Electroactive chiral oligo- and polymer layers for electrochemical enantiorecognition

Electronically conducting polymer (ECP) and oligomer films are one of the most popular classes of artificial materials for electrode surface modification and nanostructured electroactive film preparation for use as active layers in advanced sensing electrochemical devices. They can act as both receptors and transducers on account of their electroactivity and easy derivatization in a virtually unlimited structure range, and typically have low cost and easy processability. The tailoring possibilities of ECP films also make them attractive selector candidates to achieve the superior level of molecular recognition represented by enantioselective electroanalysis, implying to discriminate between specular images of a chiral molecule . This superior recognition level requires to endow them with chirality and to employ them as enantiopure films, which can be made along different strategies, with different implications in terms of enantioselectivity, kind of transduction of the recognition event, specificity vs general applicability, preparation difficulty, robustness, etc. In this context an outstanding tool is provided by the \u201cinherent chirality\u201dstrategy

"Egg of Columbus": single-step complete removal of chloride impurities from ionic liquids by AgCl deposition on silver electrode

Chloride impurities in ionic liquids (ILs), which can be present even in huge amounts depending on the IL synthetic route, are particularly critical for electrochemical processes; thus, their abatement is often mandatory. However, while their analytical quantification has been the subject of many studies involving a variety of techniques, the so far available processes for their abatement are still unsatisfactory, having low efficiency, and/or involving multiple steps, and/or being far from mild and easily scalable. In this context, like an "egg of Columbus", a quite simple and safe process for chloride abatement in ILs is proposed, practically coinciding with the electrolytic preparation of a Ag|AgCl electrode. It proceeds in a single step, at room temperature, at very low potentials, with nearly ideal current efficiencies, and with negligible side effects on the electrolyzed IL. The chloride impurities are quantitatively captured and accumulated on the silver wire and eliminated by simply removing the resulting Ag|AgCl electrode from the solution, with no need of subsequent treatments

Electrochemistry of cyclic triimidazoles and their halo derivatives: A casebook for multiple equivalent centers and electrocatalysis

A family of cyclic triazines, based on the triimidazo[1,2-a:1\u2032,2\u2032-c:1\u2033,2\u2033-e][1,3,5]triazine scaffold, has recently caught attention due to its variegated solid state photoluminescent properties (e.g., crystallization induced emission, fluomechanochromism, dual fluorescence, room temperature ultralong phosphorescence), tuned by proper functionalization of the cyclic core. From an electrochemical point of view, this family of heteroaromatic cyclic triazines is unexplored. A cyclic voltammetry study is here performed aiming to clarify structure/electroactivity relationship. The peculiar molecular structure of this class of molecules offers a multi-approach case study, spanning from multiple equivalent redox site interactions in small hoops (due to ideally C3h symmetry) to carbon-halogen bond reactivity in the presence of catalytic metal electrode surfaces (for \u2013Br and \u2013I derivatives). Results point to a poor heteroannular aromaticity along the rigid, planar cyclotrimer, with each equivalent redox site acting quite independently. An unusually higher electrocatalytic performance of gold with respect to silver electrode for the electrocleavage of carbon-halogen bonds (that decreases by increasing number of halo substituents) is tentatively explained in term of a specific interaction between gold and the nitrogen-rich planar cyclotrimer platform

Enantiomer discrimination in absorption spectroscopy and in voltammetry: highlighting fascinating similarities and connections

Absorption spectroscopy and voltammetry, of known analogies and connections, share even more fascinating similarities and connections at a higher complexity level, when "upgrading" them with the ability to discriminate between enantiomers by chiral selector implementation. In both techniques either "molecular" selectors or "electromagnetic" ones (L- versus Rcircularly polarized light components for spectroscopy, ccversus b-spin electrons for voltammetry) can be considered; moreover, external magnetic field application can replace a truly chiral actor. A tentative schematization is provided. Analogies and connections also concern molecular features of the enantiodiscrimination actors. In both techniques outstanding performances are obtained with inherently chiral molecules, in which a conjugated backbone with tailored torsion is source of chirality as well as spectroscopic and electrochemical activity, in an attractive three-fold interconnection. Their outstanding effects can be justified by a combination of chemical and electromagnetic properties (excellent potential molecular spin filters), a fascinating challenge for future developments

Neural basis of anticipatory multisensory integration

The brain is able to gather different sensory information to enhance salient event perception, thus yielding a unified perceptual experience of multisensory events. Multisensory integration has been widely studied, and the literature supports the hypothesis that it can occur across various stages of stimulus processing, including both bottom-up and top-down control. However, evidence on anticipatory multisensory integration occurring in the fore period preceding the presentation of the expected stimulus in passive tasks, is missing. By means of event-related potentials (ERPs), it has been recently proposed that visual and auditory unimodal stimulations are preceded by sensory-specific readiness activities. Accordingly, in the present study, we tested the occurrence of multisensory integration in the endogenous anticipatory phase of sensory processing, combining visual and auditory stimuli during unimodal and multimodal passive ERP paradigms. Results showed that the modality-specific pre-stimulus ERP components (i.e., the auditory positivity-aP-and the visual negativity-vN-) started earlier and were larger in the multimodal stimulation compared with the sum of the ERPs elicited by the unimodal stimulations. The same amplitude effect was also present for the early auditory N1 and visual P1 components. This anticipatory multisensory effect seems to influence stimulus processing, boosting the magnitude of early stimulus processing. This paves the way for new perspectives on the neural basis of multisensory integration

Breast tuberculosis: A case report of primary type mammary tuberculosis

Mammary tuberculosis is exceptional in developed countries. It can mimic an abscess or a granulomatous mastitis. In subjects coming from endemic areas, it is necessary to suspect a tuberculosis infection in case of recurrent mastitis refractory to antibiotics. Positivity of Quantiferon-TB Gold assay can help to confirm the clinical suspicion

Benefits and medium-term outcome of the Sorin Pericarbon Freedom stentless aortic prosthesis in cases of acute bacterial endocarditis

OBJECTIVES The aim of this study is to evaluate the ease of use and the advantages of Sorin Pericarbon Freedom (SPF) stentless valve in cases of acute bacterial endocarditis and to check the intermediate-term results after the implant of SPF with respect to resistance to infection, valve deterioration and durability. METHODS Between June 2003 and February 2015, 26 patients with active aortic valve bacterial endocarditis underwent aortic valve replacement with SPF pericardial stentless aortic prosthesis. The mean age was 57 \ub1 18 years; 73% of the patients were in preoperative NYHA class III and VI. Mean Logistic EuroSCORE was 14.2 \ub1 12.7. Endocarditis occurred in 18 patients with native valves, and in 9 patients with prosthetic valves (4 mechanical aortic valve prostheses; 5 aortic bioprostheses). Aortic root abscesses were observed in 16 cases (61.5%). Surgery was emergent in 3 cases (11.5%). Redo surgery was performed in 9 cases (35%). Cumulative follow-up was 126.8 patient-years (mean 4.9 \ub1 3.3 years). RESULTS Operative hospital mortality was 0% for all patients. Residual mean prosthetic gradient at discharge was 9.4 \ub1 3.6 mmHg. Neither residual aortic incompetence nor residual abscess cavity was observed at discharge. Mean ejection fraction at discharge was 54 \ub1 8% (Min; Max: 35%; 65%). A total of 4 patients died at follow-up, all for non-cardiac causes. One patient was lost to follow-up. Two patients (8%) underwent non-valve-related reoperation with 0% mortality. Residual mean gradient at follow-up was 7.2 \ub1 2.1 mmHg. Three patients (17%) presented with mild/moderate aortic incompetence and 89% of patients were in NYHA Class I-II at follow-up. At 9 years, actuarial freedom from valve-related reoperation and from structural valve deterioration was 100%. CONCLUSIONS The SPF aortic prosthesis is a true pericardial stentless prosthesis suitable for the treatment of acute bacterial endocarditis. Intermediate-time results in terms of freedom from reoperation, structural valve deterioration and resistance to infections are satisfactory. Haemodynamic performances are excellent since a complete exclusion of aortic root abscesses is achieved without any reduction of the aortic annular diameter, usually due to marsupialization or patch closure of the infected cavities

A Gini and concentration index decomposition with an application to the APK reranking measure

In this paper, we suggest an alternative way to calculate the concentration index and a new matrix form approach, which can be applied both to the Gini and to the concentration index. For both indices, this approach yields expressions that are decomposable by groups and easily comparable. Our findings are illustrated by applying them to the Atkinson Plotnick Kakwani (APK) reranking measur

The decomposition of the Atkinson-Plotnik-Kakwani re-ranking measure

This article introduces a new matrix approach, based on pairwise income comparisons, to decompose the Atkinson-Plotnick-Kakwani re-ranking measure when income units are gathered into groups. As it is known the Atkinson-Plotnick-Kakwani re-ranking measure is defined by the difference between the Gini index and the concentration index. Re-ranking can be exclusively decomposed as the sum of two parts: the within group and the across-group re-ranking measures. Our results are applied to a household sub-sample selected from the 2007 survey of the Panel Study on Income Dynamics (PSID). In the applied analysis our approach proves to be quite powerful. We show that in addition to providing different measures, it allows to calculate the incidence of re-ranking

Enantioselective selectors for chiral electrochemistry and electroanalysis : stereogenic elements and enantioselection performance

The ability to select among different electroactive molecules, or among different redox centers on a single molecule, in both analytical and synthetic applications, is a typical asset of electrochemistry, based on fine control of the electrode potential, possibly enhanced by the choice of appropriate electrode surfaces and media. An attractive step further, of great fundamental and applicative interest, is represented by enantioselective electrochemistry, implying the ability to discriminate the enantiomers of chiral molecules (in electroanalysis), or to selectively activate or achieve a given enantiomer of a chiral molecule controlling the electrode potential (in electrosynthesis). Since the enantiomers of a chiral molecule have identical scalar physico-chemical properties and therefore the same electrochemical behavior except when interacting with some other chiral entity, enantioselective electrochemistry necessarily implies the electron transfer process to take place in asymmetric conditions. This can be achieved by the use of a chiral electrode surface or a chiral medium. Artificial selectors are particularly interesting on account of the virtually unlimited range of tailored structures possible as well as the possibility to have both enantiomers of a given selector equally available. Among the many approaches so far proposed for this ambitious target along either of the two above ways, outstanding results have been recently obtained, based on the use of "inherently chiral molecular materials" (either as electrode surfaces or as media) in which the same structural element endows the molecule with both its key functional property and with chirality