Nanoscale water-polymer interactions tune macroscopic diffusivity of water in aqueous poly(ethylene oxide) solutions.

The separation and anti-fouling performance of water purification membranes is governed by both macroscopic and molecular-scale water properties near polymer surfaces. However, even for poly(ethylene oxide) (PEO) - ubiquitously used in membrane materials - there is little understanding of whether or how the molecular structure of water near PEO surfaces affects macroscopic water diffusion. Here, we probe both time-averaged bulk and local water dynamics in dilute and concentrated PEO solutions using a unique combination of experimental and simulation tools. Pulsed-Field Gradient NMR and Overhauser Dynamic Nuclear Polarization (ODNP) capture water dynamics across micrometer length scales in sub-seconds to sub-nanometers in tens of picoseconds, respectively. We find that classical models, such as the Stokes-Einstein and Mackie-Meares relations, cannot capture water diffusion across a wide range of PEO concentrations, but that free volume theory can. Our study shows that PEO concentration affects macroscopic water diffusion by enhancing the water structure and altering free volume. ODNP experiments reveal that water diffusivity near PEO is slower than in the bulk in dilute solutions, previously not recognized by macroscopic transport measurements, but the two populations converge above the polymer overlap concentration. Molecular dynamics simulations reveal that the reduction in water diffusivity occurs with enhanced tetrahedral structuring near PEO. Broadly, we find that PEO does not simply behave like a physical obstruction but directly modifies water's structural and dynamic properties. Thus, even in simple PEO solutions, molecular scale structuring and the impact of polymer interfaces is essential to capturing water diffusion, an observation with important implications for water transport through structurally complex membrane materials.

Modular Synthesis and Patterning of High-Stiffness Networks by Postpolymerization Functionalization with Iron-Catechol Complexes.

Bioinspired iron-catechol cross-links have shown remarkable success in increasing the mechanical properties of polymer networks, in part due to clustering of Fe3+-catechol domains which act as secondary network reinforcing sites. We report a versatile synthetic procedure to prepare modular PEG-acrylate networks with independently tunable covalent bis(acrylate) and supramolecular Fe3+-catechol cross-linking. Initial control of network structure is achieved through radical polymerization and cross-linking, followed by postpolymerization incorporation of catechol units via quantitative active ester chemistry and subsequent complexation with iron salts. By tuning the ratio of each building block, dual cross-linked networks reinforced by clustered iron-catechol domains are prepared and exhibit a wide range of properties (Young's moduli up to ∼245 MPa), well beyond the values achieved through purely covalent cross-linking. This stepwise approach to mixed covalent and metal-ligand cross-linked networks also permits local patterning of PEG-based films through masking techniques forming distinct hard, soft, and gradient regions.

Designing Solute-Tailored Selectivity in Membranes: Perspectives for Water Reuse and Resource Recovery.

Treatment of nontraditional source waters (e.g., produced water, municipal and industrial wastewaters, agricultural runoff) offers exciting opportunities to expand water and energy resources via water reuse and resource recovery. While conventional polymer membranes perform water/ion separations well, they do not provide solute-specific separation, a key component for these treatment opportunities. Herein, we discuss the selectivity limitations plaguing all conventional membranes, which include poor removal of small, neutral solutes and insufficient discrimination between ions of the same valence. Moreover, we present synthetic approaches for solute-tailored selectivity including the incorporation of single-digit nanopores and solute-selective ligands into membranes. Recent progress in these areas highlights the need for fundamental studies to rationally design membranes with selective moieties achieving desired separations.

Delivery of cardiac resynchronization therapy via the left inferior phrenic vein: a case report.

BACKGROUND: The successful implantation of cardiac resynchronization therapy (CRT) may be prevented by anatomical variations that preclude the delivery of clinically effective left ventricular (LV) pacing from within the coronary sinus (CS) or its tributaries. Failure of lead delivery, suboptimal LV capture thresholds, or intractable phrenic nerve capture with accompanying diaphragmatic twitch is often encountered. Commonly employed alternative approaches to LV lead delivery, including epicardial, trans-septal, or transapical pacing are associated with significant morbidity. CASE SUMMARY: A 74-year-old man with ischaemic heart disease, prior mitral valve repair, long-standing atrial fibrillation, and severe symptomatic LV systolic dysfunction, underwent single chamber pacemaker upgrade to a CRT defibrillator. It was found not to be possible to place a CS lead during the procedure. Biventricular pacing was accomplished by the delivery of a pacing lead through the left inferior phrenic vein (LIPV). Satisfactory LV capture thresholds were obtained with the avoidance of clinically significant diaphragmatic stimulation. Following implantation, a marked clinical response to treatment was observed with improvement in both heart failure symptoms and LV ejection fraction. DISCUSSION: The LIPV is known to drain into the inferior vena cava in around one-third of examined subjects. In these individuals, LV lead delivery through the LIPV may provide an alternate route for the delivery of resynchronization therapy. This approach to the implantation of CRT may be considered when pacing via the CS or its branches are not achievable.

Striatal, Hippocampal, and Cortical Networks Are Differentially Responsive to the M4- and M1-Muscarinic Acetylcholine Receptor Mediated Effects of Xanomeline.

Preclinical and clinical data suggest that muscarinic acetylcholine receptor activation may be therapeutically beneficial for the treatment of schizophrenia and Alzheimer's diseases. This is best exemplified by clinical observations with xanomeline, the efficacy of which is thought to be mediated through co-activation of the M1 and M4 muscarinic acetylcholine receptors (mAChRs). Here we examined the impact of treatment with xanomeline and compared it to the actions of selective M1 and M4 mAChR activators on in vivo intracellular signaling cascades in mice, including 3'-5'-cyclic adenosine monophosphate response element binding protein (CREB) phosphorylation and inositol phosphate-1 (IP1) accumulation in the striatum, hippocampus, and prefrontal cortex. We additionally assessed the effects of xanomeline on hippocampal electrophysiological signatures in rats using ex vivo recordings from CA1 (Cornu Ammonis 1) as well as in vivo hippocampal theta. As expected, xanomeline's effects across these readouts were consistent with activation of both M1 and M4 mAChRs; however, differences were observed across different brain regions, suggesting non-uniform activation of these receptor subtypes in the central nervous system. Interestingly, despite having nearly equal in vitro potency at the M1 and the M4 mAChRs, during in vivo assays xanomeline produced M4-like effects at significantly lower brain exposures than those at which M1-like effects were observed. Our results raise the possibility that clinical efficacy observed with xanomeline was driven, in part, through its non-uniform activation of mAChR subtypes in the central nervous system and, at lower doses, through preferential agonism of the M4 mAChR.

Large-scale polymeric carbon nanotube membranes with sub-1.27-nm pores.

We report the first characterization study of commercial prototype carbon nanotube (CNT) membranes consisting of sub-1.27-nm-diameter CNTs traversing a large-area nonporous polysulfone film. The membranes show rejection of NaCl and MgSO4 at higher ionic strengths than have previously been reported in CNT membranes, and specific size selectivity for analytes with diameters below 1.24 nm. The CNTs used in the membranes were arc discharge nanotubes with inner diameters of 0.67 to 1.27 nm. Water flow through the membranes was 1000 times higher than predicted by Hagen-Poiseuille flow, in agreement with previous CNT membrane studies. Ideal gas selectivity was found to deviate significantly from that predicted by both viscous and Knudsen flow, suggesting that surface diffusion effects may begin to dominate gas selectivity at this size scale.

Infrared Spectroscopy of Polybenzimidazole in the Dry and Hydrate Forms: A Combined Experimental and Computational Study.

In the present article, the infrared spectrum of polybenzimidazole (PBI) in the dry and hydrate forms has been studied both experimentally and theoretically to improve the interpretation of its complex features, especially in the ν(NH)/ν(OH) range, which is extensively affected by sorbed water and temperature. Time-resolved Fourier-transform infrared spectroscopy measurements were performed to monitor H2O sorption, whereas the temperature behavior was investigated by in situ measurements in the 100-450 °C range. Density functional theory calculations on simplified models of dry and hydrated PBI showed good agreement with experimental results and allowed a reliable interpretation of the observed effects. The combined experimental/computational analysis provided relevant structural information which suggested the possibility of modifying the diffusion properties of PBI and motivated further experimental activities.

Highly CO2-Selective Gas Separation Membranes Based on Segmented Copolymers of Poly(Ethylene oxide) Reinforced with Pentiptycene-Containing Polyimide Hard Segments.

Poly(ethylene oxide) (PEO)-containing polymer membranes are attractive for CO2-related gas separations due to their high selectivity toward CO2. However, the development of PEO-rich membranes is frequently challenged by weak mechanical properties and a high crystallization tendency of PEO that hinders gas transport. Here we report a new series of highly CO2-selective, amorphous PEO-containing segmented copolymers prepared from commercial Jeffamine polyetheramines and pentiptycene-based polyimide. The copolymers are much more mechanically robust than the nonpentiptycene containing counterparts due to the molecular reinforcement mechanism of supramolecular chain threading and interlocking interactions induced by the pentiptycene structures, which also effectively suppresses PEO crystallization leading to a completely amorphous structure even at 60% PEO weight content. Membrane transport properties are sensitively affected by both PEO weight content and PEO chain length. A nonlinear correlation between CO2 permeability with PEO weight content was observed due to the competition between solubility and diffusivity contributions, whereby the copolymers change from being size-selective to solubility-selective when PEO content reaches 40%. CO2 selectivities over H2 and N2 increase monotonically with both PEO content and chain length, indicating strong CO2-philicity of the copolymers. The copolymer film with the longest PEO sequence (PEO2000) and highest PEO weight content (60%) showed a measured CO2 pure gas permeability of 39 Barrer, and ideal CO2/H2 and CO2/N2 selectivities of 4.1 and 46, respectively, at 35 °C and 3 atm, making them attractive for hydrogen purification and carbon capture.