Photoelectrochemical cells based on a novel porphyrin containing light harvesting conducting copolymer

A copolymer of anti-5,15-bis([2′,2″:5″,2″′-terthiophene]-3″-yl)-2,8,12,18-tetra-n-butyl-3,7,13,17-tetramethylporphyrin (1) with 2,2′:5′2″-terthiophene (2) was successfully electrosynthesised and was then characterised by cyclic voltammetry, UV-Vis spectroscopy, four-point probe conductivity measurement, and scanning electron microscopy. This novel light harvesting conducting copolymer was then incorporated into photoelectrochemical cells using a liquid electrolyte and tested for photovoltaic responses. The effect of zinc incorporation into the porphyrin cavity was also investigated, and the best device generated an open circuit voltage of 185 mV, short circuit current of 881 μA cm⁻² with a fill factor of 0.36 and energy conversion efficiency of 0.12% under a halogen white light intensity of 500 W m⁻².     

Bayesian selection of threshold autoregressive models

Abstract.  An approach to Bayesian model selection in self-exciting threshold autoregressive (SETAR) models is developed within a reversible jump Markov chain Monte Carlo (RJMCMC) framework. Our approach is examined via a simulation study and analysis of the Zurich monthly sunspots series. We find that the method converges rapidly to the optimal model, whilst efficiently exploring suboptimal models to quantify model uncertainty. A key finding is that the parsimony of the model selected is influenced by the specification of prior information, which can be examined and subjected to criticism. This is a strength of the Bayesian approach, allowing physical understanding to constrain the model selection algorithm.     

Engineered Biomolecular Recognition of RDX by Using a Thermostable Alcohol Dehydrogenase as a Protein Scaffold

There are many biotechnology applications that would benefit from simple, stable proteins with engineered biomolecular recognition. Here, we explored the hypothesis that a thermostable alcohol dehydrogenase (AdhD from Pyrococcus furiosus) could be engineered to bind a small molecule instead of a cofactor or molecules involved in the catalytic transition state. We chose the explosive molecule 1,3,5‐trinitro‐1,3,5‐triazine (royal demolition explosive, RDX) as a proof‐of‐concept. Its low solubility in water was exploited for immobilization for biopanning by using ribosome display. Docking simulations were used to identify two potential binding sites in AdhD, and a randomized library focused on tyrosine or serine mutations was used to determine that RDX was binding in the substrate binding pocket of the enzyme. A fully randomized binding pocket library was selected, and affinity maturation by error‐prone PCR led to the identification of a mutant (EP‐16) that gained the ability to bind RDX with an affinity of (73±11) μm . These results underscore the way in which thermostable enzymes can be useful scaffolds for expanding the biomolecular recognition toolbox.     

Evolution of maturity levels of the particle surface and bulk during soot growth and oxidation in a flame

We performed a study of the evolution of soot composition and fine structure, i.e., maturity level, in an atmospheric ethylene-air diffusion flame. We used laser-induced incandescence (LII) to provide information about maturity level of the bulk primary particle and X-ray photoelectron spectroscopy (XPS) to provide complementary information about particle-surface-maturity level. The results demonstrate that the bulk material and the particle surface evolve separately in the flame. Increased soot-maturity level is associated with increased long-range order of the particle fine structure. This increased order leads to an increase in the absorption cross-section in the visible and near-infrared and a shift of the absorption to longer wavelengths with increasing maturity level of the bulk particle. These trends result in a decrease in the dispersion exponent (?) and increase in the absorption cross-section scaling factor (?), as inferred from LII measurements. LII measurements demonstrate that bulk-maturity level increases with height-above-the-burner (HAB) until it reaches a plateau in the center of the flame at the maximum in the soot volume fraction. Bulk-maturity level only slightly decreases as soot is oxidized at larger HABs. Increased maturity level also leads to an increase in long-range sp² hybridization. XPS measurements of the sp²/defect ratio demonstrate an increase in soot surface-maturity level with increasing HAB, but the surface-maturity level increases more gradually with HAB than the bulk-maturity level. Whereas the bulk-fine-structure order decreases slightly in the oxidation region, the surface order decreases dramatically, indicating that oxidation occurs preferentially at the surface under these conditions.

Copyright © The Authors. Published with license by American Association for Aerosol Research     

Evaluation of Elemental and Black Carbon Measurements from the GAViM and IMPROVE Networks

The GAViM program provides fine particulate and visibility data for several remote locations in Canada. Two long-term intercomparison studies between the GAViM and a major U.S. aerosol monitoring network, IMPROVE, were used to evaluate the uncertainty in the analytical data produced by proton induced x-ray emission (PIXE), proton elastic scattering analysis (PESA), and gravimetric analysis. GAViM and IMPROVE agreed well for elements from Fe to Zn where PIXE is the most sensitive; the relative difference between the 2 networks for Fe and Zn was <2%. Some lighter elements, e.g., sodium or sulphur, revealed a difference of 10-20%. Furthermore, an empiric conversion scheme for the GAViM absorption data produced by the laser integrated plate method (LIPM) was derived from the comparison to the IMPROVE thermal/optical reflectance (TOR) data. This conversion depends on the aerosol composition and is therefore site specific. It allows estimation of the elemental carbon concentrations from the historic raw light absorption values obtained by LIPM. If the mass attenuation coefficient of the fine aerosol collected at the 2 remote GAViM sites is assumed to be equal to 10 m 2 /g, then the results imply that the light absorption coefficient measured by LIPM is generally higher than the true value by up to a factor of 1.3 or 1.8, respectively. In both cases, LIPM overestimated the black carbon content, mostly for the lightly loaded samples.     

Economic value and environmental impact (EVEI) analysis of biorefinery systems

The selection of product portfolios, processing routes and the combination of technologies to obtain a sustainable biorefinery design according to economic and environmental criteria represents a challenge to process engineering. The aim of this research is to generate a robust methodology that assists process engineers to conceptually optimise the environmental and economic performances of biorefinery systems. A novel economic value and environmental impact (EVEI) analysis methodology is presented in this paper. The EVEI analysis is a tool that emerges from the combination of the value analysis method for the evaluation of economic potential with environmental footprinting for impact analysis. The methodology has been effectively demonstrated by providing insights into the performance of a bioethanol plant as a case study. The systematisation of the methodology allowed its implementation and integration into a computer-aided process engineering (CAPE) tool in the spreadsheet environment.     

An improved accelerated weathering protocol to anticipate Florida exposure behavior of coatings

A new accelerated weathering protocol has been developed which closely replicates the performance of automotive and aerospace coating systems exposed in South Florida. IR spectroscopy was used to verify that the chemical composition changes that occurred during accelerated weathering in devices with a glass filter that produced a high fidelity reproduction of sunlight’s UV spectrum matched those that occurred during natural weathering. Gravimetric water absorption measurements were used to tune the volume of water absorption during accelerated weathering to match that which occurred during natural weathering in South Florida. The frequency of water exposure was then scaled to the appropriate UV dose. A variety of coating systems were used to verify the correlation between the physical failures observed in the accelerated weathering protocol and natural weathering in South Florida. The new accelerated weathering protocol correctly reproduced gloss loss, delamination, cracking, blistering, and good performance in a variety of diverse coating systems. For automotive basecoat/clearcoat paint systems, the new weathering protocol shows significant acceleration over both Florida and previous accelerated weathering tests. For monocoat aerospace systems, the new weathering protocol showed less acceleration than for automotive coatings, but was still an improvement over previous accelerated tests and was faster than Florida exposure.     

Obesity: Prevalence,Theories, Medical Consequences,Management, and Research Directions

Obesity and its associated disorders are a growing epidemic across the world. Many genetic, physiological, and behavioral factors play a role in the etiology of obesity. Diet and exercise are known to play a valuable role in the treatment and prevention of obesity and associated disorders such as hypertension, heart disease, and diabetes. Therefore, the purpose of this review is to examine the prevalence, etiology, consequences, and treatment of obesity.     

Low Dietary c9t11-Conjugated Linoleic Acid Intake from Dairy Fat or Supplements Reduces Inflammation in Collagen-Induced Arthritis

Dietary cis‐9,trans‐11 (c9t11) conjugated linoleic acid (CLA) fed at 0.5 % w/w was previously shown to attenuate inflammation in the murine collagen‐induced (CA) arthritis model, and growing evidence implicates c9t11‐CLA as a major anti‐inflammatory component of dairy fat. To understand c9t11‐CLA's contribution to dairy fat's anti‐inflammatory action, the minimum amount of dietary c9t11‐CLA needed to reduce inflammation must be determined. This study had two objectives: (1) determine the minimum dietary anti‐inflammatory c9t11‐CLA intake level in the CA model, and (2) compare this to anti‐inflammatory effects of dairy fat (non‐enriched, naturally c9t11‐CLA‐enriched, or c9t11‐CLA‐supplemented). Mice received the following dietary fat treatments (w/w) post arthritis onset: corn oil (6 % CO), 0.125, 0.25, 0.375, and 0.5 % c9t11‐CLA, control butter (6 % CB), c9t11‐enriched butter (6 % EB), or c9t11‐CLA‐supplemented butter (6 % SB, containing 0.2 % c9t11‐CLA). Paw arthritic severity and pad swelling were scored and measured, respectively, over an 84‐day study period. All c9t11‐CLA and butter diets decreased the arthritic score (25–51 %, P < 0.01) and paw swelling (8–11 %, P < 0.01). Throughout the study, plasma tumor necrosis factor (TNFα) was elevated in CO‐fed arthritic mice compared to non‐arthritic (NA) mice but was reduced in 0.5 % c9t11‐CLA‐ and EB‐fed mice. Interleukin‐1β and IL‐6 were increased in arthritic CO‐fed mice compared to NA mice but were reduced in 0.5 % c9t11‐CLA‐ and EB‐fed mice through day 42. In conclusion, 0.125 % c9t11‐CLA reduced clinical arthritis as effectively as higher doses, and decreased arthritis in CB‐fed mice suggested that the minimal anti‐inflammatory levels of c9t11‐CLA might be below 0.125 %.     

Development and Validation of an Artificial Mechanical Skin Model for the Study of Interactions between Skin and Microneedles

Microneedles are small needle‐like structures that are almost invisible to the naked eye. They have an immense potential to serve as a valuable tool in many medical applications, such as painless vaccination. Microneedles work by breaking through the stratum corneum, the outermost barrier layer of the skin, and providing a direct path for drug delivery into the skin. A lot of research has been presented over the past two decades on the applications of microneedles, yet the fundamental mechanism of how they interact, pressure, and penetrate the skin in its native state is worth examining further. As such, a major difficulty with understanding the mechanism of microneedle–skin interaction is the lack of an artificial mechanical human skin model to use as a standardized substrate. In this research news, the development of an artificial mechanical skin model based on a thorough mechanical study of fresh human and porcine skin samples is presented. The artificial mechanical skin model can be used to study the mechanical interactions between microneedles and skin, but not diffusion of molecules across skin. This model can assist in improving the performance of microneedles by enhancing the reproducibility of microneedle depth insertions for optimal drug delivery and biosensing.