Layer-by-Layer Nanocoatings with Flame Retardant and Oxygen Barrier Properties: Moving Toward Renewable Systems

Numerous studies have focused on enhancing the flame retardant behavior of cotton and polyurethane foam. Some of the most commonly used treatments (e.g., brominated compounds) have raised concerns with regard to toxicity and environmental persistence. These concerns have led to significant research into the use of alternative approaches, including polymer nanocomposites prepared from more environmentally benign nanoparticles. These particles migrate to the surface from the bulk during fire exposure to form a barrier on the surface that protects the underlying polymer. This theory of fire suppression in bulk nanocomposites inspired the use of layer-by-layer (LbL) assembly to create nanocoatings in an effort to produce more effective and environmentally-benign flame retardant treatments. Negatively charged silica nanoparticles of two different sizes were paired with either positively charged silica or cationic polyethylenimine (PEI) to create thin film assemblies. When applying these films to cotton fabric, all coated fabrics retained their weave structure after being exposed to a vertical flame test, while uncoated cotton was completely destroyed. Micro combustion calorimetry confirmed that coated fabrics exhibited a reduced peak heat release rate, by as much as 20% relative to the uncoated control. Even so, this treatment would not pass the standard UL94 vertical flame test, necessitating a more effective treatment. Positively- charged chitosan (CH) was paired with montmorillonite (MMT) clay to create a renewable flame retardant nanocoating for polyurethane foam. This coating system completely stops the melting of a flexible polyurethane foam when exposed to direct flame from a butane torch, with just 10 bilayers (~ 30 nm thick). The same coated foam exhibited a reduced peak heat release rate, by as much as 52%, relative to the uncoated control. This same nanobrick wall coating is able to impart gas barrier to permeate plastic film. Multilayered thin films were assembled with "green" food contact approved materials (i.e., chitosan, polyacrylic acid (PAA) and montmorillonite clay). Only ten CH-PAA-CH-MMT quadlayers (~90 nm thick) cause polylactic acid (PLA) film to behave like PET in terms of oxygen barrier. A thirty bilayer CH-MMT assembly (~100 nm thick) on PLA exhibits an oxygen transmission rate (OTR) below the detection limit of commercial instrumentation (<= 0.005 cm^3/(m^2*day*atm)). This is the same recipe used to impart flame retardant behavior to foam, but it did not provide effective FR to cotton fabric, so a very different recipe was used. Thin films of fully renewable electrolytes, chitosan and phytic acid (PA), were deposited on cotton fabric in an effort to reduce flammability through an intumescent effect. Altering the pH of aqueous deposition solutions modifies the composition of the final nanocoating. Fabrics coated with highest PA content multilayers completely extinguished the flame and reduced peak heat release (pkHRR) and total heat release of 60% and 76%, respectively. This superior performance is believed to be due to high phosphorus content that enhances the intumescent behavior of these nanocoatings

Novel Oncogenic Transcription Factor Cooperation in RB-Deficient Cancer

The retinoblastoma tumor suppressor (RB) is a critical regulator of E2F-dependent transcription, controlling a multitude of protumorigenic networks including but not limited to cell-cycle control. Here, genome-wide assessment of E2F1 function after RB loss in isogenic models of prostate cancer revealed unexpected repositioning and cooperation with oncogenic transcription factors, including the major driver of disease progression, the androgen receptor (AR). Further investigation revealed that observed AR/E2F1 cooperation elicited novel transcriptional networks that promote cancer phenotypes, especially as related to evasion of cell death. These observations were reflected in assessment of human disease, indicating the clinical relevance of the AR/E2F1 cooperome in prostate cancer. Together, these studies reveal new mechanisms by which RB loss induces cancer progression and highlight the importance of understanding the targets of E2F1 function. SIGNIFICANCE: This study identifies that RB loss in prostate cancer drives cooperation between AR and E2F1 as coregulators of transcription, which is linked to the progression of advanced disease

Exceptionally Flame Retardant Sulfur-Based Multilayer Nanocoating for Polyurethane Prepared from Aqueous Polyelectrolyte Solutions

Many current flame retardant (FR) strategies for polymers contain environmentally harmful compounds and/or negatively impact processing and mechanical properties. In an effort to overcome these issues, a effective flame retardant nanocoating comprised of positively charged chitosan (CH) and anionic poly­(vinyl sulfonic acid sodium salt) (PVS) was deposited onto flexible polyurethane foam using layer-by-layer (LbL) assembly. This coating system completely stops foam melt dripping upon exposure to the direct flame from a butane torch. Furthermore, 10 CH-PVS bilayers (∼30 nm thick) add only 5.5% to the foam’s weight and completely stop flame propagating on the foam due to the fuel dilution effect from non flammable gases (e.g, water, sulfur oxides, and ammonia) released from the coating during degradation. Cone calorimetry reveals that this same coated foam has a 52% reduction in peak heat release rate relative to an uncoated control. This water-based, environmentally benign nanocoating provides an effective postprocess flame retardant treatment for a variety of complex substrates (foam, fabric, etc.)

Clay–Chitosan Nanobrick Walls: Completely Renewable Gas Barrier and Flame-Retardant Nanocoatings

Thin films prepared via a layer-by-layer (LbL) assembly of renewable materials exhibit exceptional oxygen barrier and flame-retardant properties. Positively charged chitosan (CH), at two different pH levels (pH 3 and pH 6), was paired with anionic montmorillonite (MMT) clay nanoplatelets. Thin-film assemblies prepared with CH at high pH are thicker, because if the low polymer charge density. A 30-bilayer (CH pH 6-MMT) nanocoating (∼100 nm thick) reduces the oxygen permeability of a 0.5-mm-thick polylactic acid film by four orders of magnitude. This same coating system completely stops the melting of a flexible polyurethane foam, when exposed to direct flame from a butane torch, with just 10 bilayers (∼30 nm thick). Cone calorimetry confirms that this coated foam exhibited a reduced peak heat-release rate, by as much as 52%, relative to the uncoated control. These environmentally benign nanocoatings could prove beneficial for new types of food packaging or a replacement for environmentally persistent antiflammable compounds

Exceptionally Flame Retardant Sulfur-Based Multilayer Nanocoating for Polyurethane Prepared from Aqueous Polyelectrolyte Solutions

Many current flame retardant (FR) strategies for polymers contain environmentally harmful compounds and/or negatively impact processing and mechanical properties. In an effort to overcome these issues, a effective flame retardant nanocoating comprised of positively charged chitosan (CH) and anionic poly­(vinyl sulfonic acid sodium salt) (PVS) was deposited onto flexible polyurethane foam using layer-by-layer (LbL) assembly. This coating system completely stops foam melt dripping upon exposure to the direct flame from a butane torch. Furthermore, 10 CH-PVS bilayers (∼30 nm thick) add only 5.5% to the foam’s weight and completely stop flame propagating on the foam due to the fuel dilution effect from non flammable gases (e.g, water, sulfur oxides, and ammonia) released from the coating during degradation. Cone calorimetry reveals that this same coated foam has a 52% reduction in peak heat release rate relative to an uncoated control. This water-based, environmentally benign nanocoating provides an effective postprocess flame retardant treatment for a variety of complex substrates (foam, fabric, etc.)

Exceptionally Flame Retardant Sulfur-Based Multilayer Nanocoating for Polyurethane Prepared from Aqueous Polyelectrolyte Solutions

Many current flame retardant (FR) strategies for polymers contain environmentally harmful compounds and/or negatively impact processing and mechanical properties. In an effort to overcome these issues, a effective flame retardant nanocoating comprised of positively charged chitosan (CH) and anionic poly­(vinyl sulfonic acid sodium salt) (PVS) was deposited onto flexible polyurethane foam using layer-by-layer (LbL) assembly. This coating system completely stops foam melt dripping upon exposure to the direct flame from a butane torch. Furthermore, 10 CH-PVS bilayers (∼30 nm thick) add only 5.5% to the foam’s weight and completely stop flame propagating on the foam due to the fuel dilution effect from non flammable gases (e.g, water, sulfur oxides, and ammonia) released from the coating during degradation. Cone calorimetry reveals that this same coated foam has a 52% reduction in peak heat release rate relative to an uncoated control. This water-based, environmentally benign nanocoating provides an effective postprocess flame retardant treatment for a variety of complex substrates (foam, fabric, etc.)