Electrospinning of plant oil‐based,non‐isocyanate polyurethanes for biomedical applications

Non‐isocyanate polyurethanes (NIPU) have rapidly emerged as a sustainable, less toxic, and environmentally friendly alternative to traditional isocyanate‐based thermoplastic polyurethane (TPU) synthesis. TPU is widely used in the medical industry due to its excellent mechanical properties and elasticity. However, little work has been done to synthesize and electrospin NIPU into fibrous mats for biomedical applications. In this work, melt polymerization of a plant oil‐based cyclic carbonate monomer with polyether soft segments and various diamines yielded isocyanate‐free, segmented poly(amide hydroxyurethane)s (PAHUs). Electrospinning of segmented PAHUs afforded ductile, free‐standing fibrous mats with Young's modulus values between 7 and 8 MPa, suitable for tissue scaffold applications. PAHU fiber mats exhibited 3–4 times greater water uptake than the electrospun TPU control, demonstrating potential utility in drug delivery. Fibroblasts adhered to electrospun PAHU fibrous mats with viability values over 90% after 72‐h, validating its biocompatibility. The results highlight the high performance and potential of electrospun isocyanate‐free polyurethanes mats for biomedical application. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46464.     

Effect of additive structure and size on SiO2 formation in polymer‐derived SiOC ceramics

Silicon oxycarbide (SiOC) ceramics with highly adjustable properties and microstructures have many promising applications in batteries, catalysis, gas separation, and supercapacitors. In this study, additive structures on the nucleation and growth of SiO₂ within SiOC ceramics are investigated by adding cyclic tetramethyl‐tetravinylcyclotetrasiloxane (TMTVS) or caged octavinyl‐polyhedral oligomeric silsesquioxane (POSS) to a base polysiloxane (PSO) precursor. The effects of the 2 additives on the polymer‐to‐ceramic transformation and the phase formation within the SiOC are discussed. POSS encourages SiO₂ nucleation and leads to more SiO₂ formation with significantly increased ceramic yield, which subsequently leads to higher specific surface of 1557 m²/g with a larger pore size of ～1.8 nm for the porous SiOC. High TMTVS content decreases both the specific surface area and pore volume of the resulting porous SiOCs. This study demonstrates a new approach of using Si‐rich additive POSS to increase the SiOC yield while maintaining or even increasing the specific surface area.     

Conditions for imaging emulsions in the environmental scanning electron microscope

Environmental scanning electron microscopy (ESEM) is a technique capable of imaging volatile and/or insulating samples in their natural state, without prior specimen preparation. It is thus a powerful potential tool for the study of the structure and dynamics of emulsions and other complex liquid systems, at a resolution greater than that obtainable by conventional optical microscopy. We present images of a variety of liquid systems containing micron-scale and smaller features. The morphology of these systems may be clearly discerned. The contrast observed between the liquid phases was consistent with the model proposed by Stokes et al. (1998). The limits of resolution were determined by sample motion and by beam damage effects; under optimum conditions, resolution of a few tens of nanometers was obtained. This compares favourably with conventional and confocal optical microscopy. In some samples, thin films (solid or liquid) could be observed at the liquid/gas interface. Some of these films were so thin that they did not completely obscure the underlying structure of the bulk sample.     

Early stage dissolution characteristics of aluminosilicate glasses with blast furnace slag‐ and fly‐ash‐like compositions

Supplementary cementitious materials (SCM) have been used by the cement industry for decades to partly replace the portland cement fraction of concrete binders. This is particularly important today in addressing CO₂ emissions from the cement manufacturing process. However, defining the reactivity of these mainly aluminosilicate‐based materials and their influence on portland cement hydration chemistry has challenged the research community and has limited SCM replacement levels in cementitious binders. In this study, aluminosilicate glasses as models for blast furnace slag and fly‐ash systems were synthesized and exposed to different activator solutions in a continuously stirred closed system reactor for a period up to 3 hours. Solution compositions were measured from the very first minutes of dissolution and correlated with results from complementary solid surface analysis. Initial Ca concentration maxima in the first 30 minutes of exposure to the activating solution was a common feature in most dissolution profiles with a subsequent rapid decline attributable to Ca‐reincorporation on the reacting surface. Surface‐specific analysis confirmed Ca and Al enrichment at the surface, suggesting the formation of a Ca‐modified aluminosilicate layer, supporting a dissolution‐reprecipitation mechanism for SCM reactivity. Differing chemistries are thought to be responsible for the Ca and Al reintegration on the reacting surface depending on the pH of the solution; near‐neutral conditions favor Ca‐readsorption and surface condensation reactions, whereas alkaline solutions favor Ca‐reintegration via covalently bound phases.     

The economic effect of age and education on the regional flows of Black human capital

This paper quantifies and analyzes the flow of human capital caused by the migration of Blacks within the U.S. over time. Detailed characteristics of migration flows for Blacks moving in and out of each of the nine divisions in the U. S. were determined and multiplied by the appropriate value of human capital (discounted earnings approach). These flows were then summed to determine the aggregate inter-regional flows of Black human capital. The effects of age and education on these flows are analyzed as are the probable effects of such flows on regional economic growth.Results of the study show that there is a significant ageeducation interaction effect for Blacks. In addition, these interregional flows suggest that there is a substantial flow of Black human capital from the South to the North and West, and from the North to the West. Significant losses in Black human capital on the part of the South have several rather important public policy implications.     

The uptake of chemical elements from coal ash and settling basin effluent by primary producers II. Relation between concentrations in ash deposits and tissues of grasses growing on the ash

A number of reports of biomagnification of trace metals by plants indicate that elements are selectively concentrated within certain tissues when plants grow on coal ash. This study determined the uptake by, and tissue bioaccumulation of, 15 chemical elements within broom sedge and nut grass growing in the drainage system of a coal ash basin. Biomagnification of these elements by the grasses was compared to concentrations of these elements found in duckweed within the same system.Aluminium, arsenic, barium, cadmium, cobalt, chromium, copper, iron, mercury, manganese, molybdenum, selenium, strontium, titanium, and zinc were measured by neutron activation analysis in roots, stems, leaves and fruit of the grasses which grew in sediments within the effluent. Mercury and zinc were biomagnified in both grasses and duckweed to a level exceeding the concentration in sediment. All elements were biomagnified above the water concentration in all parts of the plants. Bioaccumulation of elements in the leaves and fruit of these plants provides a concentrated source of potentially toxic chemical elements for passage to animals which may consume these plants. The mechanisms of movement of potentially toxic elements from coal ash or water into food webs need additional study as utilization of coal is increased.     

Silver complexation in river waters of central New York

The dissolved component of the apparent silver complexation capacity was determined for Susquehanna and Chenango River water samples collected over a 3-month period in the vicinity of Binghamton, New York. Silver ion activities detected by the Ag⁺/S^2? ion selective electrode during potentiometric titration of the river water with AgNO₃ were lower than Ag⁺ activities calculated with an inorganic equilibrium speciation model. The maximum difference in Ag⁺ activity, which ranged from 1.5 × 10^?8 to 8.4 × 10^?8, was attributed to the presence of a constituent or constituents in the river water which strongly bind Ag, perhaps dissolved organic matter and/or colloidal material. Variation in apparent complexation capacity between river water samples was explained by different concentrations of the ligands complexing Ag. A tentative extrapolation of the dissolved Ag speciation to Ag concentrations in natural river water suggested that most of the Ag would be complexed by Cl^? and an unidentified constituent or constituents.     

Continued development of a mass balance model of chemical fate in a sewage treatment plant

Chemicals that pass through a sewage treatment plant (STP) and into receiving waters lead to exposure of human and ecological receptors. Most countries require that such chemicals and especially those that are new to commerce be assessed for their treatability in STPs using a screening-level model. The STP model has been widely used for such assessments in Canada, the US and elsewhere. It is important for both industry and regulators that such a model be simple, accurate and applicable even with the limited data available for most chemicals. The STP model has been upgraded to include the capability to handle ionizing chemicals, and a variety of treatment plant configurations commonly used in Canada and elsewhere around the world. A scheme for obtaining appropriate biodegradation half-lives for the different treatment options from available aqueous biodegradation half-lives or standard biodegradability tests is suggested. Model simulations show good agreement with pilot-scale experimental data from literature for 20 organic chemicals with widely varying physico-chemical properties.     

Impact of geochemical stressors on shallow groundwater quality

Groundwater monitoring wells (about 70 wells) were extensively installed in 28 sites surrounding Lake Texoma, located on the border of Oklahoma and Texas, to assess the impact of geochemical stressors to shallow groundwater quality. The monitoring wells were classified into three groups (residential area, agricultural area, and oil field area) depending on their land uses. During a 2-year period from 1999 to 2001 the monitoring wells were sampled every 3 months on a seasonal basis. Water quality assay consisted of 25 parameters including field parameters, nutrients, major ions, and trace elements. Occurrence and level of inorganics in groundwater samples were related to the land use and temporal change. Groundwater of the agricultural area showed lower levels of ferrous iron and nitrate than the residential area. The summer season data revealed more distinct differences in inorganic profiles of the two land use groundwater samples. There is a possible trend that nitrate concentrations in groundwater increased as the proportions of cultivated area increased. Water-soluble ferrous iron occurred primarily in water samples with a low dissolved oxygen concentration and/or a negative redox potential. The presence of brine waste in shallow groundwater was detected by chloride and conductivity in oil field area. Dissolved trace metals and volatile organic carbons were not in a form of concentration to be stressors. This study showed that the quality of shallow ground water could be related to regional geochemical stressors surrounding the lake.