Re-weighted random series path integral simulations of molecular clusters: Applications to lithium solvated by a mixed Stockmayer cluster

Nuclear quantum effects in finite temperature simulations of molecular clusters are determined by taking advantage of a recently developed method based on the Feynman Path Integral. The structural and thermodynamic properties, including the nuclear quantum effects are determined for three Stockmayer clusters. The ionic system contain a lithium ion solvated by six strong dipoles and 12 weaker ones. The presence of the ion in the mixed Stockmayer cluster drastically enhances the fluxional nature of the less polar components which occupy the second solvation layer, whereas the neutral counterpart has the effect of reducing it. The nuclear quantum effects are significant at room temperature and above for the solvated ionic system. These are attributable to two factors: (a) the lightness of the lithium ion and (b) the stiffness of the ion-dipole interactions. At 300 K, the difference between the fully converged quantum and the classical heat capacities is about 1.3 K_B for the ionic cluster. This difference is about 10 SDs obtained from 95% confidence estimates of the statistical fluctuations. Cubic convergence is confirmed for temperatures as low as 50 K by regression analysis. The nuclear quantum effects do not change the peak melting temperature of the cluster.     

Individual‐Molecule Perspective Analysis of Chemical Reaction Networks: The Case of a Light‐Driven Supramolecular Pump

The first study in which stochastic simulations of a two‐component molecular machine are performed in the mass‐action regime is presented. This system is an autonomous molecular pump consisting of a photoactive axle that creates a directed flow of rings through it by exploiting light energy away from equilibrium. The investigation demonstrates that the pump can operate in two regimes, both experimentally accessible, in which light‐driven steps can be rate‐determining or not. The number of photons exploited by an individual molecular pump, as well as the precision of cycling and the overall efficiency, critically rely on the operating regime of the machine. This approach provides useful information not only to guide the chemical design of a self‐assembling molecular device with desired features, but also to elucidate the effect of the environment on its performance, thus facilitating its experimental investigation.     

Measurement of Very Fast Exchange Rates of Individual Amide Protons in Proteins by NMR Spectroscopy

NMR spectroscopy is a pivotal technique to measure hydrogen exchange rates in proteins. However, currently available NMR methods to measure backbone exchange are limited to rates of up to a few per second. To raise this limit, we have developed an approach that is capable of measuring proton exchange rates up to approximately 10⁴ s⁻¹. Our method relies on the detection of signal loss due to the decorrelation of antiphase operators 2N_xH_z by exchange events that occur during a series of pi pulses on the ¹⁵N channel. In practice, signal attenuation was monitored in a series of 2D H(CACO)N spectra, recorded with varying pi-pulse spacing, and the exchange rate was obtained by numerical fitting to the evolution of the density matrix. The method was applied to the small calcium-binding protein Calbindin D_9k, where exchange rates up to 600 s⁻¹ were measured for amides, where no signal was detectable in ¹⁵N−¹H HSQC spectra. A temperature variation study allowed us to determine apparent activation energies in the range 47–69 kJ mol⁻¹ for these fast exchanging amide protons, consistent with hydroxide-catalyzed exchange.     

The experimental design approach to the optimization of a simple quick easy cheap effective rugged and safe method for the analysis of phytoestrogens in complex soy‐based food

The present paper deals with the multivariate optimization of an extraction‐purification strategy for the determination of phytoestrogens (daidzein, genistein, coumestrol, formononetin, and biochanin A) in soy‐based meat substitutes by high performance liquid chromatography with tandem mass spectrometry. For a reliable quantitation of these new concerning compounds in such a complex matrix, recovery and matrix effect must be carefully evaluated. Therefore, two sequential experimental designs were used to optimize the sample‐pretreatment of soy‐based burgers: the chosen technique was the quick, easy, cheap, effective, rugged and safe methodology, which does not require any particular facility or instrumentation. Thanks to the first screening design (Plackett‐Burman), the significant factors influencing the studied responses were identified and further investigated through a response surface design (Box‐Behnken). The optimal values of the variables (volume of extraction solvent mix/sample mass ratio and two clean‐up sorbents) led to quantitative recoveries (97–104%) and low ion suppression (matrix effect 60–93%) for all analytes. This optimized method was characterized by low detection limits (0.2–1.5 ng/g) and excellent intraday precision (RSD 2–4%). It was applied to the determination of the considered compounds in several soy‐burgers from the Italian market, detecting low ng/g levels (up to 40 ng/g) of coumestrol, formononetin, and biochanin A, and high concentrations (7.9–78 µg/g) of genistein and daidzein.     

Parton distributions and new physics searches: the Drell–Yan forward–backward asymmetry as a case study

We present the first unquenched lattice-QCD calculation of the form factors for the decay \(B\rightarrow D^*\ell \nu \) at nonzero recoil. Our analysis includes 15 MILC ensembles with \(N_f=2+1\) flavors of asqtad sea quarks, with a strange quark mass close to its physical mass. The lattice spacings range from \(a\approx 0.15\) fm down to 0.045 fm, while the ratio between the light- and the strange-quark masses ranges from 0.05 to 0.4. The valence b and c quarks are treated using the Wilson-clover action with the Fermilab interpretation, whereas the light sector employs asqtad staggered fermions. We extrapolate our results to the physical point in the continuum limit using rooted staggered heavy-light meson chiral perturbation theory. Then we apply a model-independent parametrization to extend the form factors to the full kinematic range. With this parametrization we perform a joint lattice-QCD/experiment fit using several experimental datasets to determine the CKM matrix element \(|V_{cb}|\). We obtain \(\left| V_{cb}\right| = (38.40 \pm 0.68_{\text {th}} \pm 0.34_{\text {exp}} \pm 0.18_{\text {EM}})\times 10^{-3}\). The first error is theoretical, the second comes from experiment and the last one includes electromagnetic and electroweak uncertainties, with an overall \(\chi ^2\text {/dof} = 126/84\), which illustrates the tensions between the experimental data sets, and between theory and experiment. This result is in agreement with previous exclusive determinations, but the tension with the inclusive determination remains. Finally, we integrate the differential decay rate obtained solely from lattice data to predict \(R(D^*) = 0.265 \pm 0.013\), which confirms the current tension between theory and experiment.

     

A Stable Porphyrin Functionalized Graphite Electrode Used at the Oxygen Evolution Reaction Potential

Many researches have been devoted to rechargeable power generators that can store (but also release) energy. This availability is ensured through (e. g.) the oxygen evolution reaction (OER). However, (i) large values of the overpotentials and (ii) a progressive detriment of the anode (graphite) electrode limit the ultimate device. In view of enhancing the electrode performances, graphite was protected by following different strategies, which oblige to follow precise preparation protocols. Here, we prove that a thin layer of free-base porphyrin molecules is able to protect the underneath graphite electrode from detriment even if many (about 100) electrochemical cycles are performed.     

Phase equilibria in the Sm–Al–Si system at 500 °C

The isothermal section at 500 °C of the Sm–Al–Si system has been experimentally investigated by using scanning electron microscopy, electron microprobe analysis and X-ray powder diffraction. Four intermetallic compounds have been confirmed: τ₁-SmAl₂Si₂ (hP5-CaAl₂Si₂ type), τ₂-SmAl_xSi_1?x (tI12-Th₂Si type), τ₄-SmAl_0.5Si_0.5 (oS8-CrB type) and τ₅-Sm₆Al₃Si (tI80-Tb₆Al₃Si type). A new ternary intermediate has been found: τ₃-Sm₄Al₃Si₃ that crystallizes orthorhombic isostructural with Pr₄Al₃Ge₃.     

Hardware-in-the-loop simulation of wave energy converters based on dielectric elastomer generators

Dielectric elastomer generators (DEGs) are soft electrostatic generators based on low-cost electroactive polymer materials. These devices have attracted the attention of the marine energy community as a promising solution to implement economically viable wave energy converters (WECs). This paper introduces a hardware-in-the-loop (HIL) simulation framework for a class of WECs that combines the concept of the oscillating water columns (OWCs) with the DEGs. The proposed HIL system replicates in a laboratory environment the realistic operating conditions of an OWC/DEG plant, while drastically reducing the experimental burden compared to wave tank or sea tests. The HIL simulator is driven by a closed-loop real-time hydrodynamic model that is based on a novel coupling criterion which allows rendering a realistic dynamic response for a diversity of scenarios, including large scale DEG plants, whose dimensions and topologies are largely different from those available in the HIL setup. A case study is also introduced, which simulates the application of DEGs on an OWC plant installed in a mild real sea laboratory test-site. Comparisons with available real sea-test data demonstrated the ability of the HIL setup to effectively replicate a realistic operating scenario. The insights gathered on the promising performance of the analysed OWC/DEG systems pave the way to pursue further sea trials in the future.

     

Direct flow injection profiling of acyl glycerols from food products using isopropanol as solvent

This work proposes a novel method for the direct flow injection profiling of acylglycerols in edible oils and fats without preliminary extraction and consequent reconstitution in the injection solvent. The work exploits the outstanding performance of high‐resolution mass spectrometry to target unique elemental compositions even in the most complex matrices. The performance of isopropanol as the unique solvent for both the solubilization and analysis of acylglycerols was investigated in comparison with other classical methods involving preliminary extractions, sample recovery, and analysis. The calibrations of two triglyceride standards (triolein and trilinolenin) were successfully performed in presence and absence of oil matrix. As final application, the effects on the acylglycerol fraction of a heat treatment on three different fat samples (extra virgin olive oil, lard oil, and fat from dry cured ham—speck) were monitored. The proposed method is therefore suitable for a rapid evaluation of acylglycerol fractions in food lipid samples.