Learning from Tomorrow's Recyclers: Extension of Hands-on Recycled Waste Activity.

We previously developed a plastic sorting activity for high school students. In that activity, several tools were provided to separate plastic waste materials based on their physical properties while considering the time and cost for each separation step. Here, we aimed to understand the impact of this activity on the awareness of and learning about plastic sorting in a younger age group (8 to 11 years old) and explored how parental involvement influenced students' interest in the topic. The activity was part of the STEM Zone Saturday program at the University of Houston. Pre- and post-evaluations were used to assess students' understanding of plastic sorting and overall experiences. While some insights into plastic sorting were derived from previous experiences, the activity improved awareness among students, particularly regarding sorting based on physical properties. The involvement of parents encouraged exploration, discovery, and enjoyment. These findings underscore the importance of early education and community engagement in fostering sustainable practices and advancing toward a circular economy.

Hands-On Activity Illustrating the Sorting Process of Recycled Waste and Its Role in Promoting Sustainable Solutions.

Effective recycling is not merely a matter of collecting waste; it also requires meticulous categorization to maximize the potential for reusing material and minimizing waste sent to landfills. Education and awareness of the sorting and recycling process bottlenecks need to be emphasized and extended beyond higher educational contexts (e.g., in multiple stages of educational pathways, such as middle or high school). Hence, this project introduces a hands-on plastic sorting activity where students use recycled waste to be sorted based on their physical properties. Several tools were provided to perform the separation, such as water, sieves, magnets, and manual/visual separation while considering the time and cost associated with each tool. The activity was evaluated by pre- and post-evaluations based on Likert-scale and open-ended questions grouped in several categories related to the sorting process. In several categories, we observed that the activity enhanced student knowledge (e.g., general sorting understanding), while in other categories, there was no growth. From open-ended questions, students expressed an understanding of how to sort recycled waste and an appreciation for the trade-offs in developing sorting solutions. This activity effectively enhanced students' awareness of the sorting process of recycled waste. It lays the foundation for future inquiry and outreach project design.

Pressure Indicator Composite Films via Compressive Deformation of a Translucent Matrix Containing a Contrasting Filler.

A neglected mechanism for pressure-responsive color change is demonstrated using cellulose acetate composites prepared by direct (solvent) immersion annealing (DIA), with different loadings of activated charcoal filler. Namely, compressive plastic deformation of the translucent cellulose acetate leads to a decrease in the optical path length and a concomitant increase in the visibility of the opaque contrasting filler. Composites bearing 1-7 wt% activated charcoal exhibited a linear relationship between applied pressure and resulting pressure mark brightness in the range of 12-56 MPa. Comparison of pressure mark patterns with cross-sectional scanning electron microscopy (SEM) supports the importance of the porous morphology arising from DIA for the tuning of the pressure indicator sensitivity. A simple ball drop test is used to illustrate the robustness and utility of these indicators in optical impact assessment.

Increasing Naloxone Access and Prescribing for Patients on High-Dose Opioids From a Managed Care Pharmacy Health Plan Perspective.

Background: Opioid overdoses decrease when communities have access to naloxone. Clinicians play a key role in offering naloxone to high-risk chronic opioid patients. Managed care pharmacists within our health plan noted disproportionate processing for claims of opioid utilizers compared to claims of naloxone prescriptions. Objective: To increase naloxone access and prescribing to members who classify at a dosage with a higher risk for opioid overdose, defined as over 90 morphine milligram equivalents (MME). Methods: Multiple system-wide initiatives were implemented to improve naloxone access. A claims file was pulled monthly to identify members on opioids meeting MME criteria >90 MME per day excluding members with cancer, sickle cell disease, or on hospice. A separate report was then matched to naloxone claims and prescribing percentages calculated. Results: 12 444 utilizing members on opioids were identified from June 2019 prescription claims data. Of these, 131 were on opioids exceeding 90 MME per day, or 1.05% of utilizers, and the percentage of members exceeding 90 MME per day prescribed naloxone was 6.87%. By May 2023, the percentage of opioid utilizers exceeding 90 MME per day decreased to 0.58%. Naloxone prescribing increased to 41.18%. Conclusion: A multi-pronged approach to improve access to naloxone and continued educational efforts by our health plan increased naloxone prescribing in members on opioids exceeding 90 MME per day.

Shaping the Structure and Response of Surface-Grafted Polymer Brushes via the Molecular Weight Distribution.

Breadth in the molecular weight distribution is an inherent feature of synthetic polymer systems. While in the past this was typically considered as an unavoidable consequence of polymer synthesis, multiple recent studies have shown that tailoring the molecular weight distribution can alter the properties of polymer brushes grafted to surfaces. In this Perspective, we describe recent advances in synthetic methods to control the molecular weight distribution of surface-grafted polymers and highlight studies that reveal how shaping this distribution can generate novel or enhanced functionality in these materials.

Fouling Resistance and Release Properties of Poly(sulfobetaine) Brushes with Varying Alkyl Chain Spacer Lengths and Molecular Weights.

We examined the effects of alkyl carbon spacer length (CSL) and molecular weight on fouling resistance and release properties of zwitterionic poly(sulfobetaine methacrylate) brushes. Using surface-initiated atom transfer radical polymerization, we synthesized two series of brushes with CSL = 3 and 4 and molecular weight from 19 to 1500 kg ·mol-1, corresponding to dry brush thickness from around 6 to 180 nm. The brush with CSL = 3 was nearly completely wet with water (independent of molecular weight), whereas the brush with CSL = 4 exhibited a strong increase in water contact angle with molecular weight. Though the two-brush series had distinct wetting properties, both series of brushes exhibited similarly great resistance against fouling by Staphylococcus epidermidis bacteria and Aspergillus niger fungi spores when submerged in water, indicating that neither molecular weight nor CSL strongly affected the antifouling behavior. We also compared the efficacy of brushes against fouling by fungi and silicon oil in air. Brushes grafted to filter paper were strongly fouled by fungi and silicon oil in air. Grafting the polymers to the filter paper, however, greatly enhanced removal of the foulant upon rinsing. The removal of fungi and silicon oil when rinsed with a salt solution was enhanced by 219 and 175%, respectively, as compared to a blank filter paper control. Thus, our results indicate that these zwitterionic brushes can promote foulant removal for dry applications in addition to their well-known fouling resistance in submerged conditions.

Effect of Dispersity on the Conformation of Spherical Polymer Brushes.

We show that dispersity (D̵) markedly alters the conformation of spherical polymer brushes. The average lengths (lb) of poly(tert-butyl acrylate) (PtBA) brushes of varying D̵ grafted to nanoparticles were measured using dynamic light scattering. In the semidilute polymer brush (SDPB) regime, the lb of PtBA and polymers from earlier studies of various D̵ could be cleanly collapsed onto a master curve as a function of the scaling variable Nwσ1/3, where Nw is the weight-average degree of polymerization and σ is the grafting density. In the concentrated polymer brush (CPB) regime, however, lb collapsed onto a bifurcated curve as a function of the scaling variable Nwσ1/2, indicating D̵ more strongly affects the average length of brushes with low Nwσ1/2. We propose that the stretching of the stem near the particle surface due to interchain interactions in the CPB regime leads to greater lb in broad dispersity brushes of low but not high Nwσ1/2.

Hydrolysis and Solvolysis as Benign Routes for the End-of-Life Management of Thermoset Polymer Waste.

The production of thermoset polymers is increasing globally owing to their advantageous properties, particularly when applied as composite materials. Though these materials are traditionally used in more durable, longer-lasting applications, ultimately, they become waste at the end of their usable lifetimes. Current recycling practices are not applicable to traditional thermoset waste, owing to their network structures and lack of processability. Recently, researchers have been developing thermoset polymers with the right functionalities to be chemically degraded under relatively benign conditions postuse, providing a route to future management of thermoset waste. This review presents thermosets containing hydrolytically or solvolytically cleavable bonds, such as esters and acetals. Hydrolysis and solvolysis mechanisms are discussed, and various factors that influence the degradation rates are examined. Degradable thermosets with impressive mechanical, thermal, and adhesion behavior are discussed, illustrating that the design of material end-of-life need not limit material performance.

Tuning Bacterial Attachment and Detachment via the Thickness and Dispersity of a pH-Responsive Polymer Brush.

We investigated the effect of two brush parameters, thickness and dispersity in the molecular weight distribution, on the adhesion of bacteria to pH-responsive poly(acrylic acid) (PAA) brushes synthesized using surface-initiated atom transfer radical polymerization. The attachment and detachment of Staphylococcus epidermidis to PAA brushes at pH 4 and pH 9, respectively, were examined with confocal microscopy. An optimal range of brush thickness, 13-18 nm, was identified for minimizing bacterial adhesion on PAA brushes at pH 4, and bacterial attachment did not depend on the brush dispersity. Increasing either the brush thickness or dispersity detached bacteria from the brushes when the pH was increased from 4 to 9. Bacterial detachment likely arose from an enhanced actuation effect in thick or high-dispersity brushes, as PAA brushes change conformation from collapsed to extended states when the pH is increased from 4 to 9. These results suggest that manipulating the molecular weight distribution provides a route to separately tune the attachment and detachment of bacteria.

Fluorophore exchange kinetics in block copolymer micelles with varying solvent-fluorophore and solvent-polymer interactions.

Fluorescence spectroscopy was employed to characterize the kinetics of guest exchange in diblock copolymer micelles composed of poly(ethylene oxide-b-ε-caprolactone) (PEO-PCL) diblock copolymers in water/tetrahydrofuran (THF) mixtures which encapsulated fluorophores. The solvent composition (THF content) of the micelle solution was varied as a means of modulating the strength of interactions between the fluorophore and solvent as well as between the micelle core and solvent. A donor-acceptor fluorophore pair was employed consisting of 3,3'-dioctadecyloxacarbocyanine perchlorate (DiO, the donor) and 1,1'-dioctadecyl-3,3,3',3'-tetramethylindocarbocyanine perchlorate (DiI, the acceptor). Through the process of Förster resonance energy transfer (FRET), energy was transferred from the donor to acceptor when the fluorophores were in close proximity. A micelle solution containing DiO was mixed with a micelle solution containing DiI at t = 0, and the emission spectra of the mixed solution were monitored over time (at an excitation wavelength optimized for the donor). In micelle solutions containing 5 and 10 vol% THF in the bulk solvent, an increase in the acceptor peak intensity maximum occurred over time in the post-mixed solution, accompanied by a decrease in the donor peak intensity maximum, indicating the presence of energy transfer from the donor to the acceptor. At long times, the FRET ratios (acceptor peak intensity divided by the sum of the acceptor and donor peak intensities) were indistinguishable from that determined from pre-mixed micelle solutions of the same THF content (in pre-mixed solutions, DiO and DiI were encapsulated within the same micelle cores). In the micelle solution containing 20 vol% THF, the fluorophore exchange process occurred too quickly to be observed (the FRET ratios measured from the solutions mixed at t = 0 were commensurate to that measured from the pre-mixed solution). A time constant describing the guest exchange process was extracted from the time-dependence of the FRET ratio through fit of an exponential decay. An increase in the THF content in the micelle solution resulted in a decrease in the time constant, and the time constant varied over five orders of magnitude as the THF content was varied from 5-20 vol%.

Synthesis, Characterization, and Cross-Linking Strategy of a Quercetin-Based Epoxidized Monomer as a Naturally-Derived Replacement for BPA in Epoxy Resins.

The natural polyphenolic compound quercetin was functionalized and cross-linked to afford a robust epoxy network. Quercetin was selectively methylated and functionalized with glycidyl ether moieties using a microwave-assisted reaction on a gram scale to afford the desired monomer (Q). This quercetin-derived monomer was treated with nadic methyl anhydride (NMA) to obtain a cross-linked network (Q-NMA). The thermal and mechanical properties of this naturally derived network were compared to those of a conventional diglycidyl ether bisphenol A-derived counterpart (DGEBA-NMA). Q-NMA had similar thermal properties [i.e., glass transition (Tg ) and decomposition (Td ) temperatures] and comparable mechanical properties (i.e., Young's Modulus, storage modulus) to that of DGEBA-NMA. However, it had a lower tensile strength and higher flexural modulus at elevated temperatures. The application of naturally derived, sustainable compounds for the replacement of commercially available petrochemical-based epoxies is of great interest to reduce the environmental impact of these materials. Q-NMA is an attractive candidate for the replacement of bisphenol A-based epoxies in various specialty engineering applications.

Hysteretic memory in pH-response of water contact angle on poly(acrylic acid) brushes.

We investigated the pH-dependent response of flat polyacid brushes of varying length and dispersity in the extended brush regime. Our model system consisted of poly(acrylic acid) brushes, which change from hydrophobic and neutral at low pH to hydrophilic and negatively charged at high pH, synthesized on silicon substrates using a grafting-from approach at constant grafting density. We observed three trends in the pH-response: first, the dry brush thickness increased as the pH was increased for brushes above a critical length, and this effect was magnified as the dispersity increased; second, the water contact angle measured at low pH was larger for brushes of greater dispersity; and third, brushes of sufficient dispersity exhibited hysteretic memory behavior in the pH-dependence of the contact angle, in which the contact angle upon increasing and decreasing pH differed. As a consequence, the pKa of the brushes measured upon increasing pH was consistently higher than that measured upon decreasing pH. The observed pH response is consistent with proposed changes in the conformation and charge distribution of the polyelectrolyte brushes that depend on the direction of pH change and the dispersity of the brushes.

Thermodynamic Interactions between Polystyrene and Long-Chain Poly(n-Alkyl Acrylates) Derived from Plant Oils.

Vegetable oils and their fatty acids are promising sources for the derivation of polymers. Long-chain poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) are readily derived from fatty acids through conversion of the carboxylic acid end-group to an acrylate or methacrylate group. The resulting polymers contain long alkyl side-chains with around 10-22 carbon atoms. Regardless of the monomer source, the presence of alkyl side-chains in poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) provides a convenient mechanism for tuning their physical properties. The development of structured multicomponent materials, including block copolymers and blends, containing poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) requires knowledge of the thermodynamic interactions governing their self-assembly, typically described by the Flory-Huggins interaction parameter χ. We have investigated the χ parameter between polystyrene and long-chain poly(n-alkyl acrylate) homopolymers and copolymers: specifically we have included poly(stearyl acrylate), poly(lauryl acrylate), and their random copolymers. Lauryl and stearyl acrylate were chosen as model alkyl acrylates derived from vegetable oils and have alkyl side-chain lengths of 12 and 18 carbon atoms, respectively. Polystyrene is included in this study as a model petroleum-sourced polymer, which has wide applicability in commercially relevant multicomponent polymeric materials. Two independent methods were employed to measure the χ parameter: cloud point measurements on binary blends and characterization of the order-disorder transition of triblock copolymers, which were in relatively good agreement with one another. The χ parameter was found to be independent of the alkyl side-chain length (n) for large values of n (i.e., n > 10). This behavior is in stark contrast to the n-dependence of the χ parameter predicted from solubility parameter theory. Our study complements prior work investigating the interactions between polystyrene and short-chain polyacrylates (n ≤ 10). To our knowledge, this is the first study to explore the thermodynamic interactions between polystyrene and long-chain poly(n-alkyl acrylates) with n > 10. This work lays the groundwork for the development of multicomponent structured systems (i.e., blends and copolymers) in this class of sustainable materials.

Tough blends of polylactide and castor oil.

Poly(l-lactide) (PLLA) is a renewable resource polymer derived from plant sugars with several commercial applications. Broader implementation of the material is limited due to its inherent brittleness. We show that the addition of 5 wt % castor oil to PLLA significantly enhances the overall tensile toughness with minimal reductions in the modulus and no plasticization of the PLLA matrix. In addition, we used poly(ricinoleic acid)-PLLA diblock copolymers, synthesized entirely from renewable resources, as compatibilizers for the PLLA/castor oil blends. Ricinoleic acid, the majority fatty acid comprising castor oil, was polymerized through a lipase-catalyzed condensation reaction. The resulting polymers contained a hydroxyl end-group that was subsequently used to initiate the ring-opening polymerization of l-lactide. The binary PLLA/castor oil blend exhibited a tensile toughness seven times greater than neat PLLA. The addition of block copolymer allowed for control over the morphology of the blends, and even further improvement in the tensile toughness was realized-an order of magnitude larger than that of neat PLLA.

Phase inversion in polylactide/soybean oil blends compatibilized by poly(isoprene-b-lactide) block copolymers.

Renewable composites were prepared by melt blending of polylactide and soybean oil. The blend morphology was tuned by the addition of poly(isoprene-b-lactide) block copolymers. Due to the extreme difference in the viscosities of soybean oil and polylactide, a critical block copolymer composition was found to induce a phase inversion point at which the minor soybean oil phase became the matrix surrounding polylactide particles. This transition was due to the thermodynamic interactions between the block copolymer and the two phases and shear forces acting on the mixture during blending. The size of the soybean oil droplets in the polylactide matrix was also highly dependent on the block copolymer composition. In binary polylactide/soybean oil blends, there was a limiting concentration of soybean oil that could be incorporated into the polylactide matrix (6% of the total blend weight), which could be increased up to 20% by the addition of block copolymers.