Electrochemical structure‐switching sensing using nanoplasmonic devices

In this article, the implementation of electrochemical plasmonic nanostructures functionalized with DNA‐based structure‐switching sensors is presented. eNanoSPR devices with open and microfluidic measurement cells are developed on the base of nanohole arrays in 100 nm gold film and applied for combined microscopic and electrochemical surface plasmon (eSPR) visualization. eSPR voltammograms and spectroscopy are performed using planar three electrode schematic with plasmonic nanostructure operated as working electrode. Limit of detection of eNanoSPR devices for oligonucleotide hybridization is estimated in the low nanomolar and applications for structure‐switching electro‐plasmonic sensing in complex liquids are discussed.     

Quantum mechanical single molecule partition function from path integral Monte Carlo simulations

An algorithm for calculating the partition function of a molecule with the path integral Monte Carlo method is presented. Staged thermodynamic perturbation with respect to a reference harmonic potential is utilized to evaluate the ratio of partition functions. Parallel tempering and a new Monte Carlo estimator for the ratio of partition functions are implemented here to achieve well converged simulations that give an accuracy of 0.04 kcal/mol in the reported free energies. The method is applied to various test systems, including a catalytic system composed of 18 atoms. Absolute free energies calculated by this method lead to corrections as large as 2.6 kcal/mol at 300 K for some of the examples presented.     

On global motions of a compressible barotropic and selfgravitating gas with density-dependent viscosities

We consider the Cauchy problem for the equations of selfgravitating motions of a barotropic gas with density-dependent viscosities μ(ρ), and λ(ρ) satisfying the Bresch–Desjardins condition, when the pressure P(ρ) is not necessarily a monotone function of the density. We prove that this problem admits a global weak solution provided that the adiabatic exponent γ associated with P(ρ) satisfies ${\gamma > \frac{4}{3}}$ .     

An in situ Al K-edge XAS investigation of the local environment of H+- and Cu+-exchanged USY and ZSM-5 zeolites

Aluminum coordination in the framework of USY and ZSM-5 zeolites containing charge-compensating cations (NH4+, H+, or Cu+) was investigated by Al K-edge EXAFS and XANES. This work was performed using a newly developed in-situ cell designed especially for acquiring soft X-ray absorption data. Both tetrahedrally and octahedrally coordinated Al were observed for hydrated H-USY and H-ZSM-5, in good agreement with 27Al NMR analyses. Upon dehydration, water desorbed from the zeolite, and octahedrally coordinated Al was converted progressively to tetrahedrally coordinated Al. These observations confirmed the hypothesis that the interaction of water with Br?nsted acid protons can lead to octahedral coordination of Al without loss of Al from the zeolite lattice. When H+ is replaced with NH4+ or Cu+, charge compensating species that absorb less water, less octahedrally coordinated Al was observed. Analysis of Al K-edge EXAFS data indicates that the Al-O bond distance for tetrahedrally coordinated Al in dehydrated USY and ZSM-5 is 1.67 angstroms. Simulation of k3chi(k) for Cu+ exchanged ZSM-5 leads to an estimated distance between Cu+ and framework Al atoms of 2.79 angstroms.