Strain‐Induced Isomerization in One‐Dimensional Metal–Organic Chains

The ability to use mechanical strain to steer chemical reactions creates completely new opportunities for solution‐ and solid‐phase synthesis of functional molecules and materials. However, this strategy is not readily applied in the bottom‐up on‐surface synthesis of well‐defined nanostructures. We report an internal strain‐induced skeletal rearrangement of one‐dimensional (1D) metal–organic chains (MOCs) via a concurrent atom shift and bond cleavage on Cu(111) at room temperature. The process involves Cu‐catalyzed debromination of organic monomers to generate 1,5‐dimethylnaphthalene diradicals that coordinate to Cu adatoms, forming MOCs with both homochiral and heterochiral naphthalene backbone arrangements. Bond‐resolved non‐contact atomic force microscopy imaging combined with density functional theory calculations showed that the relief of substrate‐induced internal strain drives the skeletal rearrangement of MOCs via 1,3‐H shifts and shift of Cu adatoms that enable migration of the monomer backbone toward an energetically favorable registry with the Cu(111) substrate. Our findings on this strain‐induced structural rearrangement in 1D systems will enrich the toolbox for on‐surface synthesis of novel functional materials and quantum nanostructures.     

Finite-Temperature Dimer Method for Finding Saddle Points on Free Energy Surfaces

The dimer method and its variants have been shown to be efficient in finding saddle points on potential surfaces. In the dimer method, the most unstable direction is approximately obtained by minimizing the total potential energy of the dimer. Then, the force in this direction is reversed to move the dimer toward saddle points. When the finite-temperature effect is important for a high-dimensional system, one usually needs to describe the dynamics in a low-dimensional space of reaction coordinates. In this case, transition states are collected as saddle points on the free energy surface. The traditional dimer method cannot be directly employed to find saddle points on a free energy surface since the surface is not known a priori. Here, we develop a finite-temperature dimer method for searching saddle points on the free energy surface. In this method, a constrained rotation dynamics of the dimer system is used to sample dimer directions and an efficient average method is used to obtain a good approximation of the most unstable direction. This approximated direction is then used in reversing the force component and evolving the dimer toward saddle points. Our numerical results suggest that the new method is efficient in finding saddle points on free energy surfaces. © 2019 Wiley Periodicals, Inc.     

Improved Performance for Toluene Abatement in a Continuous-Flow Pulsed Sliding Discharge Reactor Based on Three-Electrode Configuration

Plasma Chemistry and Plasma Processing - The degradation of toluene by non-thermal plasma has been evaluated in a continuous-flow sliding dielectric barrier discharge (SLDBD) reactor based on...     

Sulfonium,an Underestimated Moiety for Structural Modification,Alters the Antibacterial Profile of Vancomycin Against Multidrug‐Resistant Bacteria

In the antibiotics arsenal, vancomycin is a last resort for the treatment of intractable infections. However, this situation is under threat because of the increasing appearance of vancomycin‐resistant bacteria (VRB). Herein, we report a series of novel vancomycin derivatives carrying a sulfonium moiety. The sulfonium–vancomycin derivatives exhibited enhanced antibacterial activity against VRB both in vitro and in vivo. These derivatives also exhibited activity against some Gram‐negative bacteria. The sulfonium modification enhanced the interaction of vancomycin with the bacterial cell membrane and disrupts membrane integrity. Furthermore, the in vivo pharmacokinetic profile, stability, and toxicity of these derivatives demonstrated good druggability of the sulfonium–vancomycin analogues. This work provides a promising strategy for combating drug‐resistant bacterial infection, and advances the knowledge on sulfonium derivatives for structural optimization and drug development.     

Solid acids assisted matrix solid‐phase dispersion microextraction of alkaloids by capillary electrophoresis coupled with quadrupole time‐of‐flight mass spectrometry

The quantification of three alkaloids is important because quantitative study is a means of assessing the reliability of the experimental method, and three alkaloids of peimine, peiminine, and peimisine are main active ingredients in Chinese Pharmacopoeia 2015. An effective method based on the matrix solid‐phase dispersion microextraction was developed for the extraction of alkaloid compounds in Fritillariae Thunbergii Bulbus. Target analytes were analyzed by capillary electrophoresis coupled with quadrupole time‐of‐flight mass spectrometry. The optimized experimental condition was that 50 mg Fritillariae Thunbergii Bulbus was blended homogeneously with 10 mg citric acid for 5 min. Two hundred microliters of water acidized by 1 mol/L hydrochloric acid (pH = 4.5) was selected to elute tested alkaloids. The results demonstrated that the investigated method had low limits of detection (1.32–1.59 ng/mL), good recoveries (86.63–98.12%), and reproducibility (relative standard deviations of peak areas < 0.87%). The proposed matrix solid‐phase dispersion microextraction coupled with capillary electrophoresis combined with quadrupole time‐of‐flight mass spectrometry was successfully applied for the extraction of alkaloids in plants.     

Discovering ordered phases of block copolymers: new results from a generic Fourier-space approach

A generic Fourier-space approach to solve the self-consistent field theory of block copolymers is developed. This approach is based on the fact that, for any computational box with periodic boundary conditions, all spatially varying functions are spanned by the Fourier series determined by the size and shape of the box. The method reproduces all known diblock copolymer phases. The application of this method to a model "frustrated" triblock copolymer leads to a phase diagram with a number of new phases. Furthermore, the capability of the method to reproduce experimentally observed structures is demonstrated using the knitting pattern of triblock copolymers.     

Slow-light delay enhancement in small-core pure silica photonic crystal fiber based on Brillouin scattering

We demonstrate that we realize large-delay slow light based on stimulated Brillouin scattering in a short length of our fabricated small-core photonic crystal fiber (PCF). The cavity effect from the partially reflective splices in the end of the PCF enhances slow-light delay significantly. Our experiments show that large slow-light delay can be easily realized in a very short length of the PCF with a moderate pump power. Up to a one-half pulse-width delay is achieved in only 50 m of PCF in a single pump segment.     

An analytical model to estimate the performance of an indoor barrier at low-medium frequencies

Indoor barriers are now widely used for sound insulation. This paper examines the performance of indoor barriers in the low-medium frequency range and analyses the interaction between different natural modes of a room-barrier-room system. Morse proposed a theoretical model to calculate the sound field in a coupled-room, but this model neglects the surface integral of the boundary values of sound pressure. To estimate the performance of a barrier in an indoor environment, an analytical model is proposed that modifies the Green’s function for a non-rigid boundary enclosure and approximates the surface integral by a pre-estimated sound pressure based on Morse’s model. An additional approximation has been made in the proposed model to neglect the coupling area in the calculation of the surface integral. The proposed model used to predict the insertion loss of the barrier is verified by the experimental results using a 1:5 scale model. The predicted results agree well with the measured results at lower frequencies.     

Runge–Kutta discontinuous Galerkin method using WENO limiters II: Unstructured meshes

In [J. Qiu, C.-W. Shu, Runge–Kutta discontinuous Galerkin method using WENO limiters, SIAM Journal on Scientific Computing 26 (2005) 907–929], Qiu and Shu investigated using weighted essentially non-oscillatory (WENO) finite volume methodology as limiters for the Runge–Kutta discontinuous Galerkin (RKDG) methods for solving nonlinear hyperbolic conservation law systems on structured meshes. In this continuation paper, we extend the method to solve two-dimensional problems on unstructured meshes, with the goal of obtaining a robust and high order limiting procedure to simultaneously obtain uniform high order accuracy and sharp, nonoscillatory shock transition for RKDG methods. Numerical results are provided to illustrate the behavior of this procedure.