Ionic liquid confined in silica nanopores: molecular dynamics in the isobaric–isothermal ensemble

Molecular dynamics simulations in the isobaric–isothermal ensemble are used to investigate the structure and dynamics of an ionic liquid confined at ambient temperature and pressure in hydroxylated amorphous silica nanopores. The use of the isobaric–isothermal ensemble allows estimating the effect of confinement and surface chemistry on the density of the confined ionic liquid. The structure of the confined ionic liquid is investigated using density profiles and structural order parameters while its dynamics is assessed by determining the mobility and ionic conductivity of the confined phase. Despite the important screening of the electrostatic interactions (owing to the small Debye length in ionic liquids), the local structure of the confined ionic liquid is found to be mostly driven by electrostatic interactions. We show that both the structure and dynamics of the confined ionic liquid can be described as the sum of a surface contribution arising from the ions in contact with the surface and a bulk-like contribution arising from the ions located in the pore centre; as a result, most properties of the confined ionic liquid are a simple function of the surface-to-volume ratio of the host porous material. In contrast, the ionic conductivity of the confined ionic liquid, which is a collective dynamical property, is found to be similar to the bulk. This study sheds light on the complex behaviour of hybrid materials made up of ionic liquid confined in inorganic porous materials.     

Calixrotanes: Calixarenes Incorporating Spiro-Linked Cyclopropyl Groups

Macrocyclic compounds (calix[4]- and calix[6]arene derivatives) with aryl rings interconnected by spirocyclopropyl groups have been synthesized and structurally characterized. The compounds were prepared by the reaction of dichlorocarbene with calixarenes possessing exocyclic double bonds at the bridges, followed by reductive perdechlorination of the spirocyclopropyl groups. In all systems, pairs of geminal rings connected to the quaternary spiro carbon atoms are oriented anti, and the methylene groups of the cyclopropyl rings are located in isoclinal positions. Calix[6]rotane adopts in the crystal and in solution a 1,3,5-alternate conformation. The presence of the spirocyclopropyl groups increases the rigidity of the macrocyclic ring.     

Ring Size Determines the Conformation,Global Aromaticity and Photophysical Properties of Macrocyclic Oligofurans

In π-conjugated macrocycles, there is a trade-off between the global and local expression of effects such as aromaticity, with the outcome of the trade-off determined by the geometry and aromaticity of the constituent units. Compared with other aromatic rings, the aromatic character of furan is relatively small, and therefore global effects in macrocyclic furans are expected to be more pronounced. Following our introduction of macrocyclic oligofuran, we present the first synthesis of a series of π-conjugated bifuran macrocycles of various ring sizes, from trimer to hexamer, and characterize them using both computational and experimental methods. The properties of macrocyclic oligofurans change considerably with size: The smaller trimer is rigid, weakly emissive and planar as revealed by its single crystal structure, and displays global antiaromaticity. In contrast, the larger pentamer and hexamer are flexible, emissive, have non-planar structures, and exhibit local aromaticity. The results are supported by NICS and ACID calculations that indicate the global antiaromaticity of planar furan macrocycles, and by transient absorption measurements showing sharp absorption band for the trimer and only the internal conversion decay pathway.     

Zn Nanoparticles Modified Screen Printed Carbon Electrode as a Promising Sensor for Insulin Determination

Screen printed carbon electrodes (SPCEs) modified by a combination of chitosan, multi walled carbon nanotubes (MWCNTs) and zinc nanoparticles (ZnNPs) were studied for the first time as a suitable candidate for non-enzymatic insulin determination. In an effort to find the most suitable modification for electrochemical insulin determination, the stability, analytical characteristics, and selectivity were determined. The results confirmed that the ZnNPs/chitosan-MWCNTs prepared with the Zn deposition time of 45 s displayed the best electrocatalytic activity towards insulin oxidation in a wide linear concentration range (0.5 μM to 5 μM), with low limit of detection and high sensitivity.     

Perfluorophenyl‐Bifuran: A Stable and Fluorescent Material Exhibiting Mechanofluorochromic Behavior

π‐Conjugated oligomers and polymers consisting of bifuran units are applied in optoelectronic devices, because bifuran units endow such devices with superior properties compared with their thiophene analogs. However, as is true for most furan oligomers, bifuran oligomers suffer from low photostability, which restricts their application. In this work, we present the synthesis and the photophysical and structural characterization of perfluorinated phenyl bifuran ( PFB‐2F ), which displays high photostability, while maintaining strong fluorescence quantum efficiency in both solution and the solid state. X‐Ray crystallography reveals that, unlike its thiophene analog, PFB‐2F has a completely planar backbone, with slip‐stacked packing and short interplanar distances. PFB‐2F crystals display mechanofluorochromic behavior, which renders perfluorophenyl‐substituted oligofurans potential candidates for both stable optoelectronic devices and responsive optical materials.     

Lifetimes of electronically excited NO2 in a collision-free differentially pumped supersonic molecular beam

The lifetimes of rotationally cooled NO₂ were measured in the spectral region 5710–5960 Å in a differentially pumped collision- free supersonic molecular beam. Lifetime values (rotationally independent) between 25 and 260 μs were obtained. Over narrow spectral regions, the product of the fluorescence amplitude and the lifetime squared is vibrationally independent, as predicted by theory.     

Passively mode-locked ytterbium fiber laser utilizing chirped-fiber-Bragg-gratings for dispersion control

A robust, self-starting picosecond pulse source based on ytterbium (Yb³⁺) doped fiber laser is described. Utilizing a chirped-fiber-Bragg-grating (C-FBG) for dispersion control, solitary mode-locking is obtained without bulk dispersion compensation elements. A semiconductor saturable absorber (SESAM) is used for stable self-starting. 3.6 ps pulses are produced, with 45 MHz basic repetition-rate and mW scale average output power at 1060 nm. Detailed numerical simulations based on the modified nonlinear Schrödinger equation agree well with the experimental results and are used as a design tool for the solitary mode-locked picosecond laser. The presented design can be simply employed in an all-fiber environmentally-stable system.