Microbial susceptibility of various polymers and evaluation of thermoplastic elastomers with antimicrobial additives

The incursion of microbial growth on polymeric products can deteriorate their performance and lead to the development of undesirable staining and odors. A growing trend in the industry has aimed to reduce microbial populations on high-touch surfaces via the use of antimicrobials to protect material aesthetics and durability or to prevent the spread of pathogenic microorganisms. In this study, a variety of plastic substrates (30 unique polymer compounds), including poly(acrylonitrile-co-butadiene-co-styrene), poly(butylene terephthalate), poly(etherimide), various thermoplastic elastomers (TPEs), poly(carbonates), and poly(amides), were screened for susceptibility to microbial attack using American Society for Testing and Materials (ASTM) G21 (fungi susceptibility), Japanese Industrial Standard (JIS) Z2801, and modified ASTM E1428-15a (bacterial susceptibility) test standards. TPEs were determined to be most susceptible to microbial attack under the appropriate environmental conditions. Subsequent studies assessed the use of an antimicrobial additive, zinc pyrithione (ZPT), for potential efficacy in a variety of TPE blends for diverse target market applications. ZPT proved to be very effective in protecting TPEs, reducing Staphylococcus aureus and Escherichia coli populations by 99.9% or more in JIS Z2801 testing and inhibiting fungal growth (rating = 0) according to the ASTM G21 standard.     

全透明高压反应釜甲烷水合物动力学实验

水合物的生长和分解规律对开发海洋天然气水合物资源，实现深水天然气水合物气液固多相管道输送都具有重要意义。为了进一步揭示水合物的生长和分解特性，本文采用高压全透明反应釜装置，进行了温度0～30℃、压力3.35～8.16MPa和搅拌速率200～1000r/min范围内的16组甲烷水合物生长和分解动力学实验研究。结果表明：实验过程可分为水合物诱导期、快速生长期、缓慢生长期以及分解期这4个阶段。在水合物快速生长阶段，获得了温度、压力、搅拌电机扭矩和水合物生长速率随时间的变化规律，观察到了水合物颗粒的均相和非均相分布状态。通过加热促使水合物分解，揭示了分解阶段温度、压力和分解速率等关键参数的变化规律以及水合物块的分解形态。分析表明，水合物颗粒的分布状态与水合物浆液的流动性直接相关；水合物块的静态分解过程受到分解气传质控制。     

Crack initiation,propagation, and arrest in sintering powder aggregates

Cracking during sintering is a common problem in powder processing and is usually caused by constraint that prevents the sintering material from shrinking in one or more directions. Different factors influence sintering-induced cracking, including temperature schedule, packing density, and specimen geometry. Here we use the discrete element method to directly observe the stress distribution and sinter-cracking behavior in edge notched panels sintered under a uniaxial restraint. This geometry allows an easy comparison with traditional fracture mechanics parameters, facilitating analysis of sinter-cracking behavior. We find that cracking caused by self-stress during sintering resembles the growth of creep cracks in fully dense materials. By deriving the constrained densification rate from the appropriate constitutive equations, we discover that linear shrinkage transverse to the loading axis is accelerated by a contribution from the effective Poisson's ratio of a sintering solid. Simulation of different notch geometries and initial relative densities reveals conditions that favor densification and minimize crack growth, alluding to design methods for avoiding cracking in actual sintering processes. We combine the far-field stress and crack length to compute the net section stress, finding that it characterizes the stress profile between the notches and correlates with the sinter-crack growth rate, demonstrating its potential to quantitatively describe sinter-cracking.     

The dorsolateral pre‑frontal cortex bi‑polar error‑related potential in a locked‑in patient implanted with a daily use brain–computer interface

While brain computer interfaces (BCIs) offer the potential of allowing those suffering from loss of muscle control to once again fully engage with their environment by bypassing the affected motor system and decoding user intentions directly from brain activity, they are prone to errors. One possible avenue for BCI performance improvement is to detect when the BCI user perceives the BCI to have made an unintended action and thus take corrective actions. Error-related potentials (ErrPs) are neural correlates of error awareness and as such can provide an indication of when a BCI system is not performing according to the user’s intentions. Here, we investigate the brain signals of an implanted BCI user suffering from locked-in syndrome (LIS) due to late-stage ALS that prevents her from being able to speak or move but not from using her BCI at home on a daily basis to communicate, for the presence of error-related signals. We first establish the presence of an ErrP originating from the dorsolateral pre-frontal cortex (dLPFC) in response to errors made during a discrete feedback task that mimics the click-based spelling software she uses to communicate. Then, we show that this ErrP can also be elicited by cursor movement errors in a continuous BCI cursor control task. This work represents a first step toward detecting ErrPs during the daily home use of a communications BCI.     

Retardation of Crystallization through the Addition of Dairy Phospholipids

The objective of this work was to identify the effects that milk phospholipids (PL) have on crystallization of anhydrous milk fat (AMF). Three mixtures were prepared by adding 0%, 0.01%, and 0.1% PL to AMF. Each mixture was crystallized for 90 min at 24, 26, and 28 °C. The solid fat content was measured as a function of time and fitted to the Avrami equation. Melting point, thermal behavior, viscoelastic properties, and crystal morphology were all measured at 90 min. All assays were repeated, as well as hardness, after being stored at 5 °C for 48 hours. Samples containing PL showed slower crystallization as concentration increased especially at higher temperatures (26 and 28 °C). The addition of PL caused a difference in crystal morphology resulting in visibly larger crystals at 90 min. The elasticity and hardness at 90 min were influenced by the addition of PL at 24 °C with lower values obtained in samples with PL compared to the AMF alone. No differences in hardness nor in elasticity was observed for samples crystallized at 26 and 28 °C. A decrease in melting enthalpy was observed in samples with PL indicating a reduction in crystallization at all temperatures, which was supported by crystal morphology.     

Oxygen-Generating Cryogels Restore T Cell Mediated Cytotoxicity in Hypoxic Tumors

Solid tumors are protected from antitumor immune responses due to their hypoxic microenvironments. Weakening hypoxia-driven immunosuppression by hyperoxic breathing of 60% oxygen has shown to be effective in unleashing antitumor immune cells against solid tumors. However, efficacy of systemic oxygenation is limited against solid tumors outside of lungs and has been associated with unwanted side effects. As a result, it is essential to develop targeted oxygenation alternatives to weaken tumor hypoxia as novel approaches to restore immune responses against cancer. Herein, injectable oxygen-generating cryogels (O₂-cryogels) to reverse tumor-induced hypoxia are reported. These macroporous biomaterials are designed to locally deliver oxygen, inhibit the expression of hypoxia-inducible genes in hypoxic melanoma cells, and reduce the accumulation of immunosuppressive extracellular adenosine. The data show that O₂-cryogels enhance T cell-mediated secretion of cytotoxic proteins, restoring the killing ability of tumor-specific cytotoxic T lymphocytes, both in vitro and in vivo. In summary, O₂-cryogels provide a unique and safe platform to supply oxygen as a coadjuvant in hypoxic tumors and have the potential to improve cancer immunotherapies.     

ALGAMES: a fast augmented Lagrangian solver for constrained dynamic games

Autonomous Robots - Dynamic games are an effective paradigm for dealing with the control of multiple interacting actors. This paper introduces augmented Lagrangian GAME-theoretic solver (ALGAMES),...     

Molecular Sensing Using Hyperpolarized Xenon NMR Spectroscopy

Molecular imaging is the determination of the spatial location and concentration of specific molecules in a sample of interest. Sophisticated modern magnetic resonance imaging machines can collect NMR spectra from small-volume elements within a sample, enabling local chemical analysis. However, abundant water and fat signals limit detection of metabolites to near mM concentrations. Alternatively, targeted relaxation contrast agents enhance the relaxation of the strong water signal where they bind. A comparison of images with and without a contrast agent shows the target distribution, but high µM concentrations are needed. We have developed an approach that exploits the strong signals of hyperpolarized ¹²⁹Xe (an inert reporter introduced for imaging). The imaging contrast agents are composed of a biological recognition motif to localize the agent (antibodies or aptamers) and covalently tethered cryptophane cages. Xenon binds to the cryptophane and though chemical exchange saturation transfer creates contrast in a xenon image. Imaging agents can deliver many cages per target, giving detection limits in the pM concentration range. The evolution and principles of this approach are described herein.     

Gas permeation in thin films of “high free-volume” glassy perfluoropolymers: Part I. Physical aging

Physical aging of both thick and thin films of “high free-volume” glassy perfluoropolymers was studied by monitoring changes in pure gas permeability of O₂, N₂ and CH₄. All permeability measurements were done at a fixed temperature of 35 °C for more than 1000 h of aging. Two grades of perfluoropolymers, Teflon AF and Hyflon AD, having different comonomer structures but with similar comonomer ratios were studied to understand the effect of comonomer type and content on the aging behavior. The effect of casting process (solution vs. spin coating) and solvent type (vapor pressure and boiling point) had a significant effect on the absolute permeability of both thick and thin films; however, the aging rates were more affected by thickness and solvent type rather than the casting process for similar thicknesses. After 1000 h of aging, the relative permeability for thin films of Teflon AF 2400 was decreased by 27% compared to only 10% for thick films prepared from Novec 7500 solvent. Teflon AF, which has a higher fractional free volume (FFV) than Hyflon AD, is believed to undergo significant aging well before the initial permeability measurement could be made (after ∼ 1 h of aging) and, therefore, Teflon AF materials showed a lower decrease in relative permeability compared to Hyflon AD for the same aging time. The comonomer type and content has a significant effect on the permeability; the initial absolute oxygen permeability for AF 2400 was an order of magnitude higher compared to AD 60. The physical aging of thin films of the various glassy perfluoropolymers was also tracked by recording changes in the refractive index and thickness with time by ellipsometry. The ellipsometry data also confirmed higher aging rates in Hyflon AD compared to Teflon AF materials. The volumetric aging rate, obtained from the change in the refractive index using the Lorentz–Lorenz equation, and the permeability reduction rate from the (P_1000h/P_1h) ratio showed an excellent linear correlation. The (P_1000h/P_1h) ratio also showed a stronger correlation with (T_g−35) °C than with FFV.     

Influence of polyimide precursor synthesis route and ortho-position functional group on thermally rearranged (TR) polymer properties: Conversion and free volume

Thermal rearrangement of polyimides with ortho-position groups to polybenzoxazoles and related structures has been of recent interest for producing gas separation membranes. This study explores the influence of synthesis route and ortho-position functional group on the thermal rearrangement process and the fractional free volume of thermally rearranged (TR) polymers produced from polyimides derived from 3,3′-dihydroxy-4,4′-diamino-biphenyl and 2,2′-bis-(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (HAB–6FDA). Acetate, propanoate, and pivalate ortho-position functional groups were considered. Thermogravimetric analysis (TGA) was used to study thermal rearrangement at temperatures between 350 and 450 °C, and evolved gases from TGA were analyzed via mass spectrometry to characterize the byproducts of thermal rearrangement and thermal degradation. CO₂ was the major byproduct of thermal rearrangement for all samples, and its evolution began well before the onset of thermal degradation. When non-hydroxyl ortho-position groups were present in the polymers, several byproducts other than CO₂ were also observed due to the loss of these ortho-position groups before thermal rearrangement. Free volume generally increased with increasing extent of thermal rearrangement, but precise values of free volume could not be accurately determined for polymers with propanoate and pivalate ortho-position functional groups due to uncertainties in the chemical structure of partially converted materials. For polymers with acetate and hydroxyl ortho-position groups, free volume could be determined within the uncertainty of density measurements. Thermal rearrangement behavior and free volume results for acetate containing polymers synthesized via different routes were very similar. Based on these results, the chemical structure of the ortho-position functional group has a larger impact on TR polymer properties than the polyimide precursor synthesis route.