Ch⋯A fragments involving different Ch atoms. The functions δR−Ch and δCh⋯A were calculated by normalizing the differences between the relevant bond dR–Ch and ChB interaction dCh⋯A distances with respect to the sum of the relevant covalent (rcovR + rcovCh) and the van der Waals (vdW) radii (rvdWCh + rvdWA), respectively. A systematic comparison is presented, highlighting the role of the chalcogen involved, the role of the R atoms covalently bonded to the Ch, and the role of the A species playing the role of chalcogen bond acceptor. Based on the results obtained, an innovative approach is proposed for the evaluation and categorization of the ChB strength based on structural data

A follow-up on psychiatric symptoms and post-traumatic stress disorders in Tuareg refugees in Burkina Faso

Introduction: The aim of this study was to carry out a 2-year follow-up of refugees in a camp in Burkina Faso who had been interviewed previously. We also aimed to verify whether the general conditions in which they lived (e.g., protection by international organizations and the conclusion of negotiations and new hope of returning to Mali and reunification with surviving family members) would affect their mental health state. Methods: This is a cross-sectional study repeated over time on a cohort of refugees. People living in the Subgandé camp who had participated in the first survey in 2012 were identified using informational chains and approached for follow-up. Those who agreed were interviewed using the Short Screening Scale for post-traumatic stress disorder (PTSD) and the K6 scale, French versions, to measure general psychopathology and the level of impairment. Results: The second survey shows a dramatic decrease in psychopathological symptoms (positivity at K6 scale). Improvement was also conspicuous in the frequency of people with stress symptoms (positivity at Short Screening Scale for PTSD and simultaneous positivity to K6 scale). The frequency of people screened positive at the Short Screening Scale for PTSD had also decreased, but the level of improvement was not pronounced. Conclusion: Our findings confirm that when physical conditions improve, psychological symptoms can also improve. Although in the studied sample psychological factors, such as the hope of returning to their own land and thus the possibility of maintaining ethnic cohesion, may have played a role, future research carried out with a proper methodology and sufficient resources to identify protective factors is needed

Luminescent gold-thallium derivatives with a pyridine-containing 12-membered aza-thioether macrocycle

The coordination modes of the ligand 2, 5, 8-trithia[9](2, 6)pyridinophane (L) to thallium(i), gold(iii) and gold(i) have been studied. Thallium(i) is coordinated by the macrocyclic ligand in [Tl(L)](PF6) (1) through all the sulfur and nitrogen atoms, in a distorted square-pyramidal geometry with the thallium(i) ion in the apical position and with the presence of an inert lone pair. Gold(iii) is bonded by the ligand only through the nitrogen of the pyridine group in [AuCl3(L)] (2), whereas two AuI-C6F5fragments coordinate the sulfur atoms next to the pyridine moiety of the ligand in [{Au(C6F5)}2(µ-L)] (3), which form a linear polymer through intermolecular aurophilic contacts. The heterometallic TlI/AuIcomplex {[Au(C6F5)2Tl]2(L)}n(4) features a polymeric structural nature with a metallic pseudo-rhombic Au2Tl2core, which repeats itself forming a zig-zag polymer. In each Au2Tl2unit only one thallium atom is bonded by the NS3donor set of the macrocyclic ligand and also forms two unsupported Au-Tl bonds with two [Au(C6F5)2]-units in an overall pseudo-octahedral geometry. The other thallium atom similarly bridges the same [Au(C6F5)2]-units and links a neighbouring Au2Tl2moiety, thus exhibiting a distorted trigonal planar geometry being bonded only to three gold atoms with unsupported Au-Tl interactions. This complex displays an interesting thermochromic behaviour showing emissions mainly resulting from MM'CT transitions at room temperature. At 77 K a dual emission appears, probably arising from the two different thallium environments. DFT calculations have been carried out in the attempt to investigate the origin of the emissions of complex4. © The Royal Society of Chemistry 2021

Diradical Character of Neutral Heteroleptic Bis(1,2-dithiolene) Metal Complexes: Case Study of [Pd(Me2timdt)(mnt)] (Me2timdt = 1,3-Dimethyl-2,4,5-trithioxoimidazolidine; mnt2-= 1,2-Dicyano-1,2-ethylenedithiolate)

The reaction of the bis(1,2-dithiolene) complex [Pd(Me2timdt)2] (1; Me2timdt•- = monoreduced 1,3-dimethyl-2,4,5-trithioxoimidazolidine) with Br2 yielded the complex [Pd(Me2timdt)Br2] (2), which was reacted with Na2mnt (mnt2- = 1,2-dicyano-1,2-ethylenedithiolate) to give the neutral mixed-ligand complex [Pd(Me2timdt)(mnt)] (3). Complex 3 shows an intense solvatochromic near-infrared (NIR) absorption band falling between 955 nm in DMF and 1060 nm in CHCl3 (ϵ = 10700 M-1 cm-1 in CHCl3). DFT calculations were used to elucidate the electronic structure of complex 3 and to compare it with those of the corresponding homoleptic complexes 1 and [Pd(mnt)2] (4). An in-depth comparison of calculated and experimental structural and vis-NIR spectroscopic properties, supported by IEF-PCM TD-DFT and NBO calculations, clearly points to a description of 3 as a dithione-dithiolato complex. For the first time, a broken-symmetry (BS) procedure for the evaluation of the singlet diradical character (DC) of heteroleptic bis(1,2-dithiolene) complexes has been developed and applied to complex 3. The DC, predominant for 1 (nDC = 55.4%), provides a remarkable contribution to the electronic structures of the ground states of both 3 and 4, showing a diradicaloid nature (nDC = 24.9% and 27.5%, respectively). The computational approach developed here clearly shows that a rational design of the DC of bis(1,2-ditiolene) metal complexes, and hence their linear and nonlinear optical properties, can be achieved by a proper choice of the 1,2-dithiolene ligands based on their electronic structure

Artificial Intelligence in Acute Ischemic Stroke Subtypes According to Toast Classification: A Comprehensive Narrative Review

The correct recognition of the etiology of ischemic stroke (IS) allows tempestive interventions in therapy with the aim of treating the cause and preventing a new cerebral ischemic event. Nevertheless, the identification of the cause is often challenging and is based on clinical features and data obtained by imaging techniques and other diagnostic exams. TOAST classification system describes the different etiologies of ischemic stroke and includes five subtypes: LAAS (large-artery atherosclerosis), CEI (cardio embolism), SVD (small vessel disease), ODE (stroke of other determined etiology), and UDE (stroke of undetermined etiology). AI models, providing computational methodologies for quantitative and objective evaluations, seem to increase the sensitivity of main IS causes, such as tomographic diagnosis of carotid stenosis, electrocardiographic recognition of atrial fibrillation, and identification of small vessel disease in magnetic resonance images. The aim of this review is to provide overall knowledge about the most effective AI models used in the differential diagnosis of ischemic stroke etiology according to the TOAST classification. According to our results, AI has proven to be a useful tool for identifying predictive factors capable of subtyping acute stroke patients in large heterogeneous populations and, in particular, clarifying the etiology of UDE IS especially detecting cardioembolic sources

Washingtonia filifera seed extracts inhibit the islet amyloid polypeptide fibrils formations and α-amylase and α-glucosidase activity

Washingtonia filifera seeds have revealed to possess antioxidant properties, butyrylcholinesterase and xanthine oxidase inhibition activities. The literature has indicated a relationship between Alzheimer’s disease (AD) and type-2 diabetes (T2D). Keeping this in mind, we have now evaluated the inhibitory properties of W. filifera seed extracts on α-amylase, α-glucosidase enzyme activity and the Islet Amyloid Polypeptide (IAPP) fibrils formation. Three extracts from seeds of W. filifera were evaluated for their enzyme inhibitory effect and IC50 values were calculated for all the extracts. The inhibition mode was investigated by Lineweaver-Burk plot analysis and the inhibition of IAPP aggregate formation was monitored. W. filifera methanol seed extract appears as the most potent inhibitor of α-amylase, α-glucosidase, and for the IAPP fibril formation. Current findings indicate new potential of this extract that could be used for the identification or development of novel potential agents for T2D and AD

Amino acid-driven adsorption of emerging contaminants in water by modified graphene oxide nanosheets

Graphene oxide nanosheets have shown promising adsorption properties toward emerging organic contaminants in drinking water. Here, we report a family of graphene oxide nanosheets covalently modified with amino acids and the study on their adsorption properties toward a mixture of selected contaminants, including pharmaceuticals, additives, and dyes. Graphene oxides modified with l-glutamic acid and l-methionine (GO-Glu and GO-Met) were synthesized and purified with a scalable and fast synthetic and purification procedure, and their structure was studied by combined X-ray photoelectron spectroscopy and elemental analysis. An amino acid loading of about 5% and a slight reduction (from 27% down to 14-20% oxygen) were found and associated with the adsorption selectivity. They were compared to unmodified GO, reduced GO (rGO), GO-lysine, and to the reference sample GO-NaOH. Each type of modified GO possesses a higher adsorption capacity toward bisphenol A (BPA), benzophenone-4 (BP4), and carbamazepine (CBZ) than standard GO and rGO, and the adsorption occurred within the first hour of contact time. The maximum adsorption capacity (estimated from the adsorption isotherms) was strictly related to the amino acid loading. Accordingly, molecular dynamics simulations highlighted higher interaction energies for the modified GOs than unmodified GO, as a result of higher van der Waals and hydrophobic interactions between the contaminants and the amino acid side chains on the nanosheet surface