Quartz Crystal Microbalance Experiments Research Articles

Direct Functionalization of Polysaccharide-Based Xylan Phenyl Carbonate Nanoparticles with Tumor Cell Specific Antibodies.

An efficient and easy-to-use approach is presented for obtaining biocompatible polysaccharide-based nanoparticles (NP) that can act as tumor-specific drug delivery agents. Two antibodies are directly immobilized onto reactive xylan phenyl carbonate (XPC) NP; namely Cetuximab (CTX) that binds to human epidermal growth factor receptor (EGFR) and Atezolizumab (ATZ) that binds to programmed death-ligand 1 (PD-L1). High coupling efficiency (up to 100 %) are achieved without any pre-activation and no aggregation occurs during antibody immobilization. By quartz crystal microbalance experiments with dissipation monitoring (QCM-D), flow cytometry assays, and confocal laser scanning microscopy imaging it is demonstrated that the functionalized XPC-NP specifically bind to cells carrying the corresponding antigens. Moreover, the NP retain the antibody specific bioactivities (growth inhibition for CTX and induction of T-cell cytotoxicity for ATZ).

C60-based Multivalent Glycoporphyrins Inhibit SARS-CoV-2 Specific Interaction with the DC-SIGN Transmembrane Receptor.

Since WHO has declared the COVID-19 outbreak a global pandemic, nearly seven million deaths have been reported. This efficient spread of Severe Acute Respiratory Syndrome Coronavirus-2 (SARS-CoV-2) is facilitated by the ability of the spike glycoprotein to bind multiple cell membrane receptors. Although ACE2 is identified as the main receptor for SARS-CoV-2, other receptors could play a role in viral entry. Among others, C-type lectins such as DC-SIGN are identified as efficient trans-receptor for SARS-CoV-2 infection, so the use of glycomimetics to inhibit the infection through the DC-SIGN blockade is an encouraging approach. In this regard, multivalent nanostructures based on glycosylated [60]fullerenes linked to a central porphyrin scaffold have been designed and tested against DC-SIGN-mediated SARS-CoV-2 infection. First results show an outstanding inhibition of the trans-infection up to 90%. In addition, a deeper understanding of nanostructure-receptor binding is achieved through microscopy techniques, high-resolution NMR experiments, Quartz Crystal Microbalance experiments, and molecular dynamic simulations.

Mucoadhesive pickering nanoemulsions via dynamic covalent chemistry

Hypothesis. Submicron oil droplets stabilized using aldehyde-functionalized nanoparticles should adhere to the primary amine groups present at the surface of sheep nasal mucosal tissue via Schiff base chemistry. Experiments. Well-defined sterically-stabilized diblock copolymer nanoparticles of 20 nm diameter were prepared in the form of concentrated aqueous dispersions via reversible addition-fragmentation chain transfer (RAFT) aqueous emulsion polymerization of 2,2,2-trifluoroethyl methacrylate (TFEMA) using a water-soluble methacrylic precursor bearing cis-diol groups. Some of these hydroxyl-functional nanoparticles were then selectively oxidized using an aqueous solution of sodium periodate to form a second batch of nanoparticles bearing pendent aldehyde groups within the steric stabilizer chains. Subjecting either hydroxyl- or aldehyde-functional nanoparticles to high-shear homogenization with a model oil (squalane) produced oil-in-water Pickering macroemulsions of 20–30 µm diameter. High-pressure microfluidization of such macroemulsions led to formation of the corresponding Pickering nanoemulsions with a mean droplet diameter of around 200 nm. Quartz crystal microbalance (QCM) experiments were used to examine adsorption of both nanoparticles and oil droplets onto a model planar substrate bearing primary amine groups, while a fluorescence microscopy-based mucoadhesion assay was developed to assess adsorption of the oil droplets onto sheep nasal mucosal tissue. Findings. Squalane droplets coated with aldehyde-functional nanoparticles adhered significantly more strongly to sheep nasal mucosal tissue than those coated with the corresponding hydroxyl-functional nanoparticles. This difference was attributed to the formation of surface imine bonds via Schiff base chemistry and was also observed for the two types of nanoparticles alone in QCM studies. Preliminary biocompatibility studies using planaria indicated only mild toxicity for these new mucoadhesive Pickering nanoemulsions, suggesting potential applications for the localized delivery of hydrophobic drugs.

PH-Responsive Cobalt(II)-Coordinated Assembly Containing Quercetin for Antimicrobial Applications.

The development of novel drug delivery systems (DDSs) with promising antibacterial properties is essential for facing the emergency of increasing resistance to antimicrobial agents. The antibacterial features of quercetin and its metal complexes have been broadly investigated. However, several drawbacks affect their activity and effectiveness. In this work, we propose a DDS based on a pH-responsive cobalt(II)-coordinated assembly containing quercetin and polyacrylic acid. This system is suggested to trigger the release of the model drug in a pH-dependent mode by exploiting the localized acidic environment at the bacterial infection sites under anaerobic conditions. The delivery system has been designed by accurately examining the species and the multiple equilibria occurring in solution among the assembly components. The formation of cobalt(II) complexes with quercetin in the absence or presence of the pH-responsive polyacrylic acid was investigated in buffered aqueous solution at pH 7.4 using spectrophotometric (UV-Vis) and calorimetric (ITC) techniques. The determined binding affinities and thermodynamic parameters that resulted are essential for the development of a DDS with improved binding and release capabilities. Furthermore, the affinity of the polymer-cobalt(II) complex toward the model antimicrobial flavonoid was explored at the solid-liquid interface by quartz crystal microbalance (QCM-D) experiments, which provided marked evidence for drug loading and release under pH control.

Surfactant pretreatment as a novel fouling mitigation strategy for membrane distillation

Membrane distillation (MD) has emerged as a promising thermal desalination technology for hypersaline wastewater reclamation. However, the practical implementations of MD face a critical challenge of membrane fouling. Conventional strategy to address membrane fouling is to emphasize the progress in developing composite MD membranes, but these membranes are commercially unavailable. In this study, we introduce a new operation strategy to mitigate fouling by using surfactant pretreatment. We demonstrate that after being pretreated by 0.05 mM Triton X-100 feed solution for 10 min, a commercial polyvinylidene fluoride (PVDF) membrane can exhibit outstanding fouling resistance in MD process. Further, we elucidate the underlying working mechanism using quartz crystal microbalance (QCM) experiments, oil contact angle measurements, and force spectroscopy determinations. Specifically, in the pretreatment process, the amphiphilic surfactant adsorbs onto the hydrophobic membrane, altering the membrane surface to be hydrophilic. During the MD operations, a hydration layer forms on the hydrophilic surface, eliminating the foulant-membrane interaction and thereby achieving fouling mitigation. For effective fouling mitigation, a surfactant exhibiting a moderate hydrophilic-lipophilic balance (HLB) value (e.g., Triton X-100 with an HLB of ∼14) is required. As an easy-to-implement but effective strategy to mitigate membrane fouling, surfactant pretreatment can substantially improve the fouling resistances of commercial hydrophobic membranes, greatly facilitating the practical applications of MD and membrane contactor technologies.

Probing Interfacial Behavior and Antifouling Activity of Adsorbed Copolymers at Solid/Liquid Interfaces.

Polymers containing poly(ethylene glycol) (PEG) units can exhibit excellent antifouling properties, which have been proposed/used for coating of biomedical implants, separation membranes, and structures in marine environments, as well as active ingredients in detergent formulations to avoid soil redepositioning in textile laundry. This study aimed to elucidate the molecular behavior of a copolymer poly(MMA-co-MPEGMA) containing antiadhesive PEG side chains and a backbone of poly(methyl methacrylate), at a buried polymer/solution interface. Polyethylene terephthalate (PET) was used as a substrate to model polyester textile surfaces. Sum frequency generation (SFG) vibrational spectroscopy was applied to examine the interfacial behavior of the copolymer at PET/solution interfaces in situ and in real time. Complementarily, copolymer adsorption on PET and subsequent antiadhesion against protein foulants were probed by quartz-crystal microbalance experiments with dissipation monitoring (QCM-D). Both applied techniques show that poly(MMA-co-MPEGMA) adsorbs significantly to the PET/solution interface at bulk polymer solution concentrations as low as 2 ppm, while saturation of the surface was reached at 20 ppm. The hydrophobic MMA segments provide an anchor for the copolymer to bind onto PET in an ordered way, while the pendant PEG segments are more disordered but contain ordered interfacial water. In the presence of considerable amounts of dissolved surfactants, poly(MMA-co-MPEGMA) could still effectively adsorb on the PET surface and remained stable at the surface upon washing with hot and cold water or surfactant solution. In addition, it was found that adsorbed poly(MMA-co-MPEGMA) provided the PET surface with antiadhesive properties and could prevent protein deposition, highlighting the superior surface affinity and antifouling performance of the copolymer. The results obtained in this work demonstrate that amphiphilic copolymers containing PMMA anchors and PEG side chains can be used in detergent formulations to modify polyester surfaces during laundry and reduce deposition of proteins (and likely also other soils) on the textile.

Bottom-up evolution of perovskite clusters into high-activity rhodium nanoparticles toward alkaline hydrogen evolution

Self-reconstruction has been considered an efficient means to prepare efficient electrocatalysts in various energy transformation process for bond activation and breaking. However, developing nano-sized electrocatalysts through complete in-situ reconstruction with improved activity remains challenging. Herein, we report a bottom-up evolution route of electrochemically reducing Cs3Rh2I9 halide-perovskite clusters on N-doped carbon to prepare ultrafine Rh nanoparticles (~2.2 nm) with large lattice spacings and grain boundaries. Various in-situ and ex-situ characterizations including electrochemical quartz crystal microbalance experiments elucidate the Cs and I extraction and Rh reduction during the electrochemical reduction. These Rh nanoparticles from Cs3Rh2I9 clusters show significantly enhanced mass and area activity toward hydrogen evolution reaction in both alkaline and chlor-alkali electrolyte, superior to liquid-reduced Rh nanoparticles as well as bulk Cs3Rh2I9-derived Rh via top-down electro-reduction transformation. Theoretical calculations demonstrate water activation could be boosted on Cs3Rh2I9 clusters-derived Rh nanoparticles enriched with multiply sites, thus smoothing alkaline hydrogen evolution.

Thermal Atomic Layer Etching of MoS2 Using MoF6 and H2O.

Two-dimensional (2D) layered materials offer unique properties that make them attractive for continued scaling in electronic and optoelectronic device applications. Successful integration of 2D materials into semiconductor manufacturing requires high-volume and high-precision processes for deposition and etching. Several promising large-scale deposition approaches have been reported for a range of 2D materials, but fewer studies have reported removal processes. Thermal atomic layer etching (ALE) is a scalable processing technique that offers precise control over isotropic material removal. In this work, we report a thermal ALE process for molybdenum disulfide (MoS2). We show that MoF6 can be used as a fluorination source, which, when combined with alternating exposures of H2O, etches both amorphous and crystalline MoS2 films deposited by atomic layer deposition. To characterize the ALE process and understand the etching reaction mechanism, in situ quartz crystal microbalance (QCM), Fourier transform infrared (FTIR), and quadrupole mass spectrometry (QMS) experiments were performed. From temperature-dependent in situ QCM experiments, the mass change per cycle was -5.7 ng/cm2 at 150 °C and reached -270.6 ng/cm2 at 300 °C, nearly 50× greater. The temperature dependence followed Arrhenius behavior with an activation energy of 13 ± 1 kcal/mol. At 200 °C, QCM revealed a mass gain following exposure to MoF6 and a net mass loss after exposure to H2O. FTIR revealed the consumption of Mo-O species and formation of Mo-F and MoF x =O species following exposures of MoF6 and the reverse behavior following H2O exposures. QMS measurements, combined with thermodynamic calculations, supported the removal of Mo and S through the formation of volatile MoF2O2 and H2S byproducts. The proposed etching mechanism involves a two-stage oxidation of Mo through the ALE half-reactions. Etch rates of 0.5 Å/cycle for amorphous films and 0.2 Å/cycle for annealed films were measured by ex situ ellipsometry, X-ray reflectivity, and transmission electron microscopy. Precisely etching amorphous films and subsequently annealing them yielded crystalline, few-layer MoS2 thin films. This thermal MoS2 ALE process provides a new mechanism for fluorination-based ALE and offers a low-temperature approach for integrating amorphous and crystalline 2D MoS2 films into high-volume device manufacturing with tight thermal budgets.

Differentiating the effects of hydrophobic interaction and disulfide bond on the myofibrillar protein emulsion gels at the high temperature and the protein interfacial properties

The study presented the effects of modulating the hydrophobic interaction and disulfide bond on the properties of myofibrillar protein (MP) emulsion gels at high temperature (95 °C) and the differentiation on the contribution of non-covalent (hydrophobic interaction) and covalent intermolecular interactions (disulfide bond) to the properties of interfacial protein films were also determined. The hydrophobic interactions among MP were modulated by the addition of octenyl succinic anhydride (OSA), and the disulfide bonds were modulated by the SH/SS exchange reactions mediated by GSH. The results showed that the MP emulsion gel properties at 95 °C were improved by modulating the hydrophobic interaction or disulfide bonds, and the dynamic interfacial adsorption of MP and dissipation quartz crystal microbalance experiments showed the interfacial adsorption pattens of protein were also changed. In addition, the hydrophobic interactions putted emphasis on improving the gel matrix, whereas the disulfide bonds focused on increasing the stiffness of interfacial protein films.

Anodic electrodeposition of continuous metal-organic framework films with robust adhesion by pre-anchored strategy

Anodic electrodeposition of metal-organic framework (MOF) films is driven by the anodic dissolution of a metal substrate. However, the anodic dissolution of the substrate weakens the MOF-substrate adhesion and leads to the detachment of the MOF films, limiting the thickness of the MOF films that can be deposited with this technique. In this work, we propose a strategy to improve the adhesion of MOF films by pre-depositing MOF particles into the substrate as “anchors”. This strategy makes it possible to grow much thicker MOF films by anodic deposition (≥40 μm). Nano-scratch tests show that the MOF films on the substrate with embedded MOF particles have a much higher adhesion strength than those prepared on the non-modified substrates. Electrochemical quartz crystal microbalance (EQCM) experiments indicate that the pre-embedded MOF particles can directly grow during the anodic deposition process, which accounts for the high MOF-substrate adhesion strength. Due to the applicability of the co-deposition of metal and MOF particles, this strategy may expand to the growth of a range of MOF films on different conductive substrates.

Prediction of attachment efficiency using machine learning on a comprehensive database and its validation

Colloidal particles can attach to surfaces during transport, but the attachment depends on particle size, hydrodynamics, solid and water chemistry, and particulate matter. The attachment is quantified in filtration theory by measuring attachment or sticking efficiency (Alpha). A comprehensive Alpha database (2538 records) was built from experiments in the literature and used to develop a machine learning (ML) model to predict Alpha. The training (r-squared: 0.86) was performed using two random forests capable of handling missing data. A holdout dataset was used to validate the training (r-squared: 0.98), and the variable importance was explored for training and validation. Finally, an additional validation dataset was built from quartz crystal microbalance experiments using surface-modified polystyrene, poly (methyl methacrylate), and polyethylene. The experiments were performed in the absence or presence of humic acid. Full database regression (r-squared: 0.90) predicted Alpha for the additional validation with an r-squared of 0.23. Nevertheless, when the original database and the additional validation dataset were combined into a new database, both the training (r-squared: 0.95) and validation (r-squared: 0.70) increased. The developed ML model provides a data-driven prediction of Alpha over a big database and evaluates the significance of 22 input variables.

Nucleation and growth of molybdenum disulfide grown by thermal atomic layer deposition on metal oxides

To enable greater control over thermal atomic layer deposition (ALD) of molybdenum disulfide (MoS2), here we report studies of the reactions of molybdenum hexafluoride (MoF6) and hydrogen sulfide (H2S) with metal oxide substrates from nucleation to few-layer films. In situ quartz crystal microbalance experiments performed at 150, 200, and 250 °C revealed temperature-dependent nucleation behavior of the MoF6 precursor, which is attributed to variations in surface hydroxyl concentration with temperature. In situ Fourier transform infrared spectroscopy coupled with ex situ x-ray photoelectron spectroscopy (XPS) indicated the presence of molybdenum oxide and molybdenum oxyfluoride species during nucleation. Density functional theory calculations additionally support the formation of these species as well as predicted metal oxide to fluoride conversion. Residual gas analysis revealed reaction by-products, and the combined experimental and computational results provided insights into proposed nucleation surface reactions. With additional ALD cycles, Fourier transform infrared spectroscopy indicated steady film growth after ∼13 cycles at 200 °C. XPS revealed that higher deposition temperatures resulted in a higher fraction of MoS2 within the films. Deposition temperature was found to play an important role in film morphology with amorphous films obtained at 200 °C and below, while layered films with vertical platelets were observed at 250 °C. These results provide an improved understanding of MoS2 nucleation, which can guide surface preparation for the deposition of few-layer films and advance MoS2 toward integration into device manufacturing.

Effect of tribologically-induced changes in surface termination of silicon-containing diamond-like carbon coatings on the resistance to biomolecule adsorption

Silicon-containing diamond-like carbon (DLC) is a class of thin-film materials with excellent mechanical properties, high thermal stability, and good tribological performance over a wide range of environmental conditions. While non-alloyed/non-doped DLCs also exhibit good biocompatibility and bioinertness, our understanding of the effect of silicon in DLCs on biomolecules/DLC interactions is still elusive. Here, we evaluated the structural, mechanical, and tribological properties of Si-containing DLC coatings with silicon content fraction of 11% and 16%. Tribological tests, performed by sliding a stainless steel pin on the coatings in water, indicated a low friction response (steady-state coefficient of friction <0.11), while quartz crystal microbalance experiments indicated no adsorption of a model biomolecule, namely adenosine triphosphate (ATP), on Si-containing DLCs. Near-edge X-ray absorption fine structure spectromicroscopy analyses performed after tribological experiments provided evidence for an increase in the fraction of silanol surface terminal groups formed in the worn region upon sliding in water without any significant sp3-to-sp2 rehybridization of carbon atoms. The fraction of surface hydroxyl groups in the worn region increases with the silicon content in Si-containing DLC, which leads to a decrease in friction. This tribologically-induced change in surface termination did not lead to the adsorption of ATP upon incubation of tribotested samples in ATP solutions for several hours. These findings open the path for the use of Si-containing DLC in applications requiring good tribological properties in aqueous solution and an excellent resistance to biomolecule surface adsorption that is maintained even after tribologically-induced variations in surface termination.

Evaluating Corrosion Behaviour of Copper Under Deliquescent Drying/Wetting Cycles in Humid Air Condition

Most nuclear safety agencies around the world agree that deep geological repositories (DGRs) constructed hundreds of meters below ground in stable host rock formations are viable solutions to safely isolate used nuclear fuel. In Canada, the DGR design involves storing used nuclear fuel in sealed copper coated used fuel containers (UFC) surrounded by highly compacted bentonite blocks (HCB) ~500 m underground. Shortly after emplacement, heat generated by radioactive decay of the used fuel will warm the UFC and its surroundings, desiccating the HCB and decreasing moisture on the container surface. As water vapour is driven from the UFC surface, the presence of minor amounts of dissolved salts may cause droplet formation prior to complete evaporation, during which deposits of salts may be left behind on the UFC. Later, as conditions evolve and the relative humidity increases and the temperature decreases, condensation of liquid water on the UFC surfaces will produce droplets again, due to the deliquescence of minor salt deposits. In either the wetting or the drying scenario, secondary spreading and spatial separation of anodic and cathodic reactions and consequent non-uniform corrosion could be possible, due to the droplet geometry.To investigate this scenario, the quartz crystal microbalance (QCM) technique is being used. The QCM initially consists of a quartz plate, covered by gold electrodes on both sides where a layer of copper is deposited on the crystal by using magnetron sputtering. In this technique, the change in the resonance frequency of a vibrating quartz crystal is correlated to its mass change due to the corrosion process. To investigate the effect of salts and their deliquescence behaviours, different salts (NaCl, CaCl2, and MgCl2) and CR10-E simulated groundwater were loaded on the copper surface using an inkjet printer, and then corrosion tests were performed at different temperatures and relative humidity (RH) values. In parallel, a set of long-term vapour-phase corrosion tests was performed on wrought and cold-sprayed copper coupons at 75 °C and different RH values. As part of the post-experiment analysis, the corrosion products were analyzed using a suite of surface analysis techniques, including optical microscopy, Raman spectroscopy, and scanning electron microscopy (SEM).The results from QCM experiments at RH values below salts deliquescence point showed a low mass change that could correlate with less corrosion in comparison to the experiments at RH values above salts deliquescence point. It’s worth noting that even at RH values below the deliquescence point of the salts, a trace of corrosion was observed which could be indicative of the presence of monolayers of water on the surface. The results obtained from NaCl and CR10-E exposure conditions showed higher mass change and therefore higher corrosion in comparison to CaCl2 and MgCl2 salts. As for the long-term vapour-phase corrosion tests, Raman spectroscopy confirmed the presence of CuO and Cu2O on the surface as corrosion products. Further surface characterizations and mass loss measurements are underway to determine the extent of corrosion on the copper coupons.

Affinity Recognition Based Gravimetric Nanosensor for Equilin Detection

The estrogenic hormones that are widely used in postmenopausal hormone supplements for women contaminate natural water resources. Equilin (Equ) is one of the estrogenic hormones that have a maximum contaminant level of 0.35 µg/L in the chemical pollutants list. In this study, estrogenic hormones were precisely detected in a short time by affinity-recognition-based interactions in Quartz Crystal Microbalance (QCM) sensors. The QCM sensors were modified with 11-mercaptoundecanoic acid forming a self-assembled monolayer and with amino acids, namely tyrosine, tryptophan and phenylalanine. The affinity interactions between Equ and amino acids were studied using docking tools and confirmed by QCM experiments. The LODs of Equ were obtained as 4.59, 5.05 and 6.30 ng/L for tyrosine-, tryptophan- and phenylalanine-modified QCM nanosensors, respectively, with linear dynamic detection in the range of 25–500 nM. In terms of the LOD, selectivity and sensitivity calculations, the tyrosine-modified QCM nanosensor was found to have the highest performance for Equ detection compared to the tryptophan- and phenylalanine-modified ones.

Laser-Fabricated 2D Molybdenum Disulfide Electronic Sensor Arrays for Rapid, Low-Cost, Ultrasensitive Detection of Influenza A and SARS-Cov-2.

Multiplex electronic antigen sensors for detection of SARS‐Cov‐2 spike glycoproteins and hemagglutinin from influenza A are fabricated using scalable processes for straightforward transition to economical mass‐production. The sensors utilize the sensitivity and surface chemistry of a 2D MoS2 transducer for attachment of antibody fragments in a conformation favorable for antigen binding with no need for additional linker molecules. To make the devices, ultra‐thin layers (3 nm) of amorphous MoS2 are sputtered over pre‐patterned metal electrical contacts on a glass chip at room temperature. The amorphous MoS2 is then laser annealed to create an array of semiconducting 2H‐MoS2 transducer regions between metal contacts. The semiconducting crystalline MoS2 region is functionalized with monoclonal antibody fragments complementary to either SARS‐CoV‐2 S1 spike protein or influenza A hemagglutinin. Quartz crystal microbalance experiments indicate strong binding and maintenance of antigen avidity for antibody fragments bound to MoS2. Electrical resistance measurements of sensors exposed to antigen concentrations ranging from 2–20 000 pg mL−1 reveal selective responses. Sensor architecture is adjusted to produce an array of sensors on a single chip suited for detection of analyte concentrations spanning six orders of magnitude from pg mL−1 to µg mL−1.

Cholesterol Hinders the Passive Uptake of Amphiphilic Nanoparticles into Fluid Lipid Membranes.

Plasma membranes represent pharmacokinetic barriers for the passive transport of site-specific drugs within cells. When engineered nanoparticles (NPs) are considered as transmembrane drug carriers, the plasma membrane composition can affect passive NP internalization in many ways. Among these, cholesterol-regulated membrane fluidity is probably one of the most biologically relevant. Herein, we consider small (2–5 nm in core diameter) amphiphilic gold NPs capable of spontaneously and nondisruptively entering the lipid bilayer of plasma membranes. We study their incorporation into model 1,2-dioleoyl-sn-glycero-3-phosphocholine membranes with increasing cholesterol content. We combine dissipative quartz crystal microbalance experiments, atomic force microscopy, and molecular dynamics simulations to show that membrane cholesterol, at biologically relevant concentrations, hinders the molecular mechanism for passive NP penetration within fluid bilayers, resulting in a dramatic reduction in the amount of NP incorporated.

Controlling the Carbon-Bio Interface via Glycan Functional Adlayers for Applications in Microbial Fuel Cell Bioanodes.

Surface modification of electrodes with glycans was investigated as a strategy for modulating the development of electrocatalytic biofilms for microbial fuel cell applications. Covalent attachment of phenyl-mannoside and phenyl-lactoside adlayers on graphite rod electrodes was achieved via electrochemically assisted grafting of aryldiazonium cations from solution. To test the effects of the specific bio-functionalities, modified and unmodified graphite rods were used as anodes in two-chamber microbial fuel cell devices. Devices were set up with wastewater as inoculum and acetate as nutrient and their performance, in terms of output potential (open circuit and 1 kΩ load) and peak power output, was monitored over two months. The presence of glycans was found to lead to significant differences in startup times and peak power outputs. Lactosides were found to inhibit the development of biofilms when compared to bare graphite. Mannosides were found, instead, to promote exoelectrogenic biofilm adhesion and anode colonization, a finding that is supported by quartz crystal microbalance experiments in inoculum media. These differences were observed despite both adlayers possessing thickness in the nm range and similar hydrophilic character. This suggests that specific glycan-mediated bioaffinity interactions can be leveraged to direct the development of biotic electrocatalysts in bioelectrochemical systems and microbial fuel cell devices.

Electroless Platinum Deposition Using Co3+/Co2+ Redox Couple as a Reducing Agent.

In the present work, the kinetics of electroless deposition of Pt, using a cobalt ion redox system (Co3+/Co2+) as a reducing agent, has been investigated. The deposition rate of Pt depends on the pH, concentration of reactants, and temperature. The deaeration and bubbling of the plating solution with argon play an essential role. It was found that 0.11 mg cm−2 of Pt films could be deposited on the surface of a roughed glass sheet in one hour without replenishing the solution. Additional data have been obtained on the grounds of electrochemical quartz crystal microbalance experiments. The bubbling (agitation) of the electroless Pt plating solution with argon during the deposition of Pt results in a higher deposition rate and is ca. 3 µg cm−2 min−1. The Pt deposition rate is far less, and is as low as 0.14 µg cm−2 min−1 when the electroless Pt plating solution is not bubbled with argon during the deposition of Pt.

Model Surfaces for Paper Fibers Prepared from Carboxymethyl Cellulose and Polycations.

For tailored functionalization of cellulose based papers, the interaction between paper fibers and functional additives must be understood. Planar cellulose surfaces represent a suitable model system for studying the binding of additives. In this work, polyelectrolyte multilayers (PEMs) are prepared by alternating dip-coating of the negatively charged cellulose derivate carboxymethyl cellulose and a polycation, either polydiallyldimethylammonium chloride (PDADMAC) or chitosan (CHI). The parameters varied during PEM formation are the concentrations (0.1–5 g/L) and pH (pH = 2–6) of the dipping solutions. Both PEM systems grow exponentially, revealing a high mobility of the polyelectrolytes (PEs). The pH-tunable charge density leads to PEMs with different surface topographies. Quartz crystal microbalance experiments with dissipation monitoring (QCM-D) reveal the pronounced viscoelastic properties of the PEMs. Ellipsometry and atomic force microscopy (AFM) measurements show that the strong and highly charged polycation PDADMAC leads to the formation of smooth PEMs. The weak polycation CHI forms cellulose model surfaces with higher film thicknesses and a tunable roughness. Both PEM systems exhibit a high water uptake when exposed to a humid environment, with the PDADMAC/carboxymethyl cellulose (CMC) PEMs resulting in a water uptake up to 60% and CHI/CMC up to 20%. The resulting PEMs are water-stable, but water swellable model surfaces with a controllable roughness and topography.