Microporous glassy polymer membranes suffer from physical aging, which adversely affects their performance in the short time frame. We show that the aging propensity of a model microporous polymer, poly(1-trimethylsilyl-1-propyne) (PTMSP), can be effectively mitigated by blending with as little as 5 wt % porous polymer network (PPN) composed of triptycene and isatin. The aging behavior of these materials was monitored via N pure gas permeability measurements over the course of 3 weeks, showing a 14% decline in PTMSP blended with 5 wt % PPN vs a 41% decline in neat PTMSP.
View Article and Find Full Text PDFMixed matrix materials (MMMs) containing metal-organic framework (MOF) nanoparticles are attractive for membrane carbon capture. Particularly, adding <5 mass % MOFs in polymers dramatically increased gas permeability, far surpassing the Maxwell model's prediction. However, no sound mechanisms have been offered to explain this unusual low-loading phenomenon.
View Article and Find Full Text PDFMinimal understanding of the formation mechanism and structure of polydopamine (pDA) and its natural analogue, eumelanin, impedes the practical application of these versatile polymers and limits our knowledge of the origin of melanoma. The lack of conclusive structural evidence stems from the insolubility of these materials, which has spawned significantly diverse suggestions of pDA's structure in the literature. We discovered that pDA is soluble in certain ionic liquids.
View Article and Find Full Text PDFThe consequences of crowding on the dynamic conformational ensembles of intrinsically disordered proteins (IDPs) remain unresolved because of their ultrafast motion. Here, we report crowder-induced interactions and conformational dynamics of a prototypical multistimuli-responsive IDP, Rec1-resilin. The effects of a range of crowders of varying sizes, forms, topologies, and concentrations were examined using spectroscopic, spectrofluorimetric, and contrast-matching small- and ultrasmall-angle neutron scattering investigation.
View Article and Find Full Text PDFResilin-like polypeptides (RLPs) are an important class of intrinsically disordered multistimuli-responsive bioelastomers. The nanostructure of RLPs in solution has been extensively studied in the past few years, from dilute to molecular crowding conditions, and with the addition of rigid biopolymers. Modification of the hierarchical network structure of RLP hydrogels using graphene oxide (GO) as an additive is a burgeoning prospect for their application in the bioelectronic and biomedical fields.
View Article and Find Full Text PDFBiological ion channels have remarkable ion selectivity, permeability and rectification properties, but it is challenging to develop artificial analogues. Here, we report a metal-organic framework-based subnanochannel (MOFSNC) with heterogeneous structure and surface chemistry to achieve these properties. The asymmetrically structured MOFSNC can rapidly conduct K, Na and Li in the subnanometre-to-nanometre channel direction, with conductivities up to three orders of magnitude higher than those of Ca and Mg, equivalent to a mono/divalent ion selectivity of 10.
View Article and Find Full Text PDFACS Appl Mater Interfaces
December 2019
Polymers with high permeability and strong size-sieving ability are needed for H/CO separation at temperatures ranging from 100 to 300 °C to enable an energy-efficient precombustion CO capture process. However, such polymers usually suffer from a permeability/selectivity tradeoff, that is, polymers with high permeability tend to exhibit a weak size-sieving ability and thus low selectivity. Herein, we demonstrate that carbonization of a suitable polymer precursor (i.
View Article and Find Full Text PDFHerein we report the first example of a facile biomineralization process to produce ultra-small-sized highly fluorescent aqueous dispersions of platinum noble metal quantum clusters (Pt-NMQCs) using a multi-stimulus responsive, biomimetic intrinsically disordered protein (IDP), Rec1-resilin. We demonstrate that Rec1-resilin acts concurrently as the host, reducing agent, and stabilizer of the blue-green fluorescent Pt-NMQCs once they are being formed. The photophysical properties, quantum yield, and fluorescence lifetime measurements of the synthesized Pt-NMQCs were examined using UV-Vis and fluorescence spectroscopy.
View Article and Find Full Text PDFBiological fluoride ion channels are sub-1-nanometer protein pores with ultrahigh F conductivity and selectivity over other halogen ions. Developing synthetic F channels with biological-level selectivity is highly desirable for ion separations such as water defluoridation, but it remains a great challenge. Here we report synthetic F channels fabricated from zirconium-based metal-organic frameworks (MOFs), UiO-66-X (X = H, NH, and N(CH)).
View Article and Find Full Text PDFRecent demonstrations of melting in the metal-organic framework (MOF) family have created interest in the interfacial domain between inorganic glasses and amorphous organic polymers. The chemical and physical behaviour of porous hybrid liquids and glasses is of particular interest, though opportunities are limited by the inaccessible melting temperatures of many MOFs. Here, we show that the processing technique of flux melting, 'borrowed' from the inorganic domain, may be applied in order to melt ZIF-8, a material which does not possess an accessible liquid state in the pure form.
View Article and Find Full Text PDFThe electrocatalyst layer (ECL) of the proton-exchange membrane fuel cell (PEMFC) is commonly fabricated from colloidal catalyst ink containing carbon-supported catalyst nanoparticles (NPs), ionomer stabilizer, and dispersion medium (DM). The structure, stability, and aggregate size distribution of fuel cell catalyst ink are critically dependent on the quality of DM. However, understanding of the influence of the quality of DM on the hierarchical structure of the ECL is lacking.
View Article and Find Full Text PDFTo date, only several microporous, and even fewer nanoporous, glasses have been produced, always via post synthesis acid treatment of phase separated dense materials, e.g. Vycor glass.
View Article and Find Full Text PDFThe formation of ionic liquid (IL) mixtures has been proposed as an approach to rationally fine-tune the physicochemical properties of ILs for a variety of applications. However, the effects of forming such mixtures on the resultant properties of the liquids are only beginning to be understood. Towards a more complete understanding of both the thermodynamics of mixing ILs and the effect of mixing these liquids on their structures and physicochemical properties, the spatial arrangement and free volume of IL mixtures containing the common [CCim] cation and different anions have been systematically explored using small angle X-ray scattering (SAXS), positron annihilation lifetime spectroscopy (PALS) and Xe NMR techniques.
View Article and Find Full Text PDFRegenerated Bombyx mori silk fibroin (RSF) is a widely recognized protein for biomedical applications; however, its hierarchical gel structure is poorly understood. In this paper, the hierarchical structure of photocrosslinked RSF and RSF-based hybrid hydrogel systems: (i) RSF/Rec1-resilin and (ii) RSF/poly(N-vinylcaprolactam (PVCL) is reported for the first time using small-angle scattering (SAS) techniques. The structure of RSF in dilute to concentrated solution to fabricated hydrogels were characterized using small angle X-ray scattering (SAXS), small angle neutron scattering (SANS) and ultra-small angle neutron scattering (USANS) techniques.
View Article and Find Full Text PDFPorous membranes with ultrafast ion permeation and high ion selectivity are highly desirable for efficient mineral separation, water purification, and energy conversion, but it is still a huge challenge to efficiently separate monatomic ions of the same valence and similar sizes using synthetic membranes. We report metal organic framework (MOF) membranes, including ZIF-8 and UiO-66 membranes with uniform subnanometer pores consisting of angstrom-sized windows and nanometer-sized cavities for ultrafast selective transport of alkali metal ions. The angstrom-sized windows acted as ion selectivity filters for selection of alkali metal ions, whereas the nanometer-sized cavities functioned as ion conductive pores for ultrafast ion transport.
View Article and Find Full Text PDFThe fabrication of oriented, crystalline films of metal-organic frameworks (MOFs) is a critical step toward their application to advanced technologies such as optics, microelectronics, microfluidics and sensing. However, the direct synthesis of MOF films with controlled crystalline orientation remains a significant challenge. Here we report a one-step approach, carried out under mild conditions, that exploits heteroepitaxial growth for the rapid fabrication of oriented polycrystalline MOF films on the centimetre scale.
View Article and Find Full Text PDFHighly permeable, thermally rearranged polymer membranes based on bismaleimide derivatives that exhibit excellent CO permeability up to 5440 Barrer with a high BET surface area (1130 m g) are reported for the first time. In addition, the membranes can be easily used to form semi-interpenetrating networks with other polymers endowing them with superior gas transport properties.
View Article and Find Full Text PDFIn this study, we explore the overall structural ensembles and transitions of a biomimetic, multi-stimuli-responsive, intrinsically disordered protein (IDP), Rec1-resilin. The structural transition of Rec1-resilin with change in molecular crowding and environment is evaluated using small-angle neutron scattering and small-angle X-ray scattering. The quantitative analyses of the experimental scattering data using a combination of computational models allowed comprehensive description of the structural evolution, organization, and conformational ensembles of Rec1-resilin in response to the changes in concentration, pH, and temperature.
View Article and Find Full Text PDFAdsorbents for CO2 capture need to demonstrate efficient release. Light-induced swing adsorption (LISA) is an attractive new method to release captured CO2 that utilizes solar energy rather than electricity. MOFs, which can be tailored for use in LISA owing to their chemical functionality, are often unstable in moist atmospheres, precluding their use.
View Article and Find Full Text PDFThe regulation of water content in polymeric membranes is important in a number of applications, such as reverse electrodialysis and proton-exchange fuel-cell membranes. External thermal and water management systems add both mass and size to systems, and so intrinsic mechanisms of retaining water and maintaining ionic transport in such membranes are particularly important for applications where small system size is important. For example, in proton-exchange membrane fuel cells, where water retention in the membrane is crucial for efficient transport of hydrated ions, by operating the cells at higher temperatures without external humidification, the membrane is self-humidified with water generated by electrochemical reactions.
View Article and Find Full Text PDFOptical quality metal organic framework (MOF) thin films were integrated, for the first time, to the best of our knowledge, with structured optical fiber substrates to develop MOF-fiber sensors. The MOF-fiber structure, UiO-66 (Zr-based MOF is well known for its water stability), is a thin film that acts as an effective analyte collector. This provided a Fabry-Perot sensor in which concentrations of up to 15 mM Rhodamine-B were detected via wavelength shifts in the interference spectrum.
View Article and Find Full Text PDFA facile method to improve the stability of γ-cyclodextrin metal-organic frameworks (γ-CD-MOFs) in an aqueous environment has been developed through the incorporation of hydrophobic C60 in their matrices, and the resulting hybrid materials were exploited for drug delivery applications.
View Article and Find Full Text PDFMagnetic metal-organic framework (MOF) composites show highly efficient CO2 desorption capacities upon their exposure to an alternating magnetic field, demonstrating a magnetic induction swing strategy for potentially low-energy regeneration of MOF adsorbents.
View Article and Find Full Text PDFHerein we demonstrate the green synthesis of fluorescent gold nanoclusters (AuNCs) using a multi-responsive intrinsically disordered protein (IDP) polymer, Rec1-resilin, as a multi-functional template. In a controlled environment, Rec1-resilin acts simultaneously as the directing agent and the reducer, and performs the role of a highly efficient stabilizer once AuNCs are formed. The evolution of the photophysical properties and the chemical states of AuNCs formed are measured using UV-Vis, fluorescence and X-ray photoelectron spectroscopy.
View Article and Find Full Text PDFFree-volume of polymers governs transport of penetrants through polymeric films. Control over free-volume is thus important for the development of better membranes for a wide variety of applications such as gas separations, pharmaceutical purifications and energy storage. To date, methodologies used to create materials with different amounts of free-volume are based primarily on chemical synthesis of new polymers.
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