Hydrophobic Pore Research Articles

The Significant Differences in Solvation Thermodynamics of C1–C3 Oxygenates in Hydrophilic versus Hydrophobic Pores of a Hydrophilic Ti-FAU Zeolite Model

The Significant Differences in Solvation Thermodynamics of C1–C3 Oxygenates in Hydrophilic versus Hydrophobic Pores of a Hydrophilic Ti-FAU Zeolite Model

The effect of perfluoroalkyl chain length and the type of acid group on PFAS adsorption from water

Widespread use of per- and polyfluoroalkyl substances (PFAS) poses significant ecological and health risks due to their non-degradability in the environment and consequent bioaccumulation in humans. In this work, we carried out a systematic computational study to unravel the effect of perfluorinated carbon chain length and the type of acid head group on the adsorption mechanism of PFAS from water. We considered the adsorption of perfluoroalkyl carboxylic acids (PFCA) and perfluoroalkyl sulfonic acids (PFSA) with chain lengths of three to eight perfluorinated carbons in hydrophobic all-silica zeolite Beta. Molecular dynamics (MD) simulations coupled with enhanced sampling calculations showed that adsorption free energies of both PFCA and PFSA decreased with increasing number of perfluorinated carbons. Calculated free energies further showed that PFCA and PFSA, which are anions in water, must overcome substantially large interfacial energy barriers to be adsorbed in hydrophobic pores. Subsequent ab initio MD simulations revealed that PFCA and PFSA gain a proton at the water–zeolite interface and are eventually adsorbed in neutral form. Breakdown of guest–host interaction energies into hydrophobic and polar components showed that hydrophobic interactions dominate PFCA adsorption whereas polar interactions are dominant in PFSA adsorption. This is due to sulfonic acid giving rise to stronger electrostatic interactions and the rearrangement of the electron density distribution in the perfluorinated carbon chain, which render the hydrophobic interactions relatively weaker. Our study reveals that a combination of adsorbents that provide optimized hydrophobic and polar interactions should be used for the capture of diverse PFAS from water.

Small Molecule NS11021 Promotes BK Channel Activation by Increasing Inner Pore Hydration.

The Ca2+ and voltage-gated big potassium (BK) channels are implicated in various diseases, including heart disease, asthma, epilepsy, and cancer, but remain an elusive drug target. A class of negatively charged activators (NCAs) have been demonstrated to promote the activation of several potassium channels including BK channels by binding to the hydrophobic inner pore, yet the underlying molecular mechanism of action remains poorly understood. In this work, we analyze the binding mode and potential activation mechanism of a specific NCA named NS11021 using atomistic simulations. The results show that NS11021 binding to the pore in deactivated BK channels is nonspecific and dynamic. The binding free energy of -8.3 ± 0.7 kcal/mol (KD = 0.3-3.1 μM) calculated using umbrella sampling agrees quantitatively with the experimental EC50 range of 0.4-2.1 μM. The bound NS11021 remains dynamic and is distal from the filter to significantly impact its conformation. Instead, NS11021 binding significantly enhances the pore hydration due to the charged tetrazol-phenyl group, thereby promoting the opening of the hydrophobic gate. We further show that the free energy barrier to K+ permeation is reduced by ∼3 kcal/mol regardless of the binding pose, which could explain the ∼62-fold increase in the intrinsic opening of BK channels measured experimentally. Taken together, these results support the idea that the molecular mechanism of NS11021 derives from increasing the hydration level of the conformationally closed pore, which does not depend on specific binding and likely explains the ability of NCAs to activate multiple K+ channels.

Computational investigation in inhibitory effects of amantadine on classical swine fever virus p7 ion channel activity

Classical swine fever virus (CSFV) p7 viroporin plays crucial roles in cellular ion balance and permeabilization. The antiviral drug amantadine effectively inhibits viral replication by blocking the activity of CSFV p7 viroporin. However, little information is available for the binding mode of amantadine with CSFV p7 viroporin, due to the lack of a known polymer structure for CSFV p7. In this study, we employed AlphaFold2 to predict CSFV p7 structures. Subsequently, we conducted a docking study to investigate the binding sites of amantadine to CSFV p7. Computational analysis showed that CSFV p7 forms a pore channel in a hexameric structure. Furthermore, molecular dynamics (MD) simulations and mutant analyses further suggest that CSFV p7 likely exists as a hexamer. Docking studies and MD simulations showed that amantadine interacts with the hydrophibic regions of tetramer and pentamer, as well as with the hydrophobic pore channel of the hexamer. Considering the potential hexameric assembly of CSFV p7, along with docking results, MD simulations, and the characteristics of the gated ion channels, we propose a model of CSFV p7 ion channel based on its hexameric configuration. In this model, residues E21, Y25, and R34 are suggested to selectively recruit and dehydrate ions, while residues L28 and L31 likely act as hydrophobic constrictors, thereby restricting the free movement of water. The binding of amantadine to residues I20, E21, V24 and Y25 effectively blocks ion transport. However, this proposed molecular model requires experimental validation. Our findings give a structural insight into the models of CSFV p7 as an ion channel and provide a molecular explanation for the inhibition effects of amantadine on CSFV p7-mediated ion channel conductance.

Water transport through monolayer fullerene membrane

Water transport through nanoporous materials is important in water treatment, desalination, and nanofiltration. Two-dimensional (2D) membranes such as porous graphene have been explored for high-permeance water transport. However, water transport through a new class of 2D membranes based on two-dimensional covalently linked fullerene monolayers has not been fully explored. Here we use classical molecular dynamics simulations to investigate both vapor and liquid water transport through a monolayer fullerene membrane. We find that a quasi-tetragonal phase fullerene membrane possesses the right pore size and geometry that allows fast water vapor transport (∼ 50 g m−2 day−1 Pa−1) and water liquid transport (∼ 2.0 g m−2 day−1 Pa−1). Furthermore, simulation of sea water transport through the fullerene membrane shows 100 % salt rejection. The much faster vapor transport rate is attributed to the funnel-shaped pore and the optimal size that allows free rotation of water molecules permeating through, while the slower liquid transport is due to the need to desolvate a water molecule to break its hydrogen-bond network across the hydrophobic pore. This work shows the great potential of using monolayer fullerene membranes as 2D membranes for fast and selective water transport.

External surface hydrophilic 3D-POSS-COF@GDL for the direct adsorption of bisphenols in milk samples

In case of organic frameworks (COFs) as adsorbents in the pretreatment of complex food matrices, challenges such as poor dispersion and non-specific adsorption of interfering macromolecules like proteins are often encountered. To address this issue, this work prepared a three-dimensional covalent organic framework (3D-COF) with a novel bcu topology based on polyhedral oligomeric silsesquioxane (POSS). Subsequently, gluconolactone (GDL) was modified onto the external surface of the material via the reaction with the exposed reactive residues. The resulting POSS-COF@GDL adsorbent has an enhanced hydrophilicity in the external surface, thereby significantly improves the dispersion of materials in aqueous solution and reduces the adsorption ability toward protein. Whereas, the inner of material retains hydrophobic pores that exhibit high adsorption efficiency to small hydrophobic molecules. Compared with the traditional pretreatment methods, POSS-COF@GDL can directly extract bisphenols (BPs) in milk samples without any additional treatment. The established sample pretreatment method is coupled with high-performance liquid chromatography-ultraviolet detection (HPLC-UV), resulting in recoveries of 71.8 to 93.6%, intra- and inter-day relative standard deviations (RSDs) of <8.3%, and limits of detection (LODs) of 0.042–0.16 ng∙mL−1 for four BPs.

Water at the nanoscale: From filling or dewetting hydrophobic pores and carbon nanotubes to "sliding" on graphene.

In this work, we study the effect of nanoconfinement on the hydration properties of model hydrophobic pores and carbon nanotubes, determining their wetting propensity and the conditions for geometrically induced dehydration. By employing a recently introduced water structural index, we aim at two main goals: (1) to accurately quantify the local hydrophobicity and predict the drying transitions in such systems, and (2) to provide a molecular rationalization of the wetting process. In this sense, we will further discuss the number and strength of the interactions required by the water molecules to promote wetting. In the case of graphene-like surfaces, an explanation for their unexpectedly significant hydrophilicity will also be provided. On the one hand, the structural index will show that the net attraction to the dense carbon network that a water molecule experiences through several simultaneous weak interactions is sufficient to give rise to hydrophilic behavior. On the other hand, we will show that an additional effect is also at play: the hydrating water molecule is retained on the surface by a smooth exchange of such simultaneous weak interactions, as if "sliding" on graphene.

Molecular insights into the impact of mineral pore size on methane hydrate formation

Natural gas hydrates are not only substantial energy sources but also have significant applications in the chemical industry and other fields. Although investigating hydrate formation in sediment minerals is crucial for their development and utilization, the underlying hydrate formation mechanism remains unclear. Here, molecular simulations were conducted in systems incorporating hydrophobic and hydrophilic pores of different sizes to investigate methane hydrate formation processes. The findings suggest that, as the hydrophobic slit size increases, there is a larger number of dissolved methane after the system reaches a metastable equilibrium state. The probability of cage formation indicates that hydrate cages readily form on hydrophobic surfaces or in the solution phase near the solution/gas interface. The larger slits are preferred for hydrate nucleation, regardless of whether the surface is hydrophobic, with most initial nuclei located near the liquid/methane interface. However, the interface perturbation can lead to the movement and growth of hydrate nuclei near the solution/methane interface into the bulk solution phase. Additionally, hydrate can nucleate and grow on the hydrophobic surface, facilitated by the adsorbed methane molecules and nonstandard cages. Pores hinder methane storage capacity in the hydrate phase due to the confinement effect and the amorphous nature of the hydrate formed. These molecular-level findings enhance our understanding of hydrate formation in sedimentary environments and porous materials, benefiting the development of natural gas hydrates and the use of porous materials for gas storage and transportation.

Exploring the influence of pore shape on conductance and permeation

There are increasing numbers of ion channel structures featuring heteromeric subunit assembly, exemplified by synaptic α1βB glycine and α4β2 nicotinic receptors. These structures exhibit inherent pore asymmetry, but the relevance of this to function is unknown. Furthermore, molecular dynamics simulations performed on symmetrical homomeric channels often lead to thermal distortion whereby conformations of the resulting ensemble are also asymmetrical. When functionally annotating ion channels, researchers often rely on minimal constrictions determined via radius-profile calculations performed with computer programs, such as HOLE or CHAP, coupled with an assessment of pore hydrophobicity. However, such tools typically employ spherical probe particles, limiting their ability to accurately capture pore asymmetry. Here, we introduce an algorithm that employs ellipsoidal probe particles, enabling a more comprehensive representation of the pore geometry. Our analysis reveals that the use of nonspherical ellipsoids for pore characterization provides a more accurate and easily interpretable depiction of conductance. To quantify the implications of pore asymmetry on conductance, we systematically investigated carbon nanotubes with varying degrees of pore asymmetry as model systems. The conductance through these channels shows surprising effects that would otherwise not be predicted with spherical probes. The results have broad implications not only for the functional annotation of biological ion channels but also for the design of synthetic channel systems for use in areas such as water filtration. Furthermore, we make use of the more accurate characterization of channel pores to refine a physical conductance model to obtain a heuristic estimate for single-channel conductance. The code is freely available, obtainable as pip-installable python package and provided as a web service.

Chemometrically-aided general approach to novel adsorbents studies: Case study on the adsorption of pharmaceuticals by the carbonized Ailanthus altissima leaves

A chemometrically based approach was applied to select the most efficient drug adsorbent among the biochars obtained from the novel feedstock, the leaves of the invasive plant (Ailanthus altissima). The representative target adsorbates (atenolol, paracetamol, ketorolac and tetracycline) were selected on the basis of their physicochemical properties to cover a wide chemical space, which is the usual analytical challenge. Their adsorption was investigated using design of experiments as a comprehensive approach to optimise the performance of the adsorption system, rationalise the procedure and overcome common drawbacks. Among the response surface designs, the central composite design was selected as it allows the identification of important experimental factors (solid-to-liquid ratio, pH, ionic strength) and their interactions, and allows the selection of optimal experimental conditions to maximise adsorption performance. The biochars were prepared by pyrolysis at 500 °C and 800 °C (BC-500 and BC-800) and the ZnCl2-activated biochars were prepared at 650 °C and 800 °C (AcBC-650 and AcBC-800). The FTIR spectra revealed that increasing the pyrolysis temperature without activator decreases the intensity of all bands, while activation preserves functional groups, as evidenced by the spectra of AcBC-650 and AcBC-800. High temperatures during activation promoted the development of an efficient surface area, with the maximum observed for AcBC-800 reaching 347 m2 g−1. AcBC-800 was found to be the most efficient adsorbent with removal efficiencies of 34.1, 51.3, 55.9 and 38.2 % for atenolol, paracetamol, ketorolac and tetracycline, respectively. The models describing the relationship between the removal efficiency of AcBC-800 and the experimental factors studied, showed satisfactory predictive ability (predicted R2 > 0.8) and no significant lack-of-fit was observed. The results obtained, including the mathematical models, the properties of the adsorbates and the adsorbents, clearly indicate that the adsorption mechanisms of activated biochars are mainly based on hydrophobic interactions, pore filling and hydrogen bonding.

Monitoring Poly(methyl methacrylate) and Polyvinyl Dichloride Micro/Nanoplastics in Water by Direct Solid-Phase Microextraction Coupled to Gas Chromatography-Mass Spectrometry.

A simple, sustainable, and sensitive monitoring approach of micro/nanoplastics (MNPs) in aqueous samples is crucial since it helps in assessing the extent of contamination and understanding the potential risks associated with their presence without causing additional stress to the environment. In this study, a novel strategy for qualitative and quantitative determination of MNPs in water by direct solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS) was proposed for the first time. Spherical poly(methyl methacrylate) (PMMA) and irregularly shaped polyvinyl dichloride (PVDC) were used to evaluate the feasibility and performance of the proposed method. The results demonstrated that both PMMA and PVDC MNPs were efficiently extracted by the homemade SPME coating of nitrogen-doped porous carbons (N-SPCs) and exhibited sufficient thermal decomposition in the GC-MS injection port. Excellent extraction performances of N-SPCs coating for MNPs are attributed to hydrophobic cross-linking, electrostatic forcing, hydrogen bonding, and pore trapping. Methyl methacrylate was identified as the marker for PMMA, while 1,3-dichlorobenzene and 1,3,5-trichlorobenzene were the indicators for PVDC. Under the optimal extraction and decomposition conditions, the proposed method exhibited ultrahigh sensitivity, with a limit of detection of 0.0041 μg/L for PMMA and 0.0054 μg/L for PVDC. Notably, a programmed temperature strategy for the GC-MS injector was developed to discriminate and eliminate the potential interferences of intrinsic indicator compounds. Owing to the integration of sampling, extraction, injection, and decomposition into one step by SPME, the proposed method demonstrates exceptional sensitivity, eliminating the necessity for complex sample pretreatment procedures and the use of organic solvents. Finally, the proposed method was successfully applied in the determination of PMMA and PVDC MNPs in real aqueous samples.

Adsorption efficiency and in-situ catalytic thermal degradation behaviour of microplastics from water over Fe-modified lignin-based magnetic biochar

The efficient removal and degradation of microplastics are critical for protecting aquatic ecosystems. Herein, Fe-modified magnetic biochar (MBC) was synthesized as an adsorbent for removing microplastics in water. The effects of lignin/Fe salt mass ratios, adsorbent amount, adsorption time, adsorption temperature, solution pH, and presence of coexisting anions on adsorption efficiency were investigated. The thermal degradation behaviour and recycling characteristic of microplastics was also explored. Results showed that MBC has a developed pore structure, superparamagnetic property, and abundant oxygen-containing functional groups. The removal efficiency of polystyrene microplastics using MBC-11 was 99 %, with an adsorption capacity of 68.57 mg/g, which was 25 times higher than that of unmodified lignin biochar. The kinetics of the adsorption process followed the pseudo-first kinetic model, and the equilibrium data best fitted the Freundlich model. Thermodynamic results confirmed that adsorption over MBC was a spontaneous, heat-absorbing, and entropy-increasing process. The adsorption mechanism of PS by biochar was mainly via electrostatic and hydrophobic interactions and pore throttle. The thermal-degradation products of PS were mainly hydrocarbons, including styrene, benzene, and toluene, owing to the enhanced β-scission, H-shift, and methylation reactions at MBC catalytic sites. This study provides a scientific basis for the development of control technologies for microplastics removal in water.

A Synergetic Pore Compartmentalization and Hydrophobization Strategy for Synchronously Boosting the Stability and Activity of Enzyme.

Spatial immobilization of fragile enzymes using a nanocarrier is an efficient means to design heterogeneous biocatalysts, presenting superior stability and recyclability to pristine enzymes. An immobilized enzyme, however, usually compromises its catalytic activity because of inevasible mass transfer issues and the unfavorable conformation changes in a confined environment. Here, we describe a synergetic metal-organic framework pore-engineering strategy to trap lipase (an important hydrolase), which confers lipase-boosted stability and activity simultaneously. The hierarchically porous NU-1003, featuring interconnected mesopore and micropore channels, is precisely modified by chain-adjustable fatty acids on its mesopore channel, into which lipase is trapped. The interconnected pore structure ensures efficient communication between trapped lipase and exterior media, while the fatty acid-mediated hydrophobic pore can activate the opening conformation of lipase by interfacial interaction. Such dual pore compartmentalization and hydrophobization activation effects render the catalytic center of trapped lipase highly accessible, resulting in 1.57-fold and 2.46-fold activities as native lipase on ester hydrolysis and enantioselective catalysis. In addition, the feasibility of these heterogeneous biocatalysts for kinetic resolution of enantiomer is also validated, showing much higher efficiency than native lipase.

Dynamic molecular portraits of ion-conducting pores characterize functional states of TRPV channels

Structural biology is solving an ever-increasing number of snapshots of ion channel conformational ensembles. Deciphering ion channel mechanisms, however, requires understanding the ensemble dynamics beyond the static structures. Here, we present a molecular modeling-based approach characterizing the ion channel structural intermediates, or their “dynamic molecular portraits”, by assessing water and ion conductivity along with the detailed evaluation of pore hydrophobicity and residue packing. We illustrate the power of this approach by analyzing structures of few vanilloid-subfamily transient receptor potential (TRPV) channels. Based on the pore architecture, there are three major states that are common for TRPVs, which we call α-closed, π-closed, and π-open. We show that the pore hydrophobicity and residue packing for the open state is most favorable for the pore conductance. On the contrary, the α-closed state is the most hydrophobic and always non-conducting. Our approach can also be used for structural and functional classification of ion channels.

Production of Disinfective Coating Layer to Facial Masks Supplemented with Camellia sinensis Extract.

Although usefulness of masks for protection against respiratory pathogens, accumulation of pathogens on their surface represents a source of infection spread. Here we prepared a plant extract-based disinfecting layer to be used in coating masks thus inhibiting their capacity to transmit airborne pathogens. To reach this, a polypropylene membrane base was coated with a layer of polyvinyledine difluoride polymer containing 500μg/ml of Camellia sinensis (Black tea) methanolic extract. Direct inhibitory effects of C. sinensis were initially demonstrated against Staphylococcus aureus (respiratory bacteria), influenza A virus (enveloped virus) and adenovirus 1 (non-enveloped virus) which were directly proportional to both extract concentration and incubation time with the pathogen. This was later confirmed by the capacity of the supplemented membrane with the plant extract to block infectivity of the above mentioned pathogens, recorded % inhibition values were 61, 72 and 50 for S. aureus, influenza and adenovirus, respectively. In addition to the disinfecting capacity of the membrane its hydrophobic nature and pore size (154nm) prevented penetration of dust particles or water droplets carrying respiratory pathogens. In summary, introducing this layer could protect users from infection and decrease infection risk upon handling contaminated masks surfaces.

Fractionation of biomass-burning smoke-derived dissolved organic matters on the surface of clay minerals: Variations of molecular properties and components

Biomass burning (e.g., wildfire) frequently occurs globally, inevitably produces abundant biomass-burning smoke-derived dissolved organic matters (BBS-DOMs) which eventually deposits on the surface environment. The adsorption and fractionation of BBS-DOMs on clays inevitably alter their biogeochemical process and environmental behaviors in the surface environment. It is therefore important to clarify the adsorption and fractionation of BBS-DOM on clay surfaces. This study found that the fractionation of BBS-DOMs on clays (montmorillonite and kaolinite) were controlled by their functional groups, aromaticity, molecular size and organic components. The spectral indexes (SUVA254 and S275–295) of BBS-DOMs in solution after clays adsorption suggested that with the increasing DOC concentration, the primary interaction between BBS-DOMs and clays changed from hydrogen bond to hydrophobic/pore filling effects, and the adsorption ratio of the large molecules increased, which were very different from natural fulvic acid. Furthermore, various BBS-DOMs and fulvic acid had different component fractionation behaviors during clay adsorption, because they had different abundances of protein-like matters (hydrogen bond donors), pyridine-N/pyrimidine-N (positive charge doners of electrostatic interaction), and fulvic-like matters (hydrophobic interaction and pore filling effect). Additionally, the increasing pH weakened the adsorption of bulk BBS-DOMs and enhanced the adsorption ratio of aromatic matters and smaller BBS-DOM molecules. Meanwhile, at a higher pH, the adsorption ratio of protein-like matters increased, while the adsorption ratio of humic- and fulvic-like matters decreased. The result was ascribed to the enhanced hydrogen bond between protein-like matters and clays as well as the enhanced electrostatic repulsion between humic−/fulvic-like matters and clays. This study is helpful for deeply understanding the multimedia-crossing environmental behavior of BBS-DOMs in the surface environment.

Order–disorder–order mesophase transitions in self-assembled mesoporous alumina for enhanced CO2 adsorption

The addition of a hydrophobic micelle pore expander to self-assembling mesostructured hybrid materials enables access to new combinations with differently ordered mesophases and enhanced structural properties. Here we detail our investigations into the influence of 1,3,5-trimethylbenzene (TMB) on the self-assembly behaviors of an F127 Pluronic triblock copolymer with an aluminum oxide sol additive. By varying the chemical mixing sequence, the TMB-to-F127 mass ratio and the acid-to-metal molar ratio, we observe that TMB exhibits dual roles, functioning both as a hydrophobic swelling agent and as a low dielectric co-solvent. This induces a mesophase transition from an ordered p6mm lattice to a disordered state and subsequently back to the ordered p6mm phase. We propose a structure formation mechanism based on the DLVO theory to describe the thermodynamics and kinetic mobility of the hybrid micelles during the order-disorder and ensuing disorder-order mesophase transitions. The resulting ordered mesoporous alumina structures, with considerable pore sizes (up to 12 nm), high surface areas (up to 314 m2/g) and pore volumes (up to 0.74 cm3/g), organized pore geometry and variable inorganic wall thicknesses, have shown excellent CO2 adsorption capacities and are appealing for various applications, including stable high temperature catalyst supports, separation and sensing.

Discovery of bubble accumulation behavior in catalyst layer of proton exchange membrane water electrolyzer

The presence of nano-scale oxygen bubble transport and accumulation within the anodic catalyst layer (CL) in proton exchange membrane water electrolyzer (PEMWE) remains controversial. In this study, we obtain several crucial evidence to resolve this debate using a Pt-coated mesh porous transport layer (PTL) as an oxygen sensor and with the help of multiple visualization methods. The evidence includes the oxygen reduction current detected from the anodic CL after electrolysis was stopped, continued bubble generation and growth on the CL surface when no oxygen evolution reaction happening in CL, and the gas outlet holes observed from the CL surface. The evidence supports that nano-scale oxygen bubble transport and accumulation indeed happen within anodic CL. The influence of characteristics of the CL on the reversible performance change induced by bubble accumulation behavior further reveals the possible mechanism of bubble transport in CL. The bubbles are generated at the entire CL, and its transport behavior is shaped by the porous structure of CL. Increasing the bubble transport distance, tortuosity, and pore hydrophobicity within the CL all lead to a significant increase in the rate and degree of bubble accumulation within the CL.

Dried Porous Biomaterials from Mealworm Protein Gels: Proof of Concept and Impact of Drying Method on Structural Properties and Zinc Retention.

Dried porous materials can be found in a wide range of applications. So far, they are mostly prepared from inorganic or indigestible raw materials. The aim of the presented study was to provide a proof of concept for (a) the suitability of mealworm protein gels to be turned into dried porous biomaterials by either a combination of solvent exchange and supercritical drying to obtain aerogels or by lyophilization to obtain lyophilized hydrogels and (b) the suitability of either drying method to retain trace elements such as zinc in the gels throughout the drying process. Hydrogels were prepared from mealworm protein, subsequently dried using either method, and characterized via FT-IR, BET volume, and high-resolution scanning electron microscopy. Retention of zinc was evaluated via energy-dispersive X-ray spectroscopy. Results showed that both drying methods were suitable for obtaining dried porous biomaterials and that the drying method mainly influenced the overall surface area and pore hydrophobicity but not the secondary structure of the proteins in the gels or their zinc content after drying. Therefore, a first proof of concept for utilizing mealworm protein hydrogels as a base for dried porous biomaterials was successful and elucidated the potential of these materials as future sustainable alternatives to more conventional dried porous materials.

Effect of Pore Confinement of Ionic Liquids on Solute Diffusion within Mesoporous Silica Microparticles.

The transport properties of the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) confined within silica microparticles with well-ordered, accessible mesopores (5.4 or 9 nm diameter) were investigated. [BMIM][PF6] confinement was confirmed by using differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The transport properties of the confined IL were studied using the neutral and cationic fluorescent probes 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM) and rhodamine 6G, respectively, through fluorescence recovery after photobleaching (FRAP) in confocal microscopy. The diffusivity of DCM in 9 nm pores is 0.026 ± 0.0091 μm2/s, which is 2 orders of magnitude less than in the bulk ionic liquid. The pore size did not affect the diffusivity of DCM in unmodified silica nanopores. The diffusivity of the cationic probe is reduced by 63% relative to that of the neutral probe. Diffusivity is increased with water content, where equilibrium hydration of the system leads to a 37% increase in DCM diffusivity. The most dramatic impact on diffusivity was caused by tethering an IL-like methylimidazolium chloride group to the pores, which increased the pore hydrophobicity and resulted in 3-fold higher diffusivity of DCM compared to bare silica pores. Subsequent exchange of the chloride anion from the tethering group with PF6- decreased the diffusivity to half that of bare silica. The diffusion of probe molecules is affected most strongly by the pore wall effects on probe interactions rather than by the pore size itself, which suggests that understanding pore wall diffusion is critical to the design of nanoconfined ILs for separations, catalysis, and energy storage.