Quartz Crystal Microbalance Research Articles

Self-Cleaning Highly Porous TiO2 Coating Designed by Swelling-Assisted Sequential Infiltration Synthesis (SIS) of a Block Copolymer Template.

Photocatalytic self-cleaning coatings with a high surface area are important for a wide range of applications, including optical coatings, solar panels, mirrors, etc. Here, we designed a highly porous TiO2 coating with photoinduced self-cleaning characteristics and very high hydrophilicity. This was achieved using the swelling-assisted sequential infiltration synthesis (SIS) of a block copolymer (BCP) template, which was followed by polymer removal via oxidative thermal annealing. The quartz crystal microbalance (QCM) was employed to optimize the infiltration process by estimating the mass of material infiltrated into the polymer template as a function of the number of SIS cycles. This adopted swelling-assisted SIS approach resulted in a smooth uniform TiO2 film with an interconnected network of pores. The synthesized film exhibited good crystallinity in the anatase phase. The resulting nanoporous TiO2 coatings were tested for their functional characteristics. Exposure to UV irradiation for 1 h induced an improvement in the hydrophilicity of coatings with wetting angle reducing to unmeasurable values upon contact with water droplets. Furthermore, their self-cleaning characteristics were tested by measuring the photocatalytic degradation of methylene blue (MB). The synthesized porous TiO2 nanostructures displayed promising photocatalytic activity, demonstrating the degradation of approximately 92% of MB after 180 min under ultraviolet (UV) light irradiation. Thus, the level of performance was comparable to the photoactivity of commercial anatase TiO2 nanoparticles of the same quantity. Our results highlight a new robust approach for designing hydrophilic self-cleaning coatings with controlled porosity and composition.

Nanoscale Insights into the Interaction Mechanism Underlying the Adsorption and Retention of Heavy Metal Ions by Humic Acid.

The mobility and distribution of heavy metal ions (HMs) in aquatic environments are significantly influenced by humic acid (HA), which is ubiquitous. A quantitative understanding of the interaction mechanism underlying the adsorption and retention of HMs by HA is of vital significance but remains elusive. Herein, the interaction mechanism between HA and different types of HMs (i.e., Cd(II), Pb(II), arsenate, and chromate) was quantitatively investigated at the nanoscale. Based on quartz crystal microbalance with dissipation tests, the adsorption capacities of Pb(II), Cd(II), As(V), and Cr(VI) ionic species on the HA surface were measured as ∼0.40, ∼0.25, ∼0.12, and ∼0.02 nmol cm-2, respectively. Atomic force microscopy force results showed that the presence of Pb(II)/Cd(II) cations suppressed the electrostatic double-layer repulsion during the approach of two HA surfaces and the adhesion energy during separation was considerably enhanced from ∼2.18 to ∼5.05/∼4.18 mJ m-2. Such strong adhesion stems from the synergistic metal-HA complexation and cation-π interaction, as evidenced by spectroscopic analysis and theoretical simulation. In contrast, As(V)/Cr(VI) oxo-anions could form only weak hydrogen bonds with HA, resulting in similar adhesion energies for HA-HA (∼2.18 mJ m-2) and HA-As(V)/Cr(VI)-HA systems (∼2.26/∼1.96 mJ m-2). This work provides nanoscale insights into quantitative HM-HA interactions, improving the understanding of HMs biogeochemical cycling.

Adsorption Behavior and Tribological Properties of Surface-Capped Silica Nano-Additives in Rapeseed Oil

Abstract The influence of particle size and surface modifier structure on the adsorption behavior and tribological properties of surface-capped silica nano-additives in rapeseed oil was investigated. With four kinds of SiO2 nanoparticles, methyl-modified DNS-2 (particle size 14 nm) and DNS-3 (particle size 5 nm), vinyl-modified RNS-D (particle size 5 nm), and epoxy-modified RNS-E (particle size 5 nm) as the nano-additives of rapeseed oil, their adsorption behavior in rapeseed oil was studied with a quartz crystal microbalance (QCM-D), and their tribological properties were evaluated with a four-ball friction and wear tester. DNS-2 with a larger particle size can form a high-strength tribo-film on the rubbed surface through shear sintering, thereby reducing the wear scar diameter of the steel ball. DNS-3, RNS-D, and RNS-E with smaller particle sizes can form a viscoelastic adsorption layer on the rubbed steel surface, and their equilibrium adsorption mass thereon increases with the increase of the polarity of the modifiers, which corresponds to the increases in their friction-reducing and anti-wear abilities as well as extreme pressure properties therewith. Particularly, the equilibrium adsorption mass and adsorption rate of RNS-E surface-capped by an epoxy group with the largest polarity are 16 times and 34 times higher than those of DNS-3 surface-capped by methyl. This indicates that encapsulating silica nanoparticles with strongly polar organic species could help to enhance its adsorption on rubbed metal surfaces and improve its tribological properties in rapeseed oil.

Detection of Microorganisms Using Artificial Siderophore-FeIII Complex-Modified Substrates.

Four FeIII complexes of typical artificial siderophore ligands containing catecholate and/or hydroxamate groups of tricatecholate, biscatecholate-monohydroxamate, monocatecholate-bishydroxamate, and trihydroxamate type artificial siderophores (K3[FeIIILC3], K2[FeIIILC2H1], K[FeIIILC1H2], and [FeIIILH3]) were modified on Au substrate surfaces. Their abilities to adsorb microorganisms were investigated using scanning electron microscopy, quartz crystal microbalance, and AC impedance methods. The artificial siderophore-iron complexes modified on Au substrates (FeLC3/Au, FeLC2H1/Au, FeLC1H2/Au, and FeLH3/Au) showed the selective immobilization behavior for various microorganisms, depending on the structural features of the artificial siderophores (the number of catecholate and hydroxamate arms). Their specificities corresponded well with the structural characteristics of natural siderophores released by microorganisms and used for FeIII ion uptake. These findings suggest that they were generated via specific interactions between the artificial siderophore-FeIII complexes and the receptors on microorganism surfaces. Our observations revealed that the FeL/Au systems may be potentially used as effective microbe-capturing probes that can enable rapid and simple detection and identification of various microorganisms.

Emerging Multifunctional Carbon‐Nanomaterial‐Based Biosensors for Cancer Diagnosis

Despite significant advancements in medical technology, cancer remains the world's second‐leading cause of death, largely attributed to late‐stage diagnoses. While traditional cancer detection methodologies offer foundational insights, they often lack the specificity, affordability, and sensitivity for early‐stage identification. In this context, the development of biosensors offers a distinct possibility for the precise and rapid identification of cancer biomarkers. Carbon nanomaterials, including graphene, carbon nitride, carbon quantum dots, and other carbon‐based nanostructures, are highly promising for cancer detection. Their simplicity, high sensitivity, and cost‐effectiveness contribute to their potential in this field. This review aims to elucidate the potential of emerging carbon‐nanomaterial‐based biosensors for early cancer diagnosis. The relevance of the various biosensor mechanisms and their performance to the physicochemical properties of carbon nanomaterials is discussed in depth, focusing on demonstrating broad methodologies for creating performance biosensors. Diverse carbon‐nanomaterial‐based detection techniques, such as electrochemical, fluorescence, surface plasmon resonance, electrochemiluminescence, and quartz crystal microbalance, are emphasized for early cancer detection. At last, a summary of existing challenges and future outlook in this promising field is elaborated.

Mechanism of mitigating organic fouling on an electro-conductive membrane under anaerobic conditions and cathodic operation

Anaerobic electroconductive membrane (ECM) bioreactors are promising wastewater treatment technology, yet their organic antifouling mechanism remains unclear. This research investigated the impact of reactive oxygen species (ROS) oxidation, pH alteration, and electrostatic repulsion on carbon nanotube-based ECM organic fouling. Using a decoupled anode–cathode filtration system ensured unbiased results from the anode while studying distinct conditions near the cathodic ECM surface. The results demonstrated a 50 % reduction in transmembrane pressure (TMP) onset applying potential due to electroosmosis, emphasizing its importance in fouling studies. Fouling experiments using alginate in synthetic wastewater solution showed substantial organic fouling at open circuit potential, −1 and −1.5 V, as the TMP increased by about 2.5 times than the initial value. Fouling decreased significantly at −2.5 V (vs. Ag/AgCl), as indicated by the stable TMP. Analysis of ROS effects and fouling experiments at pH 7–––12 found no influence on organic fouling. Simplified force balance analysis and filtration tests suggested electrostatic repulsion as the antifouling mechanism. At potentials below −2.5 V, electrostatic repulsion maximizes closer to the ECM surface, causing fouling from short-range attractive forces. Electrochemical quartz crystal microbalance analysis at 0.1 V (vs. Ag/AgCl) proposed that a smooth ECM surface can reduce organic fouling at lower potentials.

Understanding of the flocculating performance in varying salinity solutions of Chi-g-CPAM and CPAM

In this work, the adsorption performance of a novel chitosan-based flocculant (Chi-g-CPAM) and a cationic flocculant (CPAM) onto the kaolinite surface as well as the interaction mechanisms have been investigated by settling tests, atomic force microscopy (AFM) and quartz crystal microbalance with dissipation (QCM-D). When the KCl concentration of the solution altered from 1 mM to 100 mM, the settling rate of kaolinite suspension using CPAM deteriorated from 2.73 m/h to 1.97 m/h. However, the Chi-g-CPAM exhibited salt resistance as the settling rate changed slightly from 2.34 m/h to 2.44 m/h. From the QCM-D results, the Δf of CPAM onto silica sensor changed from − 3.6 Hz to − 33.6 Hz and -ΔD/Δf × 106 increased from 0.167 to 0.223, confirming that the CPAM layer adsorbed on the silica surface was thicker and more dissipative in 100 mM KCl solution. Meanwhile, the Δf of Chi-g-CPAM onto silica sensor changed from − 14.3 Hz to − 33.9 Hz. The conformation of Chi-g-CPAM layer changed slightly as the -ΔD/Δf × 106 increased from 0.174 to 0.186. From the AFM measurements in 1 mM and 100 mM KCl solution, the distance of adhesion forces between the silica probe and CPAM expanded from approximately 20 nm to around 50 nm, and the adhesion force changed from 1.9 nN± 0.1 nN to 21.3 nN± 0.1 nN. The interaction forces with a long range (∼100 nm) maintained at about 3 nN between the silica probe and Chi-g-CPAM. Such difference was mainly attributed to the steric hindrance effect originating from the shorter molecular chain of Chi-g-CPAM. In 100 mM KCl solution, the CPAM molecules with long chains had a more coiled conformation than Chi-g-CPAM, which resulted a train-like flat adsorption conformation and larger adhesion, and formed a loose and thick polymer layer of CPAM in high salinity. The insights into the flocculating performance in varying salinity solutions of CPAM and Chi-g-CPAM will contribute to the molecular design of chitosan-based flocculants for efficient wastewater treatment.

Polyvinylpyrrolidone-stabilised gold nanoparticle coatings inhibit blood protein adsorption

Abstract In this work, the ability of polyvinylpyrrolidone (PVP)-stabilised gold nanoparticle (AuNP) coatings to inhibit blood protein adsorption was evaluated by studying time-resolved solid–liquid interactions of the coatings with the model blood protein bovine serum albumin (BSA). Inhibiting unspecific blood protein adsorption is of crucial importance for blood-contacting implant devices, e.g. vascular grafts, stents, artificial joints, and others, as a preventive strategy for bacterial biofilm formation. A quartz crystal microbalance was used in this work to coat the AuNPs on piezoelectric sensors and to follow time-resolved solid–liquid interactions with the proteins. The AuNP coatings were evaluated for their wettability by contact angle measurements, their surface morphology by light- and atomic force microscopy, and their chemical composition by energy-dispersive X-ray spectroscopy. Results revealed a homogeneous distribution of AuNPs on the sensor surface with a dry mass coverage of 3.37 ± 1.46 µg/cm2 and a contact angle of 25.2 ± 1.1°. Solid–liquid interaction studies by quartz crystal microbalance showed a high repellence of BSA from the PVP-stabilised AuNP coatings and the importance of the PVP in the mechanism of repellence. Furthermore, the conformation of the polymer on the coatings as well as its viscoelastic properties were revealed. Finally, the activated partial thrombin time test and fibrinogen adsorption studies revealed that the AuNPs do not accelerate blood coagulation and can partially inhibit the adhesion of fibrinogen, which is a crucial factor in the common blood coagulation cascade. Such AuNPs have the potential to be used in blood-contact medical applications.

PH-dependent interactions of coacervate-forming histidine-rich peptide with model lipid membranes

Peptide-based liquid droplets (coacervates) produced by spontaneous liquid-liquid phase separation (LLPS), have emerged as a promising class of drug delivery systems due to their high entrapping efficiency and the simplicity of their formulation. However, the detailed mechanisms governing their interaction with cell membranes and cellular uptake remain poorly understood. In this study, we investigated the interactions of peptide coacervates composed of HBpep—peptide derived from the histidine-rich beak proteins (HBPs) of the Humboldt squid—with model cellular membranes in the form of supported lipid bilayers (SLBs). We employed quartz crystal microbalance with dissipation monitoring (QCM-D), neutron reflectometry (NR) and atomistic molecular dynamics (MD) simulations to reveal the nature of these interactions in the absence of fluorescent labels or tags. HBpep forms small oligomers at pH 6 whereas it forms µm-sized coacervates at physiological pH. Our findings reveal that both HBpep oligomers and HBpep-coacervates adsorb onto SLBs at pH 6 and 7.4, respectively. At pH 6, when the peptide carries a net positive charge, HBpep oligomers insert into the SLB, facilitated by the peptide’s interactions with the charged lipids and cholesterol. Importantly, however, HBpep coacervate adsorption at physiological pH, when it is largely uncharged, is fully reversible, suggesting no significant lipid bilayer rearrangement. HBpep coacervates, previously identified as efficient drug delivery vehicles, do not interact with the lipid membrane in the same manner as traditional cationic drug delivery systems or cell-penetrating peptides. Based on our findings, HBpep coacervates at physiological pH cannot cross the cell membrane by a simple passive mechanism and are thus likely to adopt a non-canonical cell entry pathway.

Dispersion of asphaltene aggregates by zwitterionic surfactants: influence of cations structure

The precipitation and deposition of asphaltenes are significant challenges in the petroleum industry resulting in substantial costs. A practical approach to addressing this issue is to use chemicals as inhabiting and dispersing agents. Zwitterionic surfactants are interesting materials in this field. In this study, three zwitterionic compounds including 2-(1-methyl-1H-imidazol-3-ium-3-yl)butane-1-sulfonate (MIBS), 4-(pyridin-1-ium-1-yl) butane-1-sulfonate (PBS), and 4-(tributylammonio)butane-1-sulfonate (TBBS) were synthesized and characterized by FT-IR, NMR spectroscopy, thermogravimetric, and differential thermal analysis. The ability of these zwitterions to prevent asphaltenes precipitation was investigated using interfacial measurements, ultraviolet spectroscopy, quartz microbalance analysis, particle size analysis, and optical microscopy. The results showed that the MIBS zwitterion, which contains an imidazole cation, was the most effective in dispersing asphaltene aggregates compared to the other two zwitterions. For instance, the UV spectroscopy results showed that the dispersion indexes for MIBS, PBS, and TBBS were 52.8%, 29.9%, and 16.3%, respectively. In addition, the size of asphaltene particles reached from 2179 nm to 622, 1489, and 2038 nm for MIBS, PBS, and TBBS, respectively. Finally, a comparison between the performance of these zwitterions with sodium dodecyl sulfonate (SDS) and tetrabutylammonium hydrogen sulfate (TBAHS) showed the following trend: MIBS (90.5%)> PBS (79.4%) > TBAHS (75%)> SDS (73.9%) >TBBS (46%).

Design and development of a portable low-cost QCM-based system for liquid biosensing

Quartz crystal microbalance (QCM) is a versatile sensing platform that has gained increasing attention for its use in bioapplications due to its high sensitivity, real-time measurement capabilities, and label-free detection. This article presents a portable QCM system for liquid biosensing that uses a modified Hartley oscillator to drive 14 mm-diameter commercial QCM sensors. The system is designed to be low-cost, easy to use, and highly sensitive, making it ideal for various bioapplications. A new flow cell design to deliver samples to the surface of the sensor has been designed, fabricated, and tested. For portability and miniaturization purposes, a micropump-based pumping system is used in the current system. The system has a built-in temperature controller allowing for accurate frequency measurements. In addition, the system can be used in benchtop mode. The capability of the present system to be used in liquid biosensing is demonstrated through an experimental test for sensitivity to changes in the viscosity of glycerol samples. It was found to have a sensitivity of 263.51 Hz/mPa.s using a 10 MHz QCM sensor. Future work regarding potential applications was suggested.Graphical

THE EFFECT OF SPIN COATING’S SPEED ON GRAPHENE-OXIDE’S LAYER TOPOGRAPHY AND QCM VISCOELASTICITY

Spin coating speed controls the deposition process, affecting the formation of the layer’s topography of graphene oxide and the viscoelastic properties of quartz crystal microbalance (QCM). In this work, the graphene oxide was deposited on the QCM surface by spin coating method with speeds ranging from 500 to 800 rpm. The layer’s surface topography was subsequently measured and analyzed using a roughness multiparameter, which included the area average (Sa), area roughness deviation (Sq), localized surface roughness (Sz), surface skewness (Ssk), and surface kurtosis (Sku). The Sa, Sq, and Sz, which were decreased as the spinning speed increased. The measurements indicated that the graphene oxide layer deposited at 500 rpm had a rough and clumpy texture, while at a high speed of 800 rpm, the layer had a much smoother texture. A detailed analysis using the Sku and Ssk parameters revealed that the clumpy texture in the 500 rpm sample contains tapered sharp graphene oxide structures and a small amount of porosity. On the other hand, the sharp structures were significantly reduced, and porosity was dominant in the sample deposited at high speeds of 700 rpm and 800 rpm. The effect of the spinning speed and the topography on the viscoelasticity was studied using an impedance analyzer. The impedance of the layer deposited at 500 rpm was relatively higher than that at 800 rpm. The frequency shift was also relatively significant for the sample deposited at low speed and was reduced at higher speed. The impedance analysis demonstrated that the layer’s viscosity is affected by its mass, roughness, texture, and porosity.

Physicochemical Features and Applicability of Newly Fabricated Phytopharmaceutical-Loaded Hydrogel Alginate Microcarriers with Viscoelastic Polyelectrolyte Coatings.

The design of novel polymeric carrier systems with functional coatings is of great interest for delivering various bioactive molecules. Microcapsules coated with polyelectrolyte (PE) films provide additional functionality and fine-tuning advantages essential for controlled drug release. We developed hydrogel microcarriers coated with functional PE films with encapsulated substances of natural origin, resveratrol (RES), curcumin (CUR), and epigallocatechin gallate (EGCG), which have cytotoxic and chemopreventive properties. Alginate (ALG) based microparticles were loaded with phytopharmaceuticals using the emulsification method, and then their surface was modified with PE coatings, such as chitosan (CHIT) or poly(allylamine hydrochloride) (PAH). The morphology and mean diameter of microcarriers were characterised by scanning electron microscopy, encapsulation efficiency was determined by UV-Vis spectroscopy, whereas the physicochemical properties of functional PE layers were studied using quartz crystal microbalance with dissipation monitoring and streaming potential measurements. The release profiles of active compounds from the hydrogel microparticles were described using the Peppas-Sahlin model. The cytotoxic effect of designed delivery systems was studied by evaluating their impact on the proliferation, mitochondrial metabolic function, and lipid peroxidation level of 5637 human bladder cancer cells. The present work demonstrates that the physicochemical and biological features of fabricated microcarriers can be controlled by the type of encapsulated anti-cancer agent and PE coating.

Development of gold nanospikes-modified quartz crystal microbalance biosensor for prostate specific antigen detection

Prostate-specific antigen (PSA) screening is vital for the early detection and assessment of prostate cancer treatment efficacy. Integrating nanotechnology into biosensor development allows for targeted biomarker detection. In this study, we present the fabrication of gold nanospikes (AuNS) structures on a quartz crystal microbalance (QCM) using the pulse current electrodeposition (PCD) technique. By varying the duty cycles of PCD, we achieved the desired nanostructure. The characteristics of the AuNS-modified QCM electrode were thoroughly investigated using various micro-structural characterization techniques such as x-ray diffraction (XRD), field emission scanning electron microscope (FESEM), atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). Prior to biomolecule immobilization, each chemical treatment was verified through contact angle and FT-IR analyses. The performance of the developed QCM biosensor was evaluated using PSA at various concentrations. The results revealed that the frequency variation of the QCM biosensor was directly proportional to the PSA concentration. Notably, the AuNS-modified QCM biosensor exhibited the highest frequency shift at a 20 % duty cycle, demonstrating a linear detection range of 0.1–100 ng mL−1 and a limit of detection (LOD) of 24 pg mL−1. The developed QCM biosensor significantly enhances detection efficiency by increasing the number of binding sites for biomolecules through an enlarged surface area. The demonstrated sensitivity of the AuNS-modified QCM biosensor indicates its potential to address the increasing demand for early diagnosis and screening in healthcare systems. This innovative biosensor technology holds promise for improving prostate cancer detection and has broader implications for the development of highly sensitive biosensors for various biomarkers.

MEMS‐Based Ultra‐High Frequency Wireless 10 × 10 QCM Sensor Array for Biochemical Sensing Applications

The quartz crystal microbalance (QCM) biosensor is one of the devices that enables label‐free evaluation of biomolecular reactions. Commercial QCM biosensors have less than 10 channels for detection and are not suitable for the screening. The sensitivity of the QCM biosensor increases as the quartz thickness becomes thinner; however, the limit of thinning is 60–330 μm. In this study, applying micromachining technology, a QCM sensor array chip of 15 mm square that had 100 ultra‐thin quartz resonators (2.5 μm) that were operated wirelessly was developed. And we succeeded in detecting the resonance spectrum through the device evaluation. © 2024 Institute of Electrical Engineers of Japan. Published by Wiley Periodicals LLC.

Malathion Detection Using Molecularly-Imprinted Polymer Quartz Crystal Microbalance Sensor

The extensive use of pesticides can result in overexposure and soil, water, and produce residues. For instance, residues of malathion were found on some vegetables. Molecularly-imprinted polymers (MIP) have been recently developed for sensing of pesticide residues. This study prepared malathion-imprinted polymers via precipitation polymerization and deposited on quartz crystal microbalance (QCM) electrodes. FTIR spectroscopy proved the incorporation and removal of malathion in the matrix of MIP. SEM images revealed that MIP particles are larger than the non-imprinted polymer (NIP) particles due to the incorporation of malathion. Binding experiments were done using standard malathion solutions of 10 to 60 ppm. The MIP-QCM sensor had a greater response than the NIP-QCM sensor. This is due to the specific binding sites in the MIP matrix. On the other hand, the response of NIP-QCM sensor is attributed to the non-specific adsorption sites in its matrix. A sensitivity and detection limit of 1.62 Hz·L/mg and 5.67 ppm, respectively were determined for the MIP-QCM sensor. Lastly, the MIP-QCM sensor is stable and reusable up to three (3) cycles.

Highly Sensitive and Selective Detection of Dimethyl Methyl Phosphonate with Copolymer‐Based QCM Sensors

AbstractIn this work, the volatile organic compounds (VOCs) sensing properties of a quartz crystal microbalance (QCM) transducer coated with six different poly(3‐methylthiophene) (P3MT) copolymerized with polypyrrole (PPy) are investigated. The sensor preparation involves the electrochemical deposition of P3MT, PPy, and P3MT‐co‐PPy on Au‐coated QCM transducers by electrochemical deposition techniques with a three‐electrode cell. The structural properties of the copolymer films are characterized using scanning electron microscopy, and their oxidation/reduction behavior is investigated through cyclic voltammetry. The copolymer‐based QCM sensors exhibit high sensitivity and selectivity to dimethyl methyl phosphonate and benzonitrile, even at low concentrations (<1 ppm) at room temperature. Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich adsorption isotherms are studied to understand the VOCs sensing mechanism machine learning classification algorithms including quadratic discriminant (QD), neural nets, K‐nearest neighbors, linear discriminant, and support vector machines are applied to classify the sensor responses for the 12 different analytes. With the help of machine learning algorithms, tested analytes are successfully classified into their groups. The highest accuracy of 97.34% is achieved using the QD method. The developed sensor, combined with machine learning algorithms, shows promising potential for accurate and reliable detection and classification of VOCs.

Improving the capacitance of hydrogel-based supercapacitors by pre-depositing a zwitterionic 3,4-ethylenedioxythiophene

Polymer hydrogel electrolytes show great advantages in the flexible electronic applications of supercapacitors, but the poor interfaces between electrode and electrolyte are limiting their energy and power densities. In this work, by taking the well-developed pair of poly(vinyl alcohol)/H2SO4 gel electrolyte and graphene film electrode as a prototype, after electrochemically depositing a functional monomer of zwitterionic 3,4-ethylenedioxythiophene (EDOTSB) onto the graphene film electrodes, the specific capacitance of supercapacitors receives a 2.5-fold increase up to 248 mF cm−2 (346 F g−1). By comparing with other pendent groups on EDOT, the decisive role of the zwitterionic group is demonstrated. Attributed to the strong hydration ability of the zwitterion group, the deposition of EDOTSB effectively improves the hydrophilicity of graphene film electrodes, so that the interfacial affinity between the electrode and hydrogel electrolyte is greatly promoted. On the one hand, the EIS measurements certify that the charge-transfer resistance is largely reduced. On the other hand, tests with electrochemical quartz crystal microbalance demonstrate that the interior of graphene film is highly accessible for EDOTSB, thereby enlarging the accessible surface area on the electrode and accelerating the electrolyte infilling process. Furthermore, the general comparison with the liquid electrolyte counterpart is also discussed. This developed method is highly universalizable and can find applications in different electrode/electrolyte supercapacitors and other high-performance flexible energy storage devices.

Effect of pH on the gelling properties of pea protein-pectin dispersions

Phase behavior of protein-polysaccharide mixtures can be controlled by adjusting parameters, such as polymer concentrations and pH. However, the relationships between these interactions and resulting microstructures and textures are not fully understood. The effects of pH (5.5, 7, and 8.5) and low-methoxyl (LM) pectin content (0.5% and 1%) on the rheological properties and microstructures of heat-induced pea protein gels were investigated. At pH 5.5, the addition of LM pectin significantly increased the size of protein aggregates, which is explained by the strong interactions between proteins and LM pectins at that pH; a quartz crystal microbalance revealed the formation of insoluble complexes with reduced solubility. The storage modulus (G′) of pea protein gels at pH 5.5 increased with 0.5% of LM pectin, whereas 1% of LM pectin led to a decreased G′ and the gels water holding capacity. At pHs 7 and 8.5, the addition of LM pectin increased the size of protein aggregates due to the segregative phase separation of negatively charged pea proteins and LM pectins. An increase in G′ with LM pectin concentrations in the gels was also observed at pHs 7 and 8.5. Gel microstructures with phase-separated zones were observed by confocal microscopy. Furthermore, the addition of LM pectin increased the digestibility of pea protein gels prepared at the three pH values under simulated gastrointestinal conditions. Better knowledge of the rheological properties and microstructures of pea protein-LM pectin mixed gels obtained under different pH conditions will allow for optimal use of protein-polysaccharide mixtures in food formulations to attain binary gel products with expected textural and nutritional properties.

Thickness dependent CO2 adsorption of poly(ethyleneimine) thin films for direct air capture

Mesoporous silica impregnated with polyethyleneimine (PEI) has been shown to be a suitable material for the direct air capture (DAC) of CO2. Factors such as CO2 concentration, temperature, and amine loading impact overall capture capacity and amine efficiency by altering diffusional resistance and reaction kinetics. When studied in the impregnated 3-dimensional sorbent material, internal diffusion impacts the evaluation of the reaction kinetics at the air/amine interface. In this work, we designed a novel tandem quartz crystal microbalance with dissipation (QCM-D) and polarization modulation infrared reflective absorption spectroscopy (PM-IRRAS) instrument. CO2 adsorption kinetics of the PEI-based amine layer in a 2-dimensional geometry were studied at a variety of film thicknesses (10 nm to 100 nm), temperatures (25 °C to 80 °C), and CO2 concentrations (5 % and 0.04 % by mole fraction). Total CO2 capture capacity increased with film thickness but decreased amine efficiency, as additional diffusional resistance for thicker films limits access to available amine sites. The capture capacity of thick films (>50 nm) is shown to be limited by amine availability, while capture of thin films (<50 nm) is limited by CO2 availability. A 50 nm PEI film was shown to be optimal for capture of 0.04 % (400 ppm) CO2. The adsorption profiles for these conditions were fitted to pseudo-first order and Avrami fractional order models. The reaction process switches between a diffusion limited reaction to a kinetic limited reaction at 80 °C when using 5 % CO2 and 55 °C when using 0.04 % CO2. These results offer accurate analysis of adsorption of CO2 at the air/amine interface of PEI films which can be used for the design of future sorbent materials.