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

Ab-Initio Calculation of Rate Constants for Molecule-Surface Reactions with Chemical Accuracy

The ab initio prediction of reaction rate constants for systems with hundreds of atoms with an accuracy that is comparable to experiment is a challenge for computational quantum chemistry. We present a divide-and-conquer strategy that departs from the potential energy surfaces obtained by standard density functional theory with inclusion of dispersion. The energies of the reactant and transition structures are refined by wavefunction-type calculations for the reaction site. Thermal effects and entropies are calculated from vibrational partition functions, and the anharmonic frequencies are calculated separately for each vibrational mode. This method is applied to a key reaction of an industrially relevant catalytic process, the methylation of small alkenes over zeolites. The calculated reaction rate constants (free energies), pre-exponential factors (entropies), and enthalpy barriers show that our computational strategy yields results that agree with experiment within chemical accuracy limits (less than one order of magnitude). A new strategy enables accurate quantum-mechanical ab initio predictions for the methylation of small alkenes over zeolite catalysts. The calculated reaction rate constants (free energies), pre-exponential factors (entropies), and enthalpy barriers show that this computational strategy yields results that agree with experiment within chemical accuracy limits

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

Physical Chemistry of Chloroquine Permeation through the Cell Membrane with Atomistic Detail

We provide a molecular-level description of the thermodynamics and mechanistic aspects of drug permeation through the cell membrane. As a case study, we considered the antimalaria FDA approved drug chloroquine. Molecular dynamics simulations of the molecule (in its neutral and protonated form) were performed in the presence of different lipid bilayers, with the aim of uncovering key aspects of the permeation process, a fundamental step for the drug’s action. Free energy values obtained by well-tempered metadynamics simulations suggest that the neutral form is the only permeating protomer, consistent with experimental data. H-bond interactions of the drug with water molecules and membrane headgroups play a crucial role for permeation. The presence of the transmembrane potential, investigated here for the first time in a drug permeation study, does not qualitatively affect these conclusions

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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