Multilayered Materials Comprising Mesoporous Thin Films and Metal Nanoparticles

A novel composite material based on metal nanoparticles (NP) and mesoporous thin films (MPTF), more specifically bilayers of MPTF with a submonolayer of NP deposited between them is introduced. By controlling the deposition conditions, it is possible to build a variety of multilayers including MPTF with different compositions (TiO₂, SiO₂) and pore sizes (templated with cetyltrimethylammonium bromide, F127, Brij 58) and NP of different characteristics and sizes (Au spheres, Au decorated SiO₂). By means of 2D small angle X‐ray scattering, transmission electron microscopy, UV–vis spectroscopy, and ellipsometric porosimetry it is demonstrated that NP and MPTF retain their structure and properties within the new material. Importantly, the NP remain accessible for further reactions, a feature that is established by Au overgrowth. Interestingly, the extent of Au growth depends on the mesoporous size and the position of the MPTF with respect to the NP. This new architecture allows the NP to be in direct contact with two different chemical environments and, as a consequence, opens up the possibility to control identity and size of the molecules that can reach them. Thus, the obtained materials may be applied in the development of highly specific sensors and catalysts, in which spatial position plays a fundamental role.     

Asymptotics of Running Maxima for φ-Subgaussian Random Double Arrays

Methodology and Computing in Applied Probability - The article studies the running maxima $Y_{m,j}=\max_{1 \le k \le m, 1 \le n \le j} X_{k,n} - a_{m,j}$ where {Xk,n,k ≥?1,n...     

Plasmon-assisted click chemistry at low temperature: an inverse temperature effect on the reaction rate

Plasmon assistance promotes a range of chemical transformations by decreasing their activation energies. In a common case, thermal and plasmon assistance work synergistically: higher temperature results in higher plasmon-enhanced catalysis efficiency. Herein, we report an unexpected tenfold increase in the reaction efficiency of surface plasmon-assisted Huisgen dipolar azide–alkyne cycloaddition (AAC) when the reaction mixture is cooled from room temperature to −35 °C. We attribute the observed increase in the reaction efficiency to complete plasmon-induced annihilation of the reaction barrier, prolongation of plasmon lifetime, and decreased relaxation of plasmon-excited-states under cooling. Furthermore, control quenching experiments supported by theoretical calculations indicate that plasmon-mediated substrate excitation to an electronic triplet state may play the key role in plasmon-assisted chemical transformation. Last but not least, we demonstrated the possible applicability of plasmon assistance to biological systems by AAC coupling of biotin to gold nanoparticles performed at −35 °C.

The decrease of reaction temperature can potentially lead to an increase of plasmon-assisted catalytic efficiency.     

Adaptive integration of molecular dynamics

This article presents a particle method framework for simulating molecular dynamics. For time integration, the implicit trapezoidal rule is employed, where an explicit predictor enables large time steps. Error estimators for both the temporal and spatial discretization are advocated, and facilitate a fully adaptive propagation. The framework is developed and exemplified in the context of the classical Liouville equation, where Gaussian phase-space packets are used as particles. Simplified variants are discussed briefly. The concept is illustrated by numerical examples for one-dimensional dynamics in double well potential.     

Impact of 1-butyl-3-methylimidazolium chloride on the electrospinning of cellulose acetate nanofibers

Additives like ionic liquids (ILs) have proven to be excellent materials useful in improving the electrospinnability and conductivity of both synthetic and biopolymers. The aim of this study is to investigate the effect of 1-buthyl-3-methylimidazolium chloride [BMIM]Cl on the electrospinnability of cellulose acetate (CA). The results showed that [BMIM]Cl has the greater effect on viscosity and conductivity of the spinning solution while the morphology of the nanofibers significantly improved as the concentration of the IL increases from 0% to 12% (v/v) of [BMIM]Cl. To understand the interaction between CA and [BMIM]Cl, Fourier-transform infrared spectroscopy (FTIR) has been used. Observations by scanning electron microscopy (SEM) suggested that [BMIM]Cl significantly altered the morphology of the CA nanofibers and 12% (v/v) of [BMIM]Cl would be an ideal concentration producing uniform fibers with a mean diameter of 180nm. In addition, the membranes showed a significant increase in conductivity (from 0 to 2.21 × 10^?7S/cm) as the concentration of ionic liquid increases up to 12% (v/v) that indicates a successful loading of IL inside the nanofibers.