Experimental methods in chemical engineering: Electron paramagnetic resonance spectroscopy-EPR/ESR

Electron paramagnetic resonance (EPR) spectroscopy, also known as electron spin resonance spectroscopy (ESR), utilizes absorption of microwave radiation by unpaired electrons in a magnetic field. The interaction between the unpaired electron(s) and nearby magnetic nuclei helps identify paramagnetic species and can provide information about the motion of the molecule and the local polarity, pH, viscosity, concentration, and accessibility to other paramagnetic species. This mini-review discusses the fundamental underpinnings of EPR needed to correctly interpret EPR spectra. We describe various types of EPR spectra encountered by chemical engineers, and use application examples drawn from the chemical engineering literature to illustrate the information available from the technique. Few chemical engineering departments or even chemistry departments have EPR instruments, which contributes to the significant barrier that prevents this being adopted as a routine measurement technique. However, in 2016 and 2017, Web of Science indexed 7000 articles that applied EPR spectroscopy. A bibliometric map categorized the keywords in four categories based on co-occurrences: magnetic properties, films, and luminescence; crystal structure, complexes, and ligands; nanoparticles, oxidation, and degradation; and, systems, radicals, and H₂ O₂ .     

Biocatalytic electrode improvement strategies in microbial fuel cell systems

Microbial fuel cells (MFCs) produce electricity as a result of the microbial metabolism of organic substrates, hence they represent a sustainable approach for energy production and waste treatment. If the technology is to be implemented in industry, low cost and sustainable bioelectrodes must be developed to increase power output, increase waste treatment capacity, and improve service intervals. Although the current application of abiotic electrode catalysts, such as platinum and electrode binders such as Nafion leads to greater MFC performance, their use is cost prohibitive. Novel bioelectrodes which use cost effective and sustainable materials are being developed. These electrodes are developed with the intention to reduce start-up time, reduce costs, extend life-span and improve core MFC performance metrics (i.e. power density, current density, chemical oxygen demand (COD) reduction and Coulombic efficiency (CE)). Comparison of different MFC systems is not an easy task. This is due to variations in MFC design, construction, operation, and different inocula (in the case of mixed-culture MFCs). This high intra-system variability should be considered when assessing MFC data, operation and performance. This review article examines the major issues surrounding bioanode and biocathode improvement in different MFC systems, with the ultimate goal of streamlining and standardising improvement processes. © 2018 Society of Chemical Industry     

Photo-mediated copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) “click” reactions for forming polymer networks as shape memory materials

The formation of polymer networks polymerized with the Copper (I) – catalyzed azide – alkyne cycloaddition (CuAAC) click reaction is described along with their accompanying utilization as shape memory polymers. Due to the click nature of the reaction and the synthetic accessibility of azide and alkyne functional-monomers, the polymer architecture was readily controlled through monomer design to manipulate crosslink density, ability for further functionalization, and the glass transition temperature (55–114 °C). Free strain recovery is used to quantify the shape memory properties of a model CuAAC network resulting in excellent shape fixity and recovery of 99%. The step growth nature of this polymerization results in homogenous network formation with narrow glass transitions ranges having half widths of the transition close to 15 °C for these materials resulting in shape recovery sharpness of 3.9%/°C in a model system comparable to similarly crosslinked chain growth polymers. Utilization of the CuAAC reaction to form shape memory materials opens a range of possibilities and behaviors that are not readily achieved in other shape memory materials such as (meth) acrylates, thiol-ene, thiol-Michael, and poly(caprolactone) based shape memory materials.     

Effect of cellulosic sugar degradation products (furfural and hydroxymethyl furfural) on acetone–butanol–ethanol (ABE) fermentation using Clostridium beijerinckii P260

Studies were performed to identify chemical compounds present in wheat straw hydrolysate (WSH) that enhance acetone butanol ethanol (ABE) productivity. These compounds were identified as furfural and hydroxymethyl furfural (HMF). Control experiment resulted in the production of 21.38 g L^?1 ABE with a productivity of 0.30 g L^?1 h^?1. WSH contained 0.04–0.34 g L^?1 furfural and 0.12–0.88 g L^?1 HMF. Addition of furfural to the fermentation medium at a concentration of 0.50 g L^?1 resulted in a productivity of 0.88 g L^?1 h^?1 which is 293% of the productivity obtained in control experiments. Supplementation with 1.00 g L^?1 HMF into the fermentation medium produced 25.27 g L^?1 ABE with a productivity of 0.68 g L^?1 h^?1. A combination of furfural (0.50 g L^?1) and HMF (0.50 g L^?1) also enhanced ABE production and productivity when added to the fermentation medium. Both furfural and HMF enhanced specific productivity (233–308%) of ABE. In brief, WSH contained an adequate concentration of furfural and HMF that enhanced ABE productivity, specific productivity, and product concentration.     

Feasibility of fast neutron analysis for the detection of explosives buried in soil

A commercialized thermal neutron analysis (TNA) sensor has been developed to confirm the presence of buried bulk explosives as part of a multi-sensor anti-tank landmine detection system. Continuing improvements to the TNA system have included the use of an electronic pulsed neutron generator that offers the possibility of applying fast neutron analysis (FNA) methods to improve the system's detection capability. This paper describes an investigation into the use of FNA as a complementary component in such a TNA system. The results of a modeling study using simple geometries and a full model of the TNA sensor head are presented, as well as preliminary results from an experimental associated particle imaging (API) system that supports the modeling study results. The investigation has concluded that the pulsed beam FNA approach would not improve the detection performance of a TNA system for landmine or buried IED detection in a confirmation role, and could not be made into a practical stand-alone detection system for buried anti-tank landmines. Detection of buried landmines and IEDs by FNA remains a possibility, however, through the use of the API technique.     

Attentional episodes in visual perception.

Is one's temporal perception of the world truly as seamless as it appears? This article presents a computationally motivated theory suggesting that visual attention samples information from temporal episodes (episodic simultaneous type/serial token model; Wyble, Bowman, & Nieuwenstein, 2009). Breaks between these episodes are punctuated by periods of suppressed attention, better known as the attentional blink (Raymond, Shapiro, & Arnell, 1992). We test predictions from this model and demonstrate that participants were able to report more letters from a sequence of 4 targets presented in a dense temporal cluster than from a sequence of 4 targets interleaved with nontargets. However, this superior report accuracy comes at a cost in impaired temporal order perception. Further experiments explore the dynamics of multiple episodes and the boundary conditions that trigger episodic breaks. Finally, we contrast the importance of attentional control, limited resources, and memory capacity constructs in the model. (PsycINFO Database Record (c) 2011 APA, all rights reserved)     

Categorically defined targets trigger spatiotemporal visual attention.

Transient attention to a visually salient cue enhances processing of a subsequent target in the same spatial location between 50 to 150 ms after cue onset (K. Nakayama & M. Mackeben, 1989). Do stimuli from a categorically defined target set, such as letters or digits, also generate transient attention? Participants reported digit targets among keyboard symbols in a changing array of 8 items. When 1 target preceded a second target in the same location at a stimulus onset asynchrony of 107 ms (but not 213 ms), the second target was reported more often than in a condition in which there was no leading target. When the 2 targets were at different locations, report of the second target was impaired. With both letters and digits as targets, the enhancement effect was shown not to be due to category priming. Critically, the attentional benefit was present whether or not participants reported the leading target. Transient attention, contingent attentional capture, popout, and Lag 1 sparing in the attentional blink may involve a common mechanism for orienting processing resources towards salient and task relevant stimuli. (PsycINFO Database Record (c) 2010 APA, all rights reserved)