Exposure to the non-phthalate plasticizer di-heptyl succinate is less disruptive to C57bl/6N mouse recovery from a myocardial infarction than DEHP, TOTM or related di-octyl succinate.

Phthalate plasticizers are incorporated into plastics to make them soft and malleable, but are known to leach out of the final product into their surroundings with potential detrimental effects to human and ecological health. The replacement of widely-used phthalate plasticizers, such as di-ethylhexyl phthalate (DEHP), that are of known toxicity, by the commercially-available alternative Tris(2-ethylhexyl) tri-mellitate (TOTM) is increasing. Additionally, several newly designed "green" plasticizers, including di-heptyl succinate (DHPS) and di-octyl succinate (DOS) have been identified as potential replacements. However, the impact of plasticizer exposure from medical devices on patient recovery is unknown and, moreover, the safety of TOTM, DHPS, and DOS is not well established in the context of patient recovery. To study the direct effect of clinically based chemical exposures, we exposed C57bl/6 N male and female mice to DEHP, TOTM, DOS, and DHPS during recovery from cardiac surgery and assessed survival, cardiac structure and function, immune cell infiltration into the cardiac wound and activation of the NLRP3 inflammasome. Male, but not female, mice treated in vivo with DEHP and TOTM had greater cardiac dilation, reduced cardiac function, increased infiltration of neutrophils, monocytes, and macrophages and increased expression of inflammasome receptors and effectors, thereby suggesting impaired recovery in exposed mice. In contrast, no impact was detected in female mice and male mice exposed to DOS and DHPS. To examine the direct effects in cells involved in wound healing, we treated human THP-1 macrophages with the plasticizers in vitro and found DEHP induced greater NLRP3 expression and activation. These results suggest that replacing current plasticizers with non-phthalate-based plasticizers may improve patient recovery, especially in the male population. In our assessment, DHPS is a promising possibility for a non-toxic biocompatible plasticizer.

All-Atom Molecular Dynamics of Pure Water-Methane Gas Hydrate Systems under Pre-Nucleation Conditions: A Direct Comparison between Experiments and Simulations of Transport Properties for the Tip4p/Ice Water Model.

(1) Background: New technologies involving gas hydrates under pre-nucleation conditions such as gas separations and storage have become more prominent. This has necessitated the characterization and modeling of the transport properties of such systems. (2) Methodology: This work explored methane hydrate systems under pre-nucleation conditions. All-atom molecular dynamics simulations were used to quantify the performance of the TIP4P/2005 and TIP4P/Ice water models to predict the viscosity, diffusivity, and thermal conductivity using various formulations. (3) Results: Molecular simulation equilibrium was robustly demonstrated using various measures. The Green-Kubo estimation of viscosity outperformed other formulations when combined with TIP4P/Ice, and the same combination outperformed all TIP4P/2005 formulations. The Green-Kubo TIP4P/Ice estimation of viscosity overestimates (by 84% on average) the viscosity of methane hydrate systems under pre-nucleation conditions across all pressures considered (0-5 MPag). The presence of methane was found to increase the average number of hydrogen bonds over time (6.7-7.8%). TIP4P/Ice methane systems were also found to have 16-19% longer hydrogen bond lifetimes over pure water systems. (4) Conclusion: An inherent limitation in the current water force field for its application in the context of transport properties estimations for methane gas hydrate systems. A re-parametrization of the current force field is suggested as a starting point. Until then, this work may serve as a characterization of the deviance in viscosity prediction.

Ethylene Glycol Dicyclopentenyl (Meth)Acrylate Homo and Block Copolymers via Nitroxide Mediated Polymerization.

Nitroxide-mediated polymerization (NMP), (homo and block copolymerization with styrene (S) and butyl methacrylate/S) of ethylene glycol dicyclopentenyl ether (meth)acrylates (EGDEA and EGDEMA) was studied using BlocBuilder alkoxyamines. EGDEA homopolymerization was not well-controlled, independent of temperature (90-120 °C), or additional free nitroxide (0-10 mol%) used. Number average molecular weights (Mn) achieved for poly(EGDEA) were 4.0-9.5 kg mol-1 and were accompanied by high dispersity (Ð = Mw/Mn = 1.62-2.09). Re-initiation and chain extension of the poly(EGDEA) chains with styrene (S) indicated some block copolymer formation, but a high fraction of chains were terminated irreversibly. EGDEA-stat-S statistical copolymerizations with a low mol fraction S in initial feed, fS,0 = 0.05, were slightly better controlled compared to poly(EGDEA) homopolymerizations (Ð was reduced to 1.44 compared to 1.62 at similar conditions). EGDEMA, in contrast, was successfully polymerized using a small fraction of S (fS,0 ~ 10 mol%) to high conversion (72%) to form well-defined EGDEMA-rich random copolymer (molar composition = FEGDEMA = 0.87) of Mn = 14.3 kg mol-1 and Ð = 1.38. EGDEMA-rich compositions were also polymerized with the unimolecular succinimidyl ester form of BlocBuilder initiator, NHS-BlocBuilder with similar results, although Ðs were higher ~1.6. Chain extensions resulted in monomodal shifts to higher molecular weights, indicating good chain end fidelity.