Crosslinkable-Chitosan-Enabled Moisture-Resistant Multilayer Gas Barrier Thin Film.

Chitosan-based films exhibit good oxygen barrier that degrades when exposed to high humidity. In an effort to overcome this drawback, a multilayer nanocoating consisting of crosslinkable chitosan (CHQ) and poly(acrylic acid) [PAA] is deposited on polyethylene terephthalate (PET) using layer-by-layer assembly. Chitosan is functionalized with glycidyl methacrylate to introduce acrylic functionalities within the film. The deposited films are crosslinked using a free radical initiator and this crosslinking is confirmed by FTIR and reduced film thickness. A 10-bilayer (BL) crosslinked CHQ/PAA film, which is only 165 nm thick, results in a 36× reduction of the oxygen transmission rate of PET at 90% relative humidity. To achieve these same results without crosslinking, a 15-BL unmodified chitosan (CH)/PAA film, which is almost 5× thicker, must be deposited on PET. This environmentally friendly, transparent nanocoating is promising for food packaging or protection of flexible electronics, especially in high-humidity environments.

Mica-Based Multilayer Nanocoating as a Highly Effective Flame Retardant and Smoke Suppressant.

Highly flammable polyurethane foam (PUF) remains a key risk factor associated with bedding and upholstered furniture, contributing to the yearly destruction of property and loss of lives. In an attempt to tackle this issue and develop a more benign flame retardant for PUF, a mica-based nanocomposite was deposited using layer-by-layer assembly. Chitosan (CH) and poly(acrylic acid) (PAA) were used to stabilize high-aspect-ratio mica. Foam treated with eight bilayers of CH- and PAA-stabilized mica preserves the porous foam structure, prevents melt dripping, and self-extinguishes during a 10 s torch test, while uncoated foam is completely consumed. When exposed to 35 kW/m2 heat flux during cone calorimetry, the peak heat release rate is reduced by 54% and less-volatile molecules are released during combustion, resulting in a 76% reduction in the total smoke release. This multilayer coating serves as an environmentally benign template for flame-retarding PUF and various other three-dimensional substrates.

Environmentally Benign and Self-Extinguishing Multilayer Nanocoating for Protection of Flammable Foam.

Most current flame-retardant nanocoatings for flexible polyurethane foam (PUF) consist of passive barriers, such as clay, graphene oxide, or metal hydroxide. In an effort to develop a polymeric and environmentally benign nanocoating for PUF, positively charged chitosan (CH) and anionic sodium hexametaphosphate (PSP) were deposited using layer-by-layer (LbL) assembly. Only six bilayers of CH/PSP film can withstand flame penetration during exposure to a butane torch (∼1400 °C) for 10 s and stop flame spread on the foam. Additionally, cone calorimetry reveals that the fire growth rate, peak heat release rate, and maximum average rate of heat emission are reduced by 55, 43, and 38%, respectively, compared with uncoated foam. This multilayer thin film quickly dehydrates to form an intumescent charred exoskeleton on the surface of the open-celled structure of polyurethane, inhibiting heat transfer and completely eliminating melt dripping. This entirely polymeric nanocoating provides a safe and effective alternative for reducing the fire hazard of polyurethane foam that is widely used for cushioning and insulation.

High Modulus, Thermally Stable, and Self-Extinguishing Aramid Nanofiber Separators.

Mechanically and thermally robust separators offer an alternative approach for preventing battery failure under extreme conditions such as high loads and temperatures. However, the trade-off between electrochemical performance and mechanical and thermal stability remains an ongoing challenge. Here, we investigate aramid nanofiber (ANF) separators that possess high moduli and self-extinguishing characteristics. The ANF separators are formed from the dissolution of bulk Kevlar fibers and their subsequent vacuum-assisted self-assembly. Thermogravimetric analysis shows a high 5 wt % decomposition temperature of 447 °C, which is over ∼175 °C higher than commercial Celgard separators. The ANF separator also possesses a high Young's modulus of 8.8 GPa, which is ∼1000% higher than commercial separators. Even when dry or when soaked in battery electrolyte, the ANF separators self-extinguish upon exposure to flame, whereas commercial separators melt or drip. We show that these features, although adventitious, present a trade-off with electrochemical performance in which a lithium nickel manganse cobalt (NMC) oxide-based battery possessed a reduced capacity of 123.4 mA h g-1. Considering the separator holistically, we propose that the ANF separator shows an excellent balance of the combined properties of high modulus, flame-resistance, thermal stability, and electrochemical stability and might be suitable for extreme environment applications with further testing.

Extreme Heat Shielding of Clay/Chitosan Nanobrick Wall on Flexible Foam.

Flexible polyurethane foam (PUF) is widely used in bedding, transportation, and furniture, despite being highly flammable. In an effort to decrease the flammability of the polymer, an environmentally friendly flame retardant coating was deposited on polyurethane foam (PUF) via layer-by-layer assembly. Treated foam was subjected to three different fire scenarios, 10 s torch test, cone calorimetry, and a 900 s burn-through test, to evaluate the thermal shielding behavior of an eight bilayer chitosan/vermiculite clay nanocoating. In each fire scenario, the nanocoating acts as a thermal shield from the flames by successfully protecting the backside of the PUF, whereas the side directly exposed to the flame results in a hollowed nanocoating that maintains the complex three-dimensional porous structure of the foam. Cone calorimetry reveals that the coating reduces the peak heat release rate and total smoke release by 53 and 63%, respectively, whereas a temperature gradient greater than 200 °C is observed across a 2.5 cm thick coated foam sample during the rigorous burn-through fire test. The thermal shielding behavior of this polymer/clay nanocoating makes this system very attractive in improving the fire safety of polyurethane foam used for insulating applications.

Quantifying the effect of covariates on concentrations and effects of steady-state phenprocoumon using a population pharmacokinetic/pharmacodynamic model.

BACKGROUND AND OBJECTIVES: The oral anticoagulant phenprocoumon, similar to other vitamin K antagonists, is characterized by pronounced interindividual variability in the doses needed to achieve the desired therapeutic effect. Previous studies assessed the effect of genetic and demographic covariates on empirical dose requirements of phenprocoumon to enable individualized dose prediction. The aim of the present study was to quantify major sources of interindividual variability separately on the pharmacokinetics and pharmacodynamics of phenprocoumon using a population pharmacokinetic-pharmacodynamic model. METHODS: A single steady-state blood sample was collected from 278 patients and assayed by liquid chromatography-tandem mass spectrometry for phenprocoumon and its metabolites. Genotyping was performed for variants of the cytochrome P450 (CYP) 2C9 (CYP2C9) and vitamin K epoxide reductase complex, subunit 1 (VKORC1) genes. Effects were quantified by international normalized ratio (INR). Data were analyzed simultaneously using NONMEM VII. RESULTS: The model confirmed CYP2C9 and VKORC1 variants as the major predictors of variability in phenprocoumon concentrations and effects, together with body weight, age, comedication with CYP3A modifiers (i.e. inhibitors or inducers) and presence of atrial fibrillation. These covariates explained 50.0 % of the observed variability in the model parameters. Phenprocoumon clearance fractions mediated per CYP2C9 allele were 13.4, 9.5 and 5.7 mL/h for the 1, 2 and 3 variants, respectively. An additional clearance fraction of 5.3 mL/h was independent of CYP2C9 activity. Homozygous VKORC1 wild-type carriers were estimated to have a 2.13-fold higher phenprocoumon exposure requirement than homozygous 1173 C>T carriers to achieve the same effect on INR. CONCLUSIONS: The model provides a deeper insight in the separate pharmacokinetic and pharmacodynamic parts of phenprocoumon action. Thus, it provides important information for individualized dose prediction, with the option to include further covariates not studied here with known effects on individual pharmacokinetic or pharmacodynamic processes.