Ionic Substrates Research Articles

The Additive to Mass Manufacturing Process of Mixed Potential Electrochemical Sensors

Additive manufacturing allows for quick turn around and low cost of production of small numbers of parts. These attributes lend the technology to prototype development, where design changes are many and production numbers are low [1]. Once design parameters have been nailed down, additive manufacturing’s low throughput and poor reproducibility limit application to high volume production.Here, we discuss the implementation of direct-write extrusion of ceramic pastes and metal inks for prototype manufacturing of mixed potential electrochemical sensors and the transition to tape casting and screen printing for high volume production. Throughout the prototyping phase, direct write extrusion enabled quick and easy production of low numbers of parts, enabling various changes in sensor design and material to improve sensor performance. Sensor design evolved from a disk shape (Fig. 1 a) to a stick with integrated heater (Fig. 1 b, c). Direct write extrusion of substrate enabled quick testing of various stabilized zirconia ceramics to improve the sensitivity of the device [2]. Limitations of additive manufacturing became apparent when attempting to integrate the heater into the device, the inconsistent linewidths led to areas of high resistance and hot spots (Fig. 1 c). Tape-casting and screen printing of the devices was adopted for three reasons, first, to improve line fidelity, which is vitally important when printing small electrodes as well as heater traces (Fig. 1 d), second, to further decrease conductivity of substrate by laminating multiple layers of different ceramic materials, and finally to increase manufacturing throughput (Fig. 1 d, e).This work was supported by US Department of Energy Award DE-FE0031864References[1] T. D. Ngo, A. Kashani, G. Imbalzano, K. T. Q. Nguyen, and D. Hui, “Additive manufacturing (3D printing): A review of materials, methods, applications and challenges,” Compos. Part B Eng., vol. 143, pp. 172–196, Jun. 2018, doi: 10.1016/j.compositesb.2018.02.012.[2] S. Halley, K. Ramaiyan, F. Garzon, and L. Tsui, “Massive enhancement in sensitivity of mixed potential sensors towards methane and natural gas through magnesia stabilized zirconia low ionic conductivity substrate,” Sens. Actuators B Chem., vol. 392, p. 134031, Oct. 2023, doi: 10.1016/j.snb.2023.134031. Figure 1

In Silico TRials guide optimal stratification of ATrIal FIbrillation patients to Catheter Ablation and pharmacological medicaTION: the i-STRATIFICATION study.

Patients with persistent atrial fibrillation (AF) experience 50% recurrence despite pulmonary vein isolation (PVI), and no consensus is established for secondary treatments. The aim of our i-STRATIFICATION study is to provide evidence for stratifying patients with AF recurrence after PVI to optimal pharmacological and ablation therapies, through in silico trials. A cohort of 800 virtual patients, with variability in atrial anatomy, electrophysiology, and tissue structure (low-voltage areas, LVAs), was developed and validated against clinical data from ionic currents to electrocardiogram. Virtual patients presenting AF post-PVI underwent 12 secondary treatments. Sustained AF developed in 522 virtual patients after PVI. Second ablation procedures involving left atrial ablation alone showed 55% efficacy, only succeeding in the small right atria (<60 mL). When additional cavo-tricuspid isthmus ablation was considered, Marshall-PLAN sufficed (66% efficacy) for the small left atria (<90 mL). For the bigger left atria, a more aggressive ablation approach was required, such as anterior mitral line (75% efficacy) or posterior wall isolation plus mitral isthmus ablation (77% efficacy). Virtual patients with LVAs greatly benefited from LVA ablation in the left and right atria (100% efficacy). Conversely, in the absence of LVAs, synergistic ablation and pharmacotherapy could terminate AF. In the absence of ablation, the patient's ionic current substrate modulated the response to antiarrhythmic drugs, being the inward currents critical for optimal stratification to amiodarone or vernakalant. In silico trials identify optimal strategies for AF treatment based on virtual patient characteristics, evidencing the power of human modelling and simulation as a clinical assisting tool.

Hydrolysis of ionic liquid–treated substrate with an Iocasia fonsfrigidae strain SP3-1 endoglucanase

Recently, we reported the discovery of a novel endoglucanase of the glycoside hydrolase family 12 (GH12), designated IfCelS12A, from the haloalkaliphilic anaerobic bacterium Iocasia fonsfrigidae strain SP3-1, which was isolated from a hypersaline pond in the Samut Sakhon province of Thailand (ca. 2017). IfCelS12A exhibits high substrate specificity on carboxymethyl cellulose and amorphous cellulose but low substrate specificity on b-1,3;1,4-glucan. Unlike some endoglucanases of the GH12 family, IfCelS12A does not exhibit hydrolytic activity on crystalline cellulose (i.e., Avicel™). High-Pressure Liquid Chromatography (HPLC) and Thin Layer Chromatography (TLC) analyses of products resulting from IfCelS12-mediated hydrolysis indicate mode of action for this enzyme. Notably, IfCelS12A preferentially hydrolyzes cellotetraoses, cellopentaoses, and cellohexaoses with negligible activity on cellobiose or cellotriose. Kinetic analysis with cellopentaose and barely b-d-glucan as cellulosic substrates were conducted. On cellopentaose, IfCelS12A demonstrates a 16-fold increase in activity (KM = 0.27 mM; kcat = 0.36 s−1; kcat/KM = 1.34 mM−1 s−1) compared to the enzymatic hydrolysis of barley b-d-glucan (KM: 0.04 mM, kcat: 0.51 s−1, kcat/KM = 0.08 mM−1 s−1). Moreover, IfCelS12A enzymatic efficacy is stable in hypersaline sodium chlorids (NaCl) solutions (up to 10% NaCl). Specifically, IfCel12A retains notable activity after 24 h at 2M NaCl (10% saline solution). IfCelS12A used as a cocktail component with other cellulolytic enzymes and in conjunction with mobile sequestration platform technology offers additional options for deconstruction of ionic liquid–pretreated cellulosic feedstock.Key points• IfCelS12A from an anaerobic alkaliphile Iocasia fronsfrigidae shows salt tolerance• IfCelS12A in cocktails with other enzymes efficiently degrades cellulosic biomass• IfCelS12A used with mobile enzyme sequestration platforms enhances hydrolysis

Evaluation of growth adaptation of Cinnamomum camphora seedlings in ionic rare earth tailings environment

The root system is an important organ for nutrient uptake and biomass accumulation in plants, while biomass allocation directly affects essential oils content, which plays an essential role in plant growth and development and resistance to adverse environmental conditions. This study was undertaken to investigate the differences and correlation of biomass allocation, root traits and essential oil content (EOC), as well as the adaptations of camphor tree with different chemical types to the ionic rare earth tailing sand habitats. Data from 1-year old cutting seedlings of C. camphora showed that the biomass of C. camphora cuttings was mainly distributed in root system, with the ratio of root biomass 49.9–72.13% and the ratio of root to canopy 1.00–2.64. The total biomass was significantly positively correlated with root length (RL), root surface area (RSA) and dry weight of fine roots (diameter ≤ 2 mm) (P < 0.05). Root biomass and leaf biomass were negatively and positively with specific root length (SRL) and specific root surface area (SRSA), respectively. Leaf biomass presented a positive effect on EOC (P < 0.05), with the correlation coefficient of 0.808. The suitability sort of these camphor trees was as follows: C. camphora β-linalool, C. camphora α-linaloolII, C. camphora α-linaloolI being better adapted to the ionic rare earth tailings substrate, C. camphora citral being the next, and C. porrectum β-linalool and C. camphora borneol being the least adaptive. EOC played a positive role in the adaptation of C. camphora (R2 = 0.6099, P < 0.05). Therefore camphor tree with linalool type is the appropriate choice in the ecological restoration of ionic rare earth tailings. The study could provide scientific recommendations for the ecological restoration of ionic rare earth tailings area combined with industrial development.

Stretchable and transparent alginate ionic gel film for multifunctional sensors and devices

Flexible and stretchable substrates based on pure natural polymers have attracted widespread attention for next-generation “green” electronics. However, fabrication of stretchable and “green” electronic sensors with integrated high stretchability, optical transmittance and good conductivity still remains tremendous challenges. Herein, alginate ionic gel films (AIGFs) with integrated high stretchability (tensile strength of 4.13 MPa and 191.1 % fracture strain) and excellent transparent properties (transparency of ∼92 %) are achieved by the glycerol inducing physical crosslinking and CaCl2 initiating ionic crosslinking, a simple soaking and drying strategy. The obtained gel films not only exhibit good ionic conductivity, but also high reliability, wide-range sensing, and multiple sensitivity to external stimulus. More importantly, these ionic conductive gel films as green substrates are successfully utilized for construction of flexible and patterned optoelectronic devices. This promising strategy will open up new powerful routes to construct highly stretchable, transparent, and ionic conductive substrates for multifunctional sensors and devices.

Polaron Mass of Carriers in a Thin Film on Ionic Substrates

Polaron Mass of Carriers in a Thin Film on Ionic Substrates

Compounds Derived from 9,9‐Dialkylfluorenes: Syntheses, Crystal Structures and Initial Binding Studies (Part II)

AbstractNew representatives of 2,4,7‐trisubstituted 9,9‐dialkyl‐9H‐fluorenes were prepared and used for crystallographic investigations as well as initial binding studies towards metal ions and carbohydrates. The binding studies, which included 1H NMR spectroscopic titrations and fluorescence measurements, demonstrated the ability of the tested fluorene‐based compounds to act as complexing agents for ionic and neutral substrates. Depending on the nature of the subunits of the fluorene derivatives, “turn on” or “turn off” fluorescent chemosensors can be developed. Compounds composed of 4,6‐dimethylpyridin‐2‐yl‐aminomethyl moieties have the potential to be used as sensitive “turn‐on” chemosensors for some metal ions.

Polaron effects created by interface phonons in thin film on ionic substrates

The effective parameter of the electron-phonon interaction in a semiconductor film on ionic substrates has been determined. It is shown that interface phonons “transfer” the polarization of the medium from the substrate to the film. As a result, the polaron binding energy and the effective mass of carriers in the same film on different substrates can vary by tens or even hundreds of percent. Conditions for the realization of strong interaction for various films are found.

Polaron Effects Induced by Interface Phonons in Thin Films on Ionic Substrates

Polaron Effects Induced by Interface Phonons in Thin Films on Ionic Substrates

Massive enhancement in sensitivity of mixed potential sensors towards methane and natural gas through magnesia stabilized zirconia low ionic conductivity substrate

Monitoring of methane leaks from natural gas (NG) sources during production and transport is vital to combating the threat of greenhouse gases to the global climate. An additive manufacturing route was developed for the printing of a CTE matched, low reactivity and low ionic conductivity magnesia stabilized zirconia (MSZ) substrate for production of a four-electrode (indium tin oxide, lanthanum strontium chromite, and Au sensing electrodes measured against a Pt negative electrode) same-side planar mixed potential electrochemical sensor (MPES) with porous 3 mol% YSZ as electrolyte. The MSZ substrate based MPES achieves a 40 ppm limit of detection for methane in a simulated natural gas mix. Additionally, a 20 times enhanced response in the ITO vs. Pt signal over sensors using yttria-stabilized zirconia (YSZ) substrates at 100 ppm CH4 in simulated natural gas is observed. This research illustrates the importance of a CTE matched, low reactivity, low conductivity substrate for optimal performance of same-side planar MPES devices for NG leak detection while allowing for application of high temperature co-fired ceramic technologies.

Characterization of Guaiacol Peroxidase Enzyme from Carambola Fruit

Carambola is a fruit grown in tropical and subtropical regions of the world. Natural antioxidants including vitamin C, carotenoids, and certain phenolic substances are abundant in carambola fruit. As antioxidants support health by acting as nutraceutical and functional food additives, they help preserve food by preventing oxidation processes. The oxidation of various organic or inorganic substrates by hydrogen peroxide or organic peroxides as terminal oxidants is a process in which peroxidase, which is abundantly present in fruits and vegetables, participates. In this study, guaiacol peroxidase enzyme from carambola fruit was partially purified and characterized. Purification procedure made up the homogenate preparation, ammonium sulfate precipitation, and dialysis. After purification, optimum ionic strength, pH and substrate concentration were investigated. These values were determined as 200 mM Tris, pH: 7.5, 7.5 mM H2O2 and 15 mM guaiacol for carambola fruit guaiacol peroxidase enzyme, respectively.

Purification and Characterization of Glutathione Reductase Enzyme from Arum Maculatum Leaf

Arum species grow in temperate and Mediterranean climates and have been used for hundreds of years for food and medicinal purposes, although they are highly toxic if not cooked using proper techniques. Glutathione reductase (GR) is a member of the pyridine nucleotide disulfide oxidoreductase family of flavoenzymes that catalyzes the reduction of glutathione disulfide (GSSG) to reduced GSH using NADPH or NADH. In this study, GR enzyme was characterized by partial purification processes including homogenate preparation, ammonium sulfate precipitation and dialysis from the leaf of Arum maculatum plant. The highest enzyme activity was found at 40-60% saturation range. Optimum ionic strength, pH and substrate concentration were investigated for GR enzyme from A. maculatum leaf. As a result of the study, these values were found to be 150 mM potassium phosphate buffer, pH 7.00, and 0.18 mM, respectively. The GR enzyme was partially purified from the leaf of the A. maculatum with a specific activity of 1.640 EU mg-1 in 34.9% yield, 1.108-fold. This study is the first study in terms of purification and characterization of GR enzyme from A. maculatum leaf.

Characterization of Catalase Enzyme from Leaf Tissue of Aronia (Aronia melanocarpa) Plant

Aronia is among the most antioxidant containing plants which is found commonly around the world. Aronia cultivation started in Turkey for the first time in 2012 at the Atatürk Central Research Institute of Garden Cultures, and a plantation was constructed in the experimental area. Since antioxidants help to preserve food by blocking oxidation processes and contributing to the health promotion provided by numerous dietary supplements, nutraceutical and functional food additives, antioxidant capacity of these plants should be well characterized. To assess and evaluate the antioxidant content of foods and plant products, many approaches are utilized. In this study, catalase (CAT) enzyme was partially purified from aronia plant leaf tissue and characterization was carried out. Purification process consisted of homogenate preparation, ammonium sulfate precipitation and dialysis. The optimal ionic strength, pH, substrate concentration and enzyme quantity were examined. These values were found to be 300 mM Tris, pH:8.0, 12 mM H2O2 and 75 μl, respectively, for the catalase enzyme of the Aronia plant leaf tissue. This study is the first in the literature dealing with the characterization of antioxidant enzyme from Aronia plant.

Tracing the transition from covalent to non-covalent functionalization of pyrene through C-, N-, and O-based ionic and radical substrates using quantum mechanical calculations.

Pyrene is one of the widely investigated aromatic hydrocarbons given its unique optical and electronic properties. Modulating inherent characteristics of pyrene via covalent or non-covalent functionalization has been attractive for a wide variety of advanced biomedical and other device applications. In this study, we have reported the functionalization of pyrene via C, N, and O based ionic and radical substrates, and emphasized the transition of covalent to non-covalent functionalization through making the modulation in the substrate. As expected, strong interactions were observed for cationic substrates, however, anionic substrates also exhibited a competitive binding strength. For instance, methyl and phenyl substituted CH3 complexes exhibited IEs in the range of -17 kcal mol-1 to -127 kcal mol-1 and -14 kcal mol-1 to -95 kcal mol-1 and for cationic and anionic substrates, respectively. The analysis of topological parameters showed that un-substituted cationic, anionic, and radical substrates interact with pyrene via covalent interactions, and further become non-covalent upon methylation and phenylation of the substrates. In cationic complexes, the polarisation component is observed to be dominating the interactions, whereas highly competitive contributions from polarization and exchange components were observed in anionic and radical complexes. The contribution of the dispersion component increases with an increase in the degree of methylation and phenylation of the substrate, and starts dominating once the interactions become non-covalent in nature.

The design of protozoan phosphoribosyltransferase inhibitors containing non-charged phosphate mimic residues

Phosphate groups play essential roles in biological processes, including retention inside biological membranes. Phosphodiesters link nucleic acids, and the reversible transfer of phosphate groups is essential in energy metabolism and cell-signalling processes. Phosphorylated metabolic intermediates are known targets for metabolic and disease-related disorders, and the enzymes involved in these pathways recognize phosphate groups in their catalytic sites. Therapeutics that target these enzymes can require charged (ionic) entities to capture the binding energy of ionic substrates. Such compounds are not cell-permeable and require pro-drug strategies for efficacy as therapeutics. Protozoan parasites such as Plasmodium and Trypanosoma spp. are unable to synthesise purines de novo and rely on the salvage of purines from the host cell to synthesise free purine bases. Purine phosphoribosyltransfereases (PPRTases) play a crucial role for purine salvage and are potential target for drug development. Here we present attempts to design inhibitors of PPRTases that are non-ionic and show affinity for the nucleotide 5′-phosphate binding site. Inhibitor design was based on known potent ionic inhibitors, reported phosphate mimics and computational modelling studies.

Ultrafast Terahertz Self-Induced Absorption and Phase Modulation on a Graphene-Based Thin Film Absorber

Interaction of intense terahertz (THz) waves with graphene based modulation devices holds great potential for the optoelectronic applications of the future. Here, we present a thin film graphene-based THz perfect absorbing device whose absorption and phase characteristics can be modulated through THz self-actions in the subps time scale. The device consists of a single-layer graphene placed on an ionic liquid substrate, back-plated by a metallic back-reflector, with the graphene doping level mediated through electrostatic gating. We experimentally record an absorption modulation of more than 3 orders of magnitude from the initial perfect absorption state, when the device is illuminated with THz field strengths in the range of 102 to 654 kV/cm. Furthermore, an absolute phase modulation of 130° is recorded. Detailed theoretical analysis indicates that the origin of the THz nonlinear response is the THz-induced heating of the graphene’s carriers that leads to a reduction of its conductivity and, consequently, to reduced absorption of the THz radiation. Our analysis also maps the temporal dynamics of the THz-induced temperature elevation of the graphene’s carriers, illustrating the ultrafast, subps nature of the overall process. These results can find applications in future dynamically controlled flat optics and spatiotemporal shaping of intense THz electric fields.

Activation Modes in Asymmetric Anion-Binding Catalysis

AbstractOver the past two decades, enantioselective anion-binding catalysis has emerged as a powerful strategy for the induction of chirality in organic transformations. The stereoselectivity is achieved in a range of different reactions by using non-covalent interactions between a chiral catalyst and an ionic substrate or intermediate, and subsequent formation of a chiral contact ion pair upon anion binding. This strategy offers vast possibilities in catalysis and the constant development of new reactions has led to various substrate activation approaches. This review provides an overview on the different activation modes in asymmetric anion-binding catalysis by looking at representative examples and recent advances made in this field.1 Introduction2 Electrophile Activation by Single Anion-Binding Catalysis2.1 Prior In Situ Charged Electrophiles2.2 Neutral Electrophile Activation via Anion Abstraction2.2.1 Anion Abstraction via an SN1 Mechanism2.2.2 Anion Abstraction via an SN2 Mechanism3 Nucleophile Activation and Delivery4 Bifunctional and Cooperative Co-catalysis Strategies4.1 Amine Groups for Bifunctional and Cooperative Catalysis4.2 Brønsted Acid Co-catalysis4.3 Lewis Acid Co-catalysis4.4 Lewis Base Co-catalysis4.5 Nucleophilic Co-catalysis for Activation of Electrophiles4.6 Cooperative Metal and Anion-Binding Catalysis4.7 Combination of Photoredox and Anion-Binding Catalysis5 Anion-π Catalysis6 Conclusion

Platinum-Based Nanoparticle Fuel Cell Catalysts Synthesized By Sputtering Onto Liquid Substrates

The quest of finding cheaper and better fuel cell catalyst materials has been long ongoing and remains a crucial step in making fuel cells a commercially viable technology. Platinum (Pt) is still the conventional catalyst used in proton exchange membrane (PEM) fuel cells, however, with slow cathode kinetics and high material cost. Platinum-rare earth (RE) and lanthanide alloys have been found to greatly enhance the catalytic activity towards the oxygen reduction reaction (ORR).1 Increases in ORR activity of up to one order of magnitude compared to pure platinum has been observed for these alloys, but high oxygen affinity of the RE alloying agents considerably complicates their synthesis. Sputter deposition into low vapor pressure liquid substrates, such as ionic liquids and certain polymers enables fabrication of clean nanoparticles, without the presence of air and other contaminates, making it a potential technique for Pt-RE nanoparticle synthesis.Here, we will present our recent work on magnetron sputtering of Pt 2 and Pt-alloys into different liquid substrates, including polyethylene glycol and three imidazolium-based ionic liquids. We have investigated the influence of substrate temperature on Pt nanoparticle growth during sputtering, and in post-sputtering heat treatment.2 We show that whilst substrate temperature influences the Pt nanoparticle size, the effect is not as great as for other materials. Better understanding the growth processes of Pt nanoparticles sputtered into liquids is an important step towards tunable sizes and catalytic activities of Pt-RE nanocatalysts. Escudero-Escribano, María, et al. "Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction." Science 352.6281 (2016): 73-76.Brown, Rosemary, et al. "Plasma-Induced Heating Effects on Platinum Nanoparticle Size During Sputter Deposition Synthesis in Polymer and Ionic Liquid Substrates." Langmuir 37.29 (2021): 8821-8828.

Foldable and Recyclable Iontronic Cellulose Nanopaper for Low‐Power Paper Electronics

AbstractAn increase in the demand for the next generation of “Internet‐of‐Things” (IoT) has motivated efforts to develop flexible and affordable smart electronic systems, in line with sustainable development and carbon neutrality. Cellulose holds the potential to fulfil such demands as a low‐cost green material due to its abundant and renewable nature and tunable properties. Here, a cellulose‐based ionic conductive substrate compatible with printing techniques that combines the mechanical robustness, thermal resistance and surface smoothness of cellulose nanofibrils nanopaper with the high capacitance of a regenerated cellulose hydrogel electrolyte, is reported. Fully screen‐printed electrolyte‐gated transistors and universal logic gates are demonstrated using the engineered ionic conductive nanopaper and zinc oxide nanoplates as the semiconductor layer. The devices exhibit low‐voltage operation (&lt;3 V), and remarkable mechanical endurance under outward folding due to the combination of the robustness of the nanopaper and the compliance of the semiconductor layer provided by the ZnO nanoplates. The printed devices and the ion‐conductive nanopaper can be efficiently recycled to fabricate new devices, which is compatible with the circular economy concept.

Transmembrane transport characterization across ionic redox transistors using surface-tracked scanning ion conductance microscopy

A fundamental understanding of ion transport at the nanoscale is critical to the development of efficient chemical separation membranes, catalysts, ionic/bio-inspired materials, and its scale up into multi-functional ionic devices. Electrochemical imaging using scanning probe microscopy hardware has provided a method to visualize and understand processes that occur at the surface of ionic active materials. The suite of scanning probe microscopy techniques developed over the last few years are limited to imaging surface-level phenomena and have not been applied to investigate transmembrane properties of synthetic and natural membranes with high spatial and temporal resolution. In this article, we demonstrate the application our recently developed ‘surface-tracked scanning ion conductance microscopy’ technique to characterize voltage-regulated ion transport in an ionic redox transistor. The ionic redox transistor exhibits controlled transmembrane ion transport as a function of its electrochemical redox state. The technique presented in this article uses shear force measured between the nanopipette and ionic substrate to image topography of the porous substrate and simultaneously characterize topography-correlated transmembrane transport through the ionic redox transistor. The transmembrane conductance measured across an array of pores within the ionic redox transistor varies from 0.004 μS/cm (OFF state) to 0.015 μS/cm (ON state). We anticipate that the spatial correlation of transmembrane ion transport in the ionic redox transistor would result in a scale up into smart membrane separators for energy storage, neuromorphic circuits, and desalination membranes.