Alkenyl-functionalized NHC iridium-based catalysts for hydrosilylation

A family of alkenyl-functionalized N-heterocyclic-carbene–iridium(I) complexes has been synthesized, providing a series of mono-coordinated, bis-chelate and pincer alkenyl-NHC species. Olefin coordination is highly influenced by the nature of the substituents on the NHC ring, and on the length of the alkenyl branch. A fluxional process involving coordination/decoordination of the olefin in bis-allyl-NHC complexes has been studied, and the activation parameters have been determined by means of VT-NMR spectroscopy. The mono-coordinated complexes are highly active in the hydrosilylation of terminal alkynes, showing high selectivity for the Z-isomers, with no a-isomers or dehydrogenative silylation processes being observed. The molecular structures reported that are representative of the species have been determined by means of X-ray crystallograph

A Counterfactual Safety Margin Perspective on the Scoring of Autonomous Vehicles' Riskiness

Autonomous Vehicles (AVs) have the potential to provide numerous societal benefits, such as decreased road accidents and increased overall transportation efficiency. However, quantifying the risk associated with AVs is challenging due to the lack of historical data and the rapidly evolving technology. This paper presents a data-driven framework for comparing the risk of different AVs' behaviors in various operational design domains (ODDs), based on counterfactual simulations of "misbehaving" road users. We introduce the concept of counterfactual safety margin, which represents the minimum deviation from normal behavior that could lead to a collision. This concept helps to find the most critical scenarios but also to assess the frequency and severity of risk of AVs. We show that the proposed methodology is applicable even when the AV's behavioral policy is unknown -- through worst- and best-case analyses -- making the method useful also to external third-party risk assessors. Our experimental results demonstrate the correlation between the safety margin, the driving policy quality, and the ODD shedding light on the relative risk associated with different AV providers. This work contributes to AV safety assessment and aids in addressing legislative and insurance concerns surrounding this emerging technology

Systematic study of the correlation between surface chemistry, conductivity and electrocatalytic properties of graphene oxide nanosheets

A main advantage of graphene oxide (GO) over other materials is the high tunability of its surface functional groups and of its electric conductivity. However, the complex chemical composition of GO renders difficult to unravel the correlation between structural and electric properties. Here, we use a combination of electron spectroscopy and electrochemistry to correlate the surface chemistry of GO to its electrical conductivity and electrocatalytic properties with respect to two molecules of high biological interest: β-nicotinamide adenine dinucleotide (NADH) and vitamin C. We demonstrate that the electrocatalytic properties of the material are due to hydroxyl, carbonyl and carboxyl groups residues that, even if already present on pristine GO, become electroactive only upon GO reduction. The results of this study demonstrate the advantages in the use of GO in amperometric biosensing and in enzymatic biofuel cells: it allows the oxidation of the target molecules at low potential values, with a sensitivity >15 times higher with respect to standard, carbon-based electrode materials. Finally, we demonstrate that the right amount of chemical groups to achieve such high performance can be obtained also by direct electrochemical exfoliation of bulk graphite, without passing through GO production, thus rendering this approach suitable for cheap, large-scale applications

An Electroactive and Self-Assembling Bio-Ink, based on Protein-Stabilized Nanoclusters and Graphene, for the Manufacture of Fully Inkjet-Printed Paper-Based Analytical Devices

Hundreds of new electrochemical sensors are reported in literature every year. However, only a few of them makes it to the market. Manufacturability, or rather the lack of it, is the parameter that dictates if new sensing technologies will remain forever in the laboratory in which they are conceived. Inkjet printing is a low-cost and versatile technique that can facilitate the transfer of nanomaterial-based sensors to the market. Herein, an electroactive and self-assembling inkjet-printable ink based on protein-nanomaterial composites and exfoliated graphene is reported. The consensus tetratricopeptide proteins (CTPRs), used to formulate this ink, are engineered to template and coordinate electroactive metallic nanoclusters (NCs), and to self-assemble upon drying, forming stable films. The authors demonstrate that, by incorporating graphene in the ink formulation, it is possible to dramatically improve the electrocatalytic properties of the ink, obtaining an efficient hybrid material for hydrogen peroxide (H2O2) detection. Using this bio-ink, the authors manufactured disposable and environmentally sustainable electrochemical paper-based analytical devices (ePADs) to detect H2O2, outperforming commercial screen-printed platforms. Furthermore, it is demonstrated that oxidoreductase enzymes can be included in the formulation, to fully inkjet-print enzymatic amperometric biosensors ready to use

Graphene-Paper-Based Electrodes on Plastic and Textile Supports as New Platforms for Amperometric Biosensing

The possibility of exfoliating graphite into graphene sheets allows the researchers to produce a material, termed “graphene paper” (G-paper), conductive as graphite but more flexible and processable. G-paper is already used for electronic applications, like conductors, antennas, and heaters, outperforming metal conductors thanks to its high flexibility, lightness, chemical stability, and compatibility with polymeric substrates. Here, the effectiveness in the use of G-paper for the realization of electrodes on flexible plastic substrates and textiles, and their applicability as amperometric sensors are demonstrated. The performance of these devices is compared with commercial platforms made of carbon-based inks, finding that they outperform commercial devices in sensing nicotinamide adenine dinucleotide (NADH), a key molecule for enzymatic biosensing; the electrodes can achieve state-of-the-art sensitivity (107.2 μA mm−1 cm−2) and limit of detection (0.6 7 10−6 m) with no need of additional functionalization. Thanks to this property, the stable deposition of a suitable enzyme, namely lactate dehydrogenase, on the electrode surface is used as a proof of concept of the applicability of this new platform for the realization of a biosensor. The possibility of having a single material suitable for antennas, electronics, and now sensing opens new opportunities for smart fabrics in wearable electronic applications

Simultaneous Detection of Glucose and Fructose in Synthetic Musts by Multivariate Analysis of Silica-Based Amperometric Sensor Signals

Silica-based electrodes which permanently include a graphite/Au nanoparticles composite were tested for non-enzymatic detection of glucose and fructose. The composite material showed an effective electrocatalytic activity, to achieve the oxidation of the two analytes at quite low potential values and with good linearity. Reduced surface passivation was observed even in presence of organic species normally constituting real samples. Electrochemical responses were systematically recorded in cyclic voltammetry and differential pulse voltammetry by analysing 99 solutions containing glucose and fructose at different concentration values. The analysed samples consisted both in glucose and fructose aqueous solutions at pH 12 and in solutions of synthetic musts of red grapes, to test the feasibility of the approach in a real frame. Multivariate exploratory analyses of the electrochemical signals were performed using the Principal Component Analysis (PCA). This gave evidence of the effectiveness of the chemometric approach to study the electrochemical sensor responses. Thanks to PCA, it was possible to highlight the different contributions of glucose and fructose to the voltammetric signal, allowing their selective determination.This research received funding from the University of Cadiz through the 'Contratos Puente 2015' postdoctoral program and from the University of Modena and Reggio Emilia (Italy) through FAR 2014

Characteristics, comorbidities and laboratory measures associated with disease severity and poor prognosis in young and elderly patients with COVID-19 admitted to medical wards in Emilia-Romagna region, Italy: a multicentre retrospective study

Background and Objectives. A relatively small number of studies have investigated the characteristics, comorbidities and laboratory measures associated with prognosis in patients with COVID-19, admitted to Internal Medicine Units (IMU) in Italy. Therefore, we performed a retrospective multicentre study to identify baseline features, predisposing to severe disease and poor outcomes, in adult individuals with SARS-CoV2 infection, hospitalized in 5 IMUs in the Emilia-Romagna region (Italy). Materials and Methods. We included 129 consecutive patients (male 75, median age 68 years) from 1st March 2020 to 31st October 2021. Patients' baseline characteristics, comorbidities, laboratory measures, and outcomes were collected. Results. At admission, the factors significantly associated with a higher risk of in-hospital mortality included: age (median 68 vs. 83 years in survived vs. dead patients, P=0.000), diabetes [Odds Ratio (OR) 4.00, P=0.016], chronic obstructive pulmonary disease (OR 4.60, P=0.022), cancer (OR 5.81, P=0.021), acute- (OR 9.88, P=0.000) and chronicrenal failure (OR 6.76, P=0.004). During the study period, 16 individuals died (12.4%), all over 70 years old. In deceased vs. non-deceased patients were detected: i) more elevated white blood cells and neutrophils-counts and lower lymphocytes count; ii) higher levels of total/direct bilirubin, creatinine, C-reactive-protein, lactate-dehydrogenase, ferritin, but only a slight Interleukin-6 increase; iii) a trend of lower vitamin D values. Conclusions. We proposed a new I index, a modified form of the Age-Adjusted Charlson Comorbidity Index, by considering pO(2)/FiO(2) ratio, to better characterize the severity of COVID-19. Furthermore, we critically discuss our results with the current assumption which considers COVID-19 as a pathological condition associated with cytokine storm

electrochemical sensing of glucose by chitosan modified graphene oxide

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A Spatially Resolved Dark- versus Light-Zone Microenvironment Signature Subdivides Germinal Center-Related Aggressive B Cell Lymphomas

We applied digital spatial profiling for 87 immune and stromal genes to lymph node germinal center (GC) dark- and light-zone (DZ/LZ) regions of interest to obtain a differential signature of these two distinct microenvironments. The spatially resolved 53-genes signature, comprising key genes of the DZmutational machinery and LZ immune and mesenchymal milieu, was applied to the transcriptomes of 543 GC-related diffuse large B cell lymphomas and double-hit ( DH) lymphomas. According to the DZ/LZ signature, the GC-related lymphomas were sub-classified into two clusters. The subgroups differed in the distribution of DH cases and survival, with most DH displaying a distinct DZ-like profile. The clustering analysis was also performed using a 25-genes signature composed of genes positively enriched in the non-B, stromal sub-compartments, for the first time achieving DZ/LZ discrimination based on stromal/immune features. The report offers new insight into the GC microenvironment, hinting at a DZ microenvironment of origin in DH lymphomas

Avaliação neuropsicomotora e classificação funcional em escolares de 10 a 12 anos da rede pública.

Neuropsychomotor development (NPMD) involves the motor and cognitive areas and is influenced by environmental and task questions, which from an expanded health point of view can be classified by the International Classification of Functioning, Disability and Health (ICF). The objective of this study was to evaluate the school’s NPMD and classify them according to the ICF. The study included 22 pre-adolescents (10-12 years) of both sexes, in the metropolitan region of Curitiba, Brazil, assessed by the Fonseca’s Psychomotor Battery, the Functional Independence Measure, semi-structured interviews and ICF checklist for children and youth (ICF-CY). We observed that most students did not show changes in the NPMD, and that the self- report identified: changes in the family model, few possibilities for sports and leisure, preference for playing as entertainment, school as the prevailing environment, good self-perception of health, accessibility problems. In addition, we identified one child with delay in some isolated psychomotor factors, but with a good general psychomotor performance. The use of the model proposed by the authors answered the demands of the ICF, indicating its applicability and possibilities of use in the school environment.O desenvolvimento neuropsicomotor (DNPM) envolve as áreas motoras e cognitivas e é influenciado por questões do ambiente e da tarefa, o que numa visão ampliada de saúde pode ser classificado por meio da Classificação Internacional de Funcionalidade, Incapacidade e Saúde (CIF). O objetivo deste estudo foi avaliar o DNPM de escolares e classificá-los de acordo com a CIF. Participaram do estudo 22 pré-adolescentes (10 a 12 anos) de ambos os sexos, na região metropolitana de Curitiba, avaliados por meio da Bateria Psicomotora de Fonseca, Medida da independência funcional, entrevista semiestruturada e check-list da CIF para crianças e jovens (CIF-CJ). Observou-se que a maioria dos estudantes não apresentou alterações no DNPM, e que o auto-relato identificou: mudança no modelo familiar, poucas possibilidades para esporte e lazer, preferência pelas brincadeiras como entretenimento, escola como ambiente predominante, boa autopercepção de saúde, dificuldade de acessibilidade. Além disso, identificou-se uma criança com atraso em fatores psicomotores isolados, mas com bom desempenho psicomotor geral. A utilização do modelo proposto pelos autores respondeu às dimensões da CIF, indicando sua aplicabilidade e possibilidades de uso em ambiente escolar