Environmental, Health, and Legislation Considerations for Rational Design of Nonreactive Flame-Retardant Additives for Polymeric Materials: Future Perspectives.

Increasing polymer usage has demanded functional additives that decrease fire hazards for end users. While traditional flame-retardant (FR) additives, such as halogenated, phosphorus, and metal hydroxides, greatly reduce flammability and associated fire hazards, research has continually exposed a litany of health and environmental safety concerns. This perspective aims to identify the key components of a successful FR additive and address material, environmental, and health concerns of existing additives. Legislation surrounding FRs and persistent organic pollutants is also discussed to highlight political perception that has resulted in the increased chemical regulations and subsequent banning of FR additives. Finally, future directions of this field regarding nonreactive additives, focusing on the use of bioinspired materials and transition metal chemistries to produce alternatives for polymers with efficacies surpassing traditional additives are presented.

Effect of Moisture Sorption on Free Volume and Relaxation of Spray Dried Dispersions: Relation to Drug Recrystallization.

The effect of vapor sorption on the free volume of drug-polymer spray-dried dispersions (SDDs) was investigated, along with the crystallization propensity of drug molecules in SDDs after exposure to humidity. Subsequently, the correlation of free volume change and relaxation time with drug recrystallization was examined. Four polymers, including polyvinylpyrrolidone, polyvinylpyrrolidone vinyl acetate copolymer, hydroxypropyl cellulose, and hydroxypropyl methylcellulose acetate succinate, and 2 drugs (indomethacin and ketoconazole) were selected for preparing SDDs. Free volume data of the exposed SDDs were obtained with positron annihilation lifetime spectroscopy, while the relaxation time was measured using a TA rheometer. Additionally, the crystallization propensity of active pharmaceutical ingredients (APIs) in the exposed SDDs was assessed using both polarized light microscopy and powder X-ray diffraction, followed by relating API crystallization inclination with expansion of holes and relaxation time. Finally, Cohen and Turnbull molecular transport model, along with its extensions by Vrentas and Duda, was qualitatively utilized for interpreting the recrystallization propensity of API molecules. In conclusion, API recrystallization is closely related to free volume change upon moisture sorption and relaxation time, but system dependent; overall, drug-hydroxypropyl methylcellulose acetate succinate SDDs appear physically stable against recrystallization due to less increase in free volume.

Why Is Amyloid-ß PET Requested After Performing CSF Biomarkers?

BACKGROUND: Amyloid-ß positron emission tomography (PET) and cerebrospinal fluid (CSF) Aß42 are considered interchangeable for clinical diagnosis of Alzheimer's disease. OBJECTIVE: To explore the clinical reasoning for requesting additional amyloid-ß PET after performing CSF biomarkers. METHODS: We retrospectively identified 72 memory clinic patients who underwent amyloid-ß PET after CSF biomarkers analysis for clinical diagnostic evaluation between 2011 and 2019. We performed patient chart reviews to identify factors which led to additional amyloid-ß PET. Additionally, we assessed accordance with appropriate-use-criteria (AUC) for amyloid-ß PET. RESULTS: Mean patient age was 62.0 (SD = 8.1) and mean Mini-Mental State Exam score was 23.6 (SD = 3.8). CSF analysis conflicting with the clinical diagnosis was the most frequent reason for requesting an amyloid-ß PET scan (n = 53, 74%), followed by incongruent MRI (n = 16, 22%), unusual clinical presentation (n = 11, 15%) and young age (n = 8, 11%). An amyloid-ß PET scan was rarely (n = 5, 7%) requested in patients with a CSF Aß+/tau+ status. Fifteen (47%) patients with a post-PET diagnosis of AD had a predominantly non-amnestic presentation. In n = 11 (15%) cases, the reason that the clinician requested amyloid-ß was not covered by AUC. This happened most often (n = 7) when previous CSF analysis did not support current clinical diagnosis, which led to requesting amyloid-ß PET. CONCLUSION: In this single-center study, the main reason for requesting an amyloid-ß PET scan after performing CSF biomarkers was the occurrence of a mismatch between the primary clinical diagnosis and CSF Aß/tau results.

Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters.

Converting biomass-based feedstocks into polymers not only reduces our reliance on fossil fuels, but also furnishes multiple opportunities to design biorenewable polymers with targeted properties and functionalities. Here we report a series of high glass transition temperature (Tg up to 184 °C) polyesters derived from sugar-based furan derivatives as well as a joint experimental and theoretical study of substituent effects on their thermal properties. Surprisingly, we find that polymers with moderate steric hindrance exhibit the highest Tg values. Through a detailed Ramachandran-type analysis of the rotational flexibility of the polymer backbone, we find that additional steric hindrance does not necessarily increase chain stiffness in these polyesters. We attribute this interesting structure-property relationship to a complex interplay between methyl-induced steric strain and the concerted rotations along the polymer backbone. We believe that our findings provide key insight into the relationship between structure and thermal properties across a range of synthetic polymers.

Fast Self-Healing of Polyelectrolyte Multilayer Nanocoating and Restoration of Super Oxygen Barrier.

A self-healable gas barrier nanocoating, which is fabricated by alternate deposition of polyethyleneimine (PEI) and polyacrylic acid (PAA) polyelectrolytes, is demonstrated in this study. This multilayer film, with high elastic modulus, high glass transition temperature, and small free volume, has been shown to be a super oxygen gas barrier. An 8-bilayer PEI/PAA multilayer assembly (≈700 nm thick) exhibits an oxygen transmission rate (OTR) undetectable to commercial instrumentation (<0.005 cc (m-2 d-1 atm-1 )). The barrier property of PEI/PAA nanocoating is lost after a moderate amount of stretching due to its rigidity, which is then completely restored after high humidity exposure, therefore achieving a healing efficiency of 100%. The OTR of the multilayer nanocoating remains below the detection limit after ten stretching-healing cycles, which proves this healing process to be highly robust. The high oxygen barrier and self-healing behavior of this polymer multilayer nanocoating makes it ideal for packaging (food, electronics, and pharmaceutical) and gas separation applications.

Thermal Conductivity Performance of Polypropylene Composites Filled with Polydopamine-Functionalized Hexagonal Boron Nitride.

Mussel-inspired approach was attempted to non-covalently functionalize the surfaces of boron nitride (BN) with self-polymerized dopamine coatings in order to reduce the interfacial thermal barrier and enhance the thermal conductivity of BN-containing composites. Compared to the polypropylene (PP) composites filled with pristine BN at the same filler content, thermal conductivity was much higher for those filled with both functionalized BN (f-BN) and maleic anhydride grafted PP (PP-g-ma) due to the improved filler dispersion and better interfacial filler-matrix compatibility, which facilitated the development of more thermal paths. Theoretical models were also applied to predict the composite thermal conductivity in which the Nielsen model was found to fit well with the experimental results, and the estimated effective aspect ratio of fillers well corresponded to the degree of filler aggregation as observed in the morphological study.

Ecofriendly Fabrication of Modified Graphene Oxide Latex Nanocomposites with High Oxygen Barrier Performance.

Large-scale industrial applications of barrier films and coatings that prevent permeation of degradative gases and moisture call for the development of cost-efficient and ecofriendly polymer nanocomposites. Herein, we report the facile fabrication of latex nanocomposites (LNCs) by incorporating surface-modified graphene oxide (mGO) at various loadings (0.025-1.2 wt %) into a styrene-acrylic latex using water as the processing solvent. LNCs fabricated with mGO exhibited significant reductions (up to 67%) in water vapor sorption, resulting in greater environmental stability when compared to LNCs fabricated with equivalent loading of hydrophilic, unmodified GO. The assembly and coalescence of the exfoliated latex/mGO dispersions during the film formation process produced highly dispersed and well-ordered mGO domains with high aspect ratios, where alignment and overlap of the mGO domains improved with increasing mGO content. The addition of only 0.7 vol % (1.2 wt %) mGO led to an 84% decrease (relative to the neat polymer latex film) in oxygen permeability of the LNC films, an excellent barrier performance attributed to the observed LNC film morphologies. This work enables ecofriendly development of mechanically flexible mGO/LNC films with superior barrier properties for many industrial applications including protective coatings, food packaging, and biomedical products.

Spray-deposition and photopolymerization of organic-inorganic thiol-ene resins for fabrication of superamphiphobic surfaces.

Superamphiphobic surfaces, exhibiting high contact angles and low contact angle hysteresis to both water and low surface tension liquids, have attracted a great deal attention in recent years because of the potential of these materials in practical applications such as liquid-resistant textiles, self-cleaning surfaces, and antifouling/anticorrosion coatings. In this work, we present a simple strategy for fabricating of superamphiphobic coatings based on photopolymerization of hybrid thiol-ene resins. Spray-deposition and UV photopolymerization of thiol-ene resins containing hydrophobic silica nanoparticles and perfluorinated thiols provide a multiscale topography and low-energy surface that endows the surface with superamphiphobicity. The wettability and chemical composition of the surfaces were characterized by contact-angle goniometry and X-ray photoelectron spectroscopy, respectively. The hierarchical roughness features of the thiol-ene surfaces were investigated with field-emission scanning electron microscopy. Droplet impact and sandpaper abrasion tests indicate the coatings respectively possess a robust antiwetting behavior and good mechanical durability.

Resonance phenomenon for the Galerkin-truncated Burgers and Euler equations.

It is shown that the solutions of inviscid hydrodynamical equations with suppression of all spatial Fourier modes having wave numbers in excess of a threshold K(G) exhibit unexpected features. The study is carried out for both the one-dimensional Burgers equation and the two-dimensional incompressible Euler equation. For large K(G) and smooth initial conditions, the first symptom of truncation, a localized short-wavelength oscillation which we call a "tyger," is caused by a resonant interaction between fluid particle motion and truncation waves generated by small-scale features (shocks, layers with strong vorticity gradients, etc.). These tygers appear when complex-space singularities come within one Galerkin wavelength λ(G)=2π/K(G) from the real domain and typically arise far away from preexisting small-scale structures at locations whose velocities match that of such structures. Tygers are weak and strongly localized at first-in the Burgers case at the time of appearance of the first shock their amplitudes and widths are proportional to K(G)(-2/3) and K(G)(-1/3), respectively-but grow and eventually invade the whole flow. They are thus the first manifestations of the thermalization predicted by T. D. Lee [Q. J. Appl. Math. 10, 69 (1952)]. The sudden dissipative anomaly-the presence of a finite dissipation in the limit of vanishing viscosity after a finite time t(⋆)-which is well known for the Burgers equation and sometimes conjectured for the three-dimensional Euler equation, has as counterpart, in the truncated case, the ability of tygers to store a finite amount of energy in the limit K(G)→∞. This leads to Reynolds stresses acting on scales larger than the Galerkin wavelength and thus prevents the flow from converging to the inviscid-limit solution. There are indications that it may eventually be possible to purge the tygers and thereby to recover the correct inviscid-limit behavior.

Characterization of mouthguard materials: thermal properties of commercialized products.

OBJECTIVES: Several mechanisms have been purported to describe how mouthguards protect the orofacial complex against injury. As the properties needed for these mechanisms to be effective are temperature and frequency dependent, the specific aim of this study was to provide a comprehensive thermal characterization of commercial mouthguard materials. METHODS: Five commercially representative thermoplastic mouthguard materials (Essix Resin, Erkoflex, Proform-regular, Proform-laminate, and Polyshok) were tested. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) techniques were implemented to measure thermal transitions and mechanical properties. Measurements were conducted three times per sample. One-way ANOVA and one-sample t-tests were used to test for differences between commercial products on selected mean thermal property values. RESULTS: The DSC measurements indicated no differences between commercial materials for mean glass transition (p=0.053), onset melt (p=0.973), or peak melt (p=0.436) temperatures. Likewise, DMA measurements revealed no differences between commercial materials for the mean glass transition (p=0.093), storage modulus (p=0.257), or loss modulus (p=0.172) properties, respectively. The one-sample t-tests revealed that glass transition temperatures were different from intra-oral temperature (p<0.005) for all materials. SIGNIFICANCE: Commercialized mouthguard materials are sensitive to repetitive heating and cooling cycles, prolonged thermal treatment, and have glass transitions well below their end-use intra-oral temperature. As such, these materials are functioning as elastomers and not optimal mechanical damping materials. Dental clinicians, healthcare practitioners, or end-users should be aware that these materials are at best problematic with respect to this protective mechanism.

Characterization of mouthguard materials: physical and mechanical properties of commercialized products.

OBJECTIVES: Contemporary mouthguard materials need to perform consistently over a wide range of possible temperatures (-20 to 40 degrees C). Therefore the specific aim of this study was to characterize commercialized mouthguard materials' properties and investigate the effect of temperature on these properties. METHODS: Five commercially representative thermoplastic mouthguard materials (Essix Resin, Erkoflex, Proform-regular, Proform-laminate, and Polyshok) were tested. The durometer hardness, water absorption, tear strength, and impact attenuation of the mouthguard materials were measured according to ASTM D2240-05, D570-98 (2005), D624-00, and ASTM D6110-06f (modified) guidelines. Tests were conducted on five separate specimens at both room 23+/-2 degrees C and intra-oral 37+/-2 degrees C temperatures. Independent t-tests (alpha=0.05) were used to test for differences between room and intra-oral temperatures. RESULTS: Material hardness decreased (p<0.05) from room to intra-oral temperatures for all mouthguard materials. Water absorption increased (p<0.05) from room to intra-oral temperatures for all mouthguard materials. Tear strength decreased (p<0.05) from room to intra-oral temperatures for all mouthguard materials. Impact attenuation between room and intra-oral temperatures was different (p<0.05) for the Erkoflex, Proform-laminate, and Polyshok material respectfully. However, there was no difference between temperatures for the Essix Resin (p=.058) or Proform-regular (p=.275) materials. SIGNIFICANCE: Temperature measureably affects the physical and mechanical properties of mouthguard materials. It is particularly noteworthy that none of the commercialized products met current ANSI and SAI standards for impact attenuation.