MICROSCOPIC SPREADING CHARACTERISTICS OF NONPOLAR PERFLUOROPOLYETHER FILMS

The surface diffusion characteristics of nonpolar perfluoropolyether (PFPE) Z on carbon surfaces are investigated in two regimes, submonolayer and multilayer, for nano-thin films. For the submonolayer regime, the two-dimensional, cubic van der Waals equation of state is applied to determine the dependence of the surface diffusion coefficient on the film thickness, as experimental surface diffusion coefficients increase with increasing film thickness. For the multilayer regime, a conventional fluid mechanics analysis with position dependent viscosity and a van der Waals disjoining pressure gradient is applied to investigate the surface diffusion characteristics. The present theoretical analysis qualitatively agrees with the experimental results.     

Lipase PS-catalyzed transesterification of citronellyl butyrate and geranyl caproate: Effect of reaction parameters

Pseudomonas sp. lipase PS was immobilized by adsorption and tested for its ability to catalyze the synthesis of citronellyl butyrate and geranyl caproate by transesterification in n-hexane. The reaction parameters investigated were: enzyme load, effect of substrate concentration, added water, temperature, time course, organic solvent, pH memory, and enzyme reuse. Yields as high as 96 and 99% were obtained for citronellyl butyrate and geranyl caproate, respectively, with 300 units (approx. 15% w/w of reactants) of lipase PS. Increasing amounts of terpene alcohol inhibited lipase activity, while excess acyl donor (triacylglycerol) concentration enhanced ester production. Optimal yields were obtained at temperatures from 30–50°C after 24-h incubation time. Yields of 90 and 99% were obtained for citronellyl and geranyl esters, respectively, with 2% added water. Solvents with log P values ≥ 2.5 showed the highest conversion yields. pH 7 and 6–8 seemed to be ideal for citronellyl butyrate and geraniol caproate, respectively. The lipase remained active after reusing 12 times.     

Sunlight photodepolymerization of transient polymers

The study and development of transient devices is an emerging field where the disposal of a device after use is desired to avoid reverse engineering and minimize the environmental impact. Polyaldehydes with phototriggers have been investigated because the radiation wavelength can be adjusted to meet the transient application. Polynuclear aromatic hydrocarbons (PAHs) were used as the optical sensitizer for photoacid generators (PAGs). Photoinduced electron transfer (PET) with an iodonium-based PAG was used to expand the spectral sensitivity range. Anthracene, tetracene, and pentacene derivatives were synthesized with appended phenylethynyl groups to improve the solubility of the sensitizer and adjust the absorption wavelength. Sensitization of the iodonium-based PAG with the PAH derivatives was found to have thermodynamically favorable PET reactions for depolymerization of poly(propylene carbonate) and poly(phthalaldehyde) (PPHA). The Rehm–Weller equation and Stern–Volmer analysis were used to study the electron transfer and the fluorescence quenching rates of the PAHs with the iodonium salts, respectively. The photosensitivity, efficiency, and byproducts of the PET reactions in the decomposable polymer films are reported. A rapid photoreaction is reported for the depolymerization of PPHA exposed to a sunlight dose of <6 J cm⁻² (i.e., 1 min of direct sunlight) with a pentacene-based sensitizer. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47141.     

Molybdenum carbide catalysts for water–gas shift

Molybdenum carbide (Mo₂C) was demonstrated to be highly active for the water–gas shift of a synthetic steam reformer exhaust stream. This catalyst was more active than a commercial Cu–Zn–Al shift catalyst under the conditions employed (220–295°C and atmospheric pressure). In addition, Mo₂C did not catalyze the methanation reaction. There was no apparent deactivation or modification of the structure during 48 h on‐stream. The results suggest that high surface area carbides are promising candidates for development as commercial water–gas shift catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

Anti-Kasha Behavior of 3-Hydroxyflavone and Its Derivatives

Excited state intramolecular proton transfer (ESIPT) in 3-hydroxyflavone (3HF) has been known for its dependence on excitation wavelength. Such a behavior violates Kasha’s rule, which states that the emission and photochemistry of a compound would only take place from its lowest excited state. The photochemistry of 3HF was studied using femtosecond transient absorption spectroscopy at a shorter wavelength excitation (266 nm), and these new experimental findings were interpreted with the aid of computational studies. These new results were compared with those from previous studies that were obtained with a longer wavelength excitation and show that there exists a pathway of proton transfer that bypasses the normal first excited state from the higher excited state to the tautomer from first excited state. The experimental data correlate with the electron density difference calculations such that the proton transfer process is faster on the longer excitation wavelength than compared to the shorter excitation wavelength.     

Impact of Intrinsic Muscle Weakness on Muscle–Bone Crosstalk in Osteogenesis Imperfecta

Bone and muscle are highly synergistic tissues that communicate extensively via mechanotransduction and biochemical signaling. Osteogenesis imperfecta (OI) is a heritable connective tissue disorder of severe bone fragility and recently recognized skeletal muscle weakness. The presence of impaired bone and muscle in OI leads to a continuous cycle of altered muscle–bone crosstalk with weak muscles further compromising bone and vice versa. Currently, there is no cure for OI and understanding the pathogenesis of the skeletal muscle weakness in relation to the bone pathogenesis of OI in light of the critical role of muscle–bone crosstalk is essential to developing and identifying novel therapeutic targets and strategies for OI. This review will highlight how impaired skeletal muscle function contributes to the pathophysiology of OI and how this phenomenon further perpetuates bone fragility.     

Insights into the Genetic Variations of Human Cytochrome P450 2C9: Structural Analysis,Characterization and Comparison

Cytochromes P450 (CYP) are one of the major xenobiotic metabolizing enzymes with increasing importance in pharmacogenetics. The CYP2C9 enzyme is responsible for the metabolism of a wide range of clinical drugs. More than sixty genetic variations have been identified in CYP2C9 with many demonstrating reduced activity compared to the wild-type (WT) enzyme. The CYP2C9*8 allele is predominantly found in persons of African ancestry and results in altered clearance of several drug substrates of CYP2C9. The X-ray crystal structure of CYP2C9*8, which represents an amino acid variation from arginine to histidine at position 150 (R150H), was solved in complex with losartan. The overall conformation of the CYP2C9*8-losartan complex was similar to the previously solved complex with wild type (WT) protein, but it differs in the occupancy of losartan. One molecule of losartan was bound in the active site and another on the surface in an identical orientation to that observed in the WT complex. However, unlike the WT structure, the losartan in the access channel was not observed in the *8 complex. Furthermore, isothermal titration calorimetry studies illustrated weaker binding of losartan to *8 compared to WT. Interestingly, the CYP2C9*8 interaction with losartan was not as weak as the CYP2C9*3 variant, which showed up to three-fold weaker average dissociation constant compared to the WT. Taken together, the structural and solution characterization yields insights into the similarities and differences of losartan binding to CYP2C9 variants and provides a useful framework for probing the role of amino acid substitution and substrate dependent activity.     

Estimation of Width and Depth of the Wetted Soil Volume Under a Surface Emitter,Considering Root Water-Uptake and Evaporation

A cylindrical flow model that describes local infiltration from a surface point source, by incorporating evaporation and water extraction by roots, was used to obtain numerical results that were the base for the development and testing of an empirical method for determining the surface and vertical components of the wetting front. The implementation of the mathematical model took place against two of the twelve USDA soil classes, using three water application rates for each one. The empirical methodology consisted of two simple, time dependent empirical relationships: a power law for the stage of the infiltration, which was applied in both directions and a polynomial for the stage after the end of the irrigation, applied only for the vertical component, to account for percolation losses. The statistical criteria used for the evaluation of the method showed good agreement between the numerical results and the values calculated by the empirical relationships. Based on the limited availability of necessary experimental data for detailed analysis of multidimensional transient infiltration, the introduction of such an empirical model, as a design tool for trickle irrigation systems, may contribute to the selection of the optimum application rate and lateral spacing.     

Stability of Tocopherols and Retinyl Palmitate in Snack Extrudates

ABSTRACT: Fish- and peanut-containing half-products were obtained by extruding and drying tocopherol- and retinyl palmitate-fortified mixtures of tapioca starch and minced fish or partially defatted peanut flour (PDPF 60:40, wet basis). Half-products were puffed by deep-fat frying. Vitamins were determined simultaneously at each step of snack production using a direct solvent extraction method. Extrusion significantly reduced the content of tocopherols and retinyl palmitate in both products. Reduction of retinyl palmitate in fish and peanut extrudates during snack production was 48% and 27%, respectively. Final products contained more tocopherol than intermediates because of the high tocopherol content in the frying oil and its uptake.     

MESOZOIC MAGMATISM IN THE FALKLAND ISLANDS (SOUTH ATLANTIC) AND THEIR OFFSHORE SEDIMENTARY BASINS

Recent mineral and hydrocarbons exploration in and around the Falkland Islands has provided data that allows correlation of the onshore and offshore histories of magmatism. New Ar‐Ar age dating of onshore dykes in East Falkland has extended their Cretaceous age range back to ca. 135 Ma (Valanginian – Hauterivian) from the previously reported age of ca. 121 Ma (Aptian). Widespread onshore, ca.188–178 Ma, Jurassic dykes are generally considered a part of the regional Karoo‐Ferrar magmatism linked to the initial break‐up of Gondwana, but we relate the Early Cretaceous dykes, with their characteristic north‐south orientation, to extension of the Falklands Plateau during initiation of spreading in the South Atlantic Ocean. The onshore dykes demonstrate east‐west Early Cretaceous extension, whilst to the north of the archipelago the offshore North Falklands Basin extended between north‐south boundary fault systems from the Late Jurassic onwards. Intrusion of Valanginian – Hauterivian dykes onshore was penecontemporaneous with the intrusion of sills and the extrusion of lavas in the Falkland Plateau Basin. This magmatism, more extensive than previously supposed, may be linked to regional uplift associated with initial opening of the South Atlantic Ocean. The uplift can be demonstrated from seismic data and DSDP boreholes to have occurred during the Berriasian – Hauterivian interval. The thermally‐driven uplift of the platform region played a crucial role in elevating potential sediment source areas and providing the large volumes of sand that were shed intermittently into the surrounding basins from the Valanginian to the Aptian or Albian.