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• Two Choline-AA based ILs were synthetized using an innovative synthetic route. • [Cho][Gly] and [Cho][Pro] were characterized by IR spectroscopy. • [Cho][Gly] and [Cho][Pro] were diluted with DMSO and tested for CO 2 absorption. • Operando IR setup monitored CO 2 -ILs chemical interaction and CO 2 concentration. • Two different mechanisms of reaction were identified on [Cho][Gly] and [Cho][Pro]. Tackling global warming through the reduction of greenhouse gases is a key challenge mankind is called to face in the close future. Carbon dioxide is one of the main causes of such temperature increase, thus avoiding its release in the atmosphere through capture and/or utilization strategies is a valuable tool to limit greenhouse effect. Presently, the applied technology for sequestrating CO 2 relies on its reaction with amines in aqueous solutions, giving rise to the formation of carbamates and carbonates. However, due to the energy intensive release step, toxicity and corrosiveness, amine scrubbing could not represent a long-term solution in CO 2 capture. Ionic liquids (ILs), organic salts in the liquid state near room temperature, are a class of emerging materials with a great potential towards CO 2 capture. Recently the combination of the choline cation with amino acids based anions gave rise to a wide set of bio-inspired ILs with low toxicity, that, due to the presence of amino groups in the amino acid moiety, are optimal candidates for CO 2 capture. In the present work, two choline-amino acids ILs were synthesized, containing glycine and proline, according to an innovative procedure, overcoming some drawbacks proper of the classical methods. A throughout IR operando study of the CO 2 absorption process in these amino acids based ILs was performed. Even though elementary reactions are the same for all the investigated systems, different absorption pathways were recognized depending on the amino acid based anion. The reversibility of the absorption process differs between the two systems as well, further remarking the role played by the selected amino acid in the overall absorption performances. Such fundamental information, still missing in the literature, will contribute to rationally develop choline-amino acids ILs with optimal CO 2 absorption/activation properties. [ABSTRACT FROM AUTHOR]

This chapter addresses the power and possibilities provided by an appropriate combination of advanced characterization techniques in understanding the environment of metal ions in different metal-zeolites, as well as in the role played by them in different catalytic reactions. Three different classes of materials are considered as case studies: (1) Cu-zeolites, where CuI and CuII ions are mainly present as counterions; (2) Fe-zeolites, often containing a wide variety of isolated, oligonuclear, and aggregated (oxide/hydroxide) FeII/FeIII species; and (3) TS-1, which is the closest to a “single-site” catalyst, mainly containing framework TiIV sites. TS-1 is studied in relation to its activity in the propene epoxidation reaction in the presence of aqueous H2O2, while Cu- and Fe-zeolites are here considered in relation to the direct conversion of methane to methanol (MTM) (a so-called dream reaction) with O2, N2O, or H2O2 as oxidizing agents. Main focus is into the nature of the active site precursors (i.e., mono or di-/trinuclear ions, oxidation state, and local environment) and into the electronic and geometric structure of the oxo species formed upon interaction with the oxidizing agents. Moreover, examples about in situ or operando experiments following changes during the reaction are reviewed. The main considered techniques are X-ray absorption spectroscopy (XAS) and resonance Raman (rR) and diffuse reflectance UV-Vis spectroscopies, often coupled to density functional theory (DFT) modeling. Depending on the studied system, results obtained with infrared, Mössbauer, X-ray emission (XES) and electron paramagnetic resonance (EPR) spectroscopies are also described. The discussion includes the open debates, the main drawbacks and potentialities of the techniques, and the related characterization challenges. [ABSTRACT FROM AUTHOR]

A set membership method for right inversion of nonlinear systems from data is proposed in the paper. Both the cases where the system to invert is known or unknown and therefore identified from data are addressed. The method does not require the invertibility of the regression function describing the system and ensures tight bounds on the inversion error. In the case of unknown system, the method allows the derivation of a robust right-inverse, guaranteeing the inversion error bound for all the systems belonging to the uncertainty set which can be defined from the available prior and experimental information. Based on such a set membership inversion, two methods for robust control of nonlinear systems from data are introduced: nonlinear feed-forward control (NFFC) and nonlinear internal model control (NIMC). Both the design methods ensure robust stability and bounded tracking errors for all the systems belonging to the involved uncertainty set. Two applicative examples of robust control from data are presented: NFFC control of semi-active suspension systems and NIMC control of vehicle lateral dynamics. [ABSTRACT FROM AUTHOR]

A vehicle equipped with a front steer-by-wire device is considered and the related control design problem dealt with by using a yaw rate feedback structure. In order to effectively handle both the system non-linearities and the input constraints, a Non-linear Model Predictive Control (NMPC) technique is adopted. A novelty of the present paper is that the vehicle model employed by the NMPC algorithm is obtained from previously collected input/output data, using a Non-linear Set Membership (NSM) identification methodology. Since the NSM approach is able to provide a model with minimal worst-case identification error, improved robustness of the closed-loop system is obtained with respect to that of an NMPC law based on a physical vehicle model. Furthermore, the measure of the model uncertainty provided by the NSM approach allows one to perform a theoretical robust stability analysis of the closed-loop system. The effectiveness of the proposed technique is shown through numerical simulations of manoeuvres using a detailed vehicle model. [ABSTRACT FROM AUTHOR]

Objective: Intraventricular hemorrhage (IVH) is a common cause of brain injury in preterm infants. Fresh human milk (HM) contains stem cells (SCs) that could potentially be delivered via intranasal HM (IHM). In this IHM pilot study, we describe outcomes., Study Design: Infants <33 weeks gestation with IVH were given IHM until maximum 28 days of age. Short-term neurologic outcomes and follow-up testing were compared to historic HM-fed infants. Longitudinal outcomes were plotted using linear mixed models. Weighted G-computation quantified treatment effects. Propensity score models calculated inverse probability weights for IVH grade, gestational age, and sex., Result: 37 infants (35.1% grade 3-4 IVH) were compared to 191 historic controls (17.8% grade 3-4 IVH). Post-hemorrhagic ventricular dilatation was common (25.7% IHM patients). Most weighted outcomes, although not significant, favored IHM at 4-12 and 18 months corrected age., Conclusion: This phase 1 study suggests powered trials of IHM for brain injury are needed. CLINICAL TRIAL REGISTRY NAME: clinicaltrials.gov identifier NCT04225286., (© 2024. The Author(s), under exclusive licence to Springer Nature America, Inc.)

Objective: There is a high burden of reintervention after repair of Tetralogy of Fallot (TOF). We compare procedural burden and late outcomes in valve sparing repair (VSR) and transannular patch (TAP) cohorts over 30 years., Methods: Patients undergoing TOF repair (1990-2021, excluding complex TOF) were included in this study (n=1239) with subsequent comparisons between TAP (n=550) and VSR (n=648) cohorts. Descriptive statistics, cumulative incidence frequencies, survival analysis and propensity matching (n=425) were used to analyze reintervention burden and survival., Results: Overall survival of the cohort was 96.7% at 15 years and 95.6% at 25 years, with similar survival between TAP and VSR cohorts (p=0.22). TAP cohort had increased incidence of procedural burden at 25 years (TAP 69.8% versus VSR 37.2%, p<0.001), with 34.6% undergoing ≥2 reinterventions. TAP cohort had higher incidence of surgical PV replacement at 15 years (TAP 20.7% versus VSR 7.6%, p<0.001) and placement of PA stents (TAP 20.2% versus VSR 4.9%, p<0.001). By contrast, VSR had higher incidence of RVOT reoperation at 15 years (VSR 7.3% versus TAP 3.6%, p=0.047). After propensity matching there was no survival advantage between the VSR and TAP cohorts (Era 2) whereas the need for RVOT reoperation was not different between the two cohorts (p=0.060)., Conclusions: The procedural burden remains high following TOF repair. TAP is associated with higher procedural burden in matched and non-matched cohorts. VSR has increased risk of reoperation for RVOT obstruction only in non-matched comparisons. Anatomical complexity and surgical repair strategy influence procedural burden following TOF repair., (Copyright © 2024. Published by Elsevier Inc.)

Objective: Blood product transfusion is a common practice in infants with hypoxic-ischemic encephalopathy (HIE) undoing therapeutic hypothermia (TH). The advantages and disadvantages of conservative or liberal transfusion practices in this fragile population are unknown. Study aims to characterize the transfusion practices in infants with HIE and investigate the association with outcome., Study Design: We conducted a retrospective cohort study at a single level IV NICU, evaluating transfusion thresholds, as well as the association between hematological abnormalities or blood product transfusions and outcomes in infants admitted with HIE., Result: By univariate analysis, FFP transfusion was associated with increased in-hospital death. However, multivariate analysis adjusting for HIE severity demonstrated no association between hematological abnormality or blood product transfusion and death, nor with neurodevelopmental impairment., Conclusion: No association was found between hematological blood product transfusion and death or neurodevelopmental impairment in a retrospective single NICU study of infants with HIE., (© 2024. The Author(s), under exclusive licence to Springer Nature America, Inc.)

Background: Long-term enlargement of the aortic arch after aortic arch reconstruction (AAR) in hypoplastic left heart syndrome (HLHS) is not well described., Methods: Aortic arch measurements for 50 patients with HLHS who achieved Fontan completion were converted to Pediatric Heart Network z-scores. Dimensions were assessed using linear mixed models and differences among time points were evaluated with F-tests. Sub-analysis was conducted comparing Norwood (n=36) vs hybrid (n=14) strategies., Results: Median time to last imaging was 6.4 (IQR, 3.5-11.3) years. Prior to intervention, the main pulmonary artery was dilated whereas the ascending aorta (AA), transverse arch (TA), and isthmus (ISTH) were hypoplastic. With AAR, there were expected increases in all arch z-scores. The aortic arch continued to dilate after AAR reaching peak values at 7 months [Neo-Aortic Complex (NAC): z= 6.9 (5.6-8.0)] or 12 months following stage I [AAo: z=6.1 (2.9-8.3); TA: z=4.7 (3.0-5.9)]. Following peak values, there was a gradual decline in z-scores with most components still at least mildly dilated at 16 years [NAC: z=3.2 (3.1-3.9), AAo: z=3.9 (3.3-4.2); TA: z=3.1 (2.5-3.7)] with abrupt calibre change at ISTH: z= -0.8 (-1.1- -0.3)]. Norwood and hybrid strategies showed similar enlargement profiles after 7 months of age., Conclusions: Neo-aortic root and aortic arch in HLHS are enlarged early after AAR and continue to enlarge out of proportion to normal controls until 12 months of age, with gradual decline in enlargement up to adolescence. Further work should focus on modifiable surgical factors which may prove important to optimize arch growth and geometry., (Copyright © 2024. Published by Elsevier Inc.)

One of the biggest obstacles to developing better zeolite-based catalysts is the lack of methods for quantitatively locating light heteroatoms on the T-sites in zeolites. Titanium silicalite-1 (TS-1) is a Ti-bearing zeolite-type catalyst commonly used in partial oxidation reactions with H 2 O 2 , such as aromatic hydroxylation and olefin epoxidation. The reaction mechanism is controlled by the configuration of titanium sites replacing silicon in the zeolite framework, but these sites remain unknown, hindering a fundamental understanding of the reaction. This study quantitatively determines heteroatoms within the zeolite-type framework using anomalous X-ray powder diffraction (AXRD) and the changes in the titanium X-ray scattering factor near the Ti K-edge (4.96 keV). Two TS-1 samples, each with approximately 2 Ti atoms per unit cell, were examined. Half of the titanium atoms are primarily split between sites T3 and T9, with the remainder dispersed among various T-sites within both MFI-type frameworks. One structure showed significant non-framework titanium in the micropores of a more distorted lattice. In both samples, isolated titanium atoms were more prevalent than dinuclear species, which could only potentially arise at site T9, but with a significant energy penalty and were not detected., (© 2024. The Author(s).)

Background: The minor G-allele of FOXO3 rs2802292 is associated with human longevity. The aim of this study was to test the protective effect of the variant against the association with type 2 Diabetes and NAFLD. Methods: rs2802292 was genotyped in a large population of middle-aged subjects (n = 650) from a small city in Southern Italy. All participants were interviewed to collect information about lifestyle and dietary habits; clinical characteristics were recorded, and blood samples were collected from all subjects. The association between rs2802292 and NAFLD or diabetes was tested using a logistic model and mediation analysis adjusted for covariates. Results: Overall, the results indicated a statistical association between diabetes and rs2802292, especially for the TT genotype (OR = 2.14, 1.01 to 4.53 95% C.I., p = 0.05) or in any case for those who possess the G-allele (OR = 0.45, 0.25 to 0.81 95% C.I., p = 0.008). Furthermore, we found a mediation effect of rs2802292 on diabetes (as mediator) and NAFLD. There is no direct relationship between rs2802292 and NAFLD, but the effect is direct (β = 0.10, -0.003 to 0.12 95% C.I., p = 0.04) on diabetes, but only in TT genotypes. Conclusions: The data on our cohort indicate that the longevity-associated FOXO3 variant may have protective effects against diabetes and NAFLD.

Colorectal cancer (CRC) ranks third in terms of cancer incidence worldwide and is responsible for 8% of all deaths globally. Approximately 10% of CRC cases are caused by inherited pathogenic mutations in driver genes involved in pathways that are crucial for CRC tumorigenesis and progression. These hereditary mutations significantly increase the risk of initial benign polyps or adenomas developing into cancer. In recent years, the rapid and accurate sequencing of CRC-specific multigene panels by next-generation sequencing (NGS) technologies has enabled the identification of several recurrent pathogenic variants with established functional consequences. In parallel, rare genetic variants that are not characterized and are, therefore, called variants of uncertain significance (VUSs) have also been detected. The classification of VUSs is a challenging task because each amino acid has specific biochemical properties and uniquely contributes to the structural stability and functional activity of proteins. In this scenario, the ability to computationally predict the effect of a VUS is crucial. In particular, in silico prediction methods can provide useful insights to assess the potential impact of a VUS and support additional clinical evaluation. This approach can further benefit from recent advances in artificial intelligence-based technologies. In this review, we describe the main in silico prediction tools that can be used to evaluate the structural and functional impact of VUSs and provide examples of their application in the analysis of gene variants involved in hereditary CRC syndromes.