Enantioselective Tail-to-Head Terpene Cyclizations by Optically Active Hexameric Resorcin[4]arene Capsule Derivatives

Molecular capsules enable the conversion of substrates inside a closed cavity, mimicking to some extent enzymatic catalysis. Chirality transfer from the molecular capsule onto the encapsulated substrate has been only studied in a few cases. Here we demonstrate that chirality transfer is possible inside a rather large molecular container of approximately 1400 Å3. Specifically, we present 1) the first examples of optically active hexameric resorcin[4]arene capsules, 2) their ability to enantioselectively catalyze tail-to-head terpene cyclizations, and 3) the surprisingly high sensitivity of enantioselectivity on the structural modifications

Overriding Intrinsic Reactivity in Aliphatic C−H Oxidation: Preferential C3/C4 Oxidation of Aliphatic Ammonium Substrates

The site-selective C−H oxidation of unactivated positions in aliphatic ammonium chains poses a tremendous synthetic challenge, for which a solution has not yet been found. Here, we report the preferential oxidation of the strongly deactivated C3/C4 positions of aliphatic ammonium substrates by employing a novel supramolecular catalyst. This chimeric catalyst was synthesized by linking the well-explored catalytic moiety Fe(pdp) to an alkyl ammonium binding molecular tweezer. The results highlight the vast potential of overriding the intrinsic reactivity in chemical reactions by guiding catalysis using supramolecular host structures that enable a precise orientation of the substrates

Validity and usability of a smart ball–driven serious game to monitor grip strength in independent elderlies

Telemonitoring is one of the most expedient answers to the strong need for preventive care imposed by the rapidly aging society. We propose an innovative solution to the detection of early signs of frailty by presenting a serious game controlled by a smart sensorized soft plastic ball, designed to achieve continuous home-based monitoring of muscle weakness in older adults. Design, development, and testing of the smart ball and of the game interface devised to guide the monitoring procedure are presented. Reliability and concurrent validity of the system in measuring maximal grip strength against the clinical standard Jamar\uae were evaluated. Serious game usability and acceptance were investigated on 26 elderlies. Smart ball and Jamar measurements were well correlated (0.76 and 0.80 for dominant and non-dominant hands) and test\u2013retest reliability of pressure measurements was excellent (intraclass correlation coefficient >0.94). The serious game was well accepted by the 96.1 percent of participants, who provided a strongly positive usability score (87.7/100). The smart ball\u2013driven serious game demonstrated excellent reliability and good validity in measuring grip strength. The proposed smart ball\u2013driven serious game can be used for home self-monitoring of grip strength in elderlies

Precision tests of the Standard Model with leptonic and semileptonic kaon decays

We present a global analysis of leptonic and semileptonic kaon decays data, including all recent results by BNL-E865, KLOE, KTeV, ISTRA+, and NA48. Experimental results are critically reviewed and combined, taking into account theoretical (both analytical and numerical) constraints on the semileptonic kaon form factors. This analysis leads to a very accurate determination of Vus and allows us to perform several stringent tests of the Standard Model

Brain Computer Interfaces for inclusion

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Confinement effects and acid strength in zeolites

Chemical reactivity and sorption in zeolites are coupled to confinement and—to a lesser extent—to the acid strength of Brønsted acid sites (BAS). In presence of water the zeolite Brønsted acid sites eventually convert into hydronium ions. The gradual transition from zeolite Brønsted acid sites to hydronium ions in zeolites of varying pore size is examined by ab initio molecular dynamics combined with enhanced sampling based on Well-Tempered Metadynamics and a recently developed set of collective variables. While at low water content (1–2 water/BAS) the acidic protons prefer to be shared between zeolites and water, higher water contents (n > 2) invariably lead to solvation of the protons within a localized water cluster adjacent to the BAS. At low water loadings the standard free energy of the formed complexes is dominated by enthalpy and is associated with the acid strength of the BAS and the space around the site. Conversely, the entropy increases linearly with the concentration of waters in the pores, favors proton solvation and is independent of the pore size/shape

Insertable cardiac monitoring results in higher rates of atrial fibrillation diagnosis and oral anticoagulation prescription after ischaemic stroke

Aims: After an ischaemic stroke, atrial fibrillation (AF) detection allows for improved secondary prevention strategies. This study aimed to compare AF detection and oral anticoagulant (OAC) initiation in patients with an insertable cardiac monitor (ICM) vs. external cardiac monitor (ECM) after ischaemic stroke. Methods and results: Medicare Fee-for-Service (FFS) insurance claims and Abbott Labs device registration data were used to identify patients hospitalized with an ischaemic stroke in 2017-2019 who received an ICM or ECM within 3 months. Patients with continuous Medicare FFS insurance and prescription drug enrolment in the prior year were included. Patients with prior AF, atrial flutter, cardiac devices, or OAC were excluded. Insertable cardiac monitor and ECM patients were propensity score matched 1:4 on demographics, comorbidities, and stroke hospitalization characteristics. The outcomes of interest were AF detection and OAC initiation evaluated with Kaplan-Meier and Cox proportional hazard regression analyses. A total of 5702 Medicare beneficiaries (ICM, n = 444; ECM, n = 5258) met inclusion criteria. The matched cohort consisted of 2210 Medicare beneficiaries (ICM, n = 442; ECM, n = 1768) with 53% female, mean age 75 years, and mean CHA2DS2-VASc score 4.6 (1.6). Insertable cardiac monitor use was associated with a higher probability of AF detection [(hazard ratio (HR) 2.88, 95% confidence interval (CI) (2.31, 3.59)] and OAC initiation [HR 2.91, CI (2.28, 3.72)] compared to patients monitored only with ECM. Conclusion: Patients with an ischaemic stroke monitored with an ICM were almost three times more likely to be diagnosed with AF and to be prescribed OAC compared to patients who received ECM only