Variation Of Ionic Strength Research Articles

Kinetic Study of Oxidation of Thiophene-2-Carbaldehyde by Imidazolium Dichromate Promoted By 1, 10-Phenanthroline

Kinetic study of oxidation of Thiophene-2-carbaldehyde by Imidazolium dichromate in aqueous acetic acid medium using 1,10-phenanthroline have been studied. In the absence of mineral acids, the oxidation kinetics of Thiophene-2-carbaldehyde acid by Imidazolium dichromate shows a first-order dependence on Imidazolium dichromate and fractional order on Thiophene-2-carbaldehyde. The variation of ionic strength, H+ and reaction product have in significant effect on reaction rate. Activation parameters have been studied for the reaction from the Arrhenius plot by studying the reaction at different temperatures.

Oxidation of glyoxal with the Mo-oxime complex in a benzalkonium chloride interface: Raghavan and Srinivasan kinetic model

Gaining an understanding of the glucose oxidation product (glyoxal) interaction with the metal–organic complex in a biological environment is pivotal to its usage. Thus, the glyoxal (Gyx) oxidation with Mo-oxime complex (MC) is studied with the spectrophotometric method, following a pseudo-phase approach. The result highlights the inclusion of hydrolysis, ion catalysis, the neutral primary salt effect, and radical generation as the essential factors in Gyx oxidation, with the exclusion of intermediate species formation. The hydrolysis of Gxy is observed to actively engage MC without charge inhibition as charge-neutral reacting species are involved, thus, implicating neutral primary salt effect where the variation of ionic strength of the system keeps the redox rate unchanged. The involvement of charge-neutral specie at the rate controlling step encouraged electrostatic attraction when Mg2+ ion additive is incorporated into the system, leading to ion catalysis. The generation of free radical from Gxy aids the emergence of formic acid. The zero intercept of Michealis-Menten type plot and the non-appreciable shift in the maximum absorption wavelength of the reaction system and MC rule-out the presence of intermediate species. The contribution of thermodynamic enthalpy is instrumental in the redox process, leading to the formic acid product. The inclusion of benzalkonium chloride (BZC) hastens the Gxy oxidation, which is supported by Raghavan and Srinivasan’s model.

Synergistic effects of temporal variations in flow and chemistry on colloid retention and remobilization in saturated porous media

Rapid infiltration due to rainfall events, groundwater pumping, and artificial recharge of groundwater result in temporal variations in both flow and chemistry in the subsurface and may lead to remobilization of retained colloids, thereby re-contaminating the groundwater resources. Many researchers have studied the effects of temporal variations in water velocity and in water chemistry separately. These variations, however, almost always occur simultaneously. To the best knowledge of the authors, there are no studies reported in the literature where the effect of simultaneous temporal variations in flow velocity and ionic strength on colloid release is investigated. One cannot assume that those effects can be simply superimposed. In fact, in this study, we show that these effects are not simply additive. We have performed eight sets of saturated column experiments on the effects of temporal variations in flow velocity alone and simultaneous temporal variations in flow velocity and ionic strength on retention and remobilization of colloids. Temporal increases in average water velocity caused an instantaneous spike release of colloids in the measured breakthrough curve, with the time to peak coinciding with the instant of velocity increase. Further, the effect of temporal variations in average water velocity on remobilization of deposited colloids is ionic-strength dependent. The simultaneous temporal increases in flow and decreases in ionic strength caused a spike release of colloids followed by long tails. The release curve for every step-change in velocity and ionic strength was unimodal for deposition ionic strengths of 100 and 10 mM, with the peak coinciding with the instant of arrival of ionic strength front at the column outlet. However, the release curve was bimodal for deposition ionic strengths of 50 and 25 mM. There, the first instantaneous spike coincided with the instant of increase in flow velocity, and the second delayed one coincided with the passage of the ionic strength front. Temporal variations in both flow and ionic strength released more colloids in the effluent than when only ionic-strength or only flow velocity was varied. This is due to the combined effects of greater hydrodynamic torque exerted on attached particles together with smaller adhesive torque.

New thermodynamic insights into pregabalin interactions with H+, Na+, Mg2+, Ca2+, Cu2+, Zn2+: Equilibrium constants, enthalpy changes and sequestering ability

The thermodynamics of the interaction between (S)-(+)-3-aminomethyl-5-methylhexanoic acid (pregabalin) and protons was studied potentiometrically at different temperatures (288.15 ≤ T/K ≤ 310.15), ionic strengths (0.16 ≤ I/mol kg−1(H2O) ≤ 0.97, NaCl), (0.11 ≤ I/mol kg−1(H2O) ≤ 1.11, (C2H5)4NI), (0.10 ≤ I/mol kg−1(H2O) ≤ 1.03, NaClO4, only at T = 298.15 K). The protonation constants at infinite dilution and the corresponding enthalpy change values were determined, as well as their parameters for the dependence on the temperature and ionic strength. The results showed that the protonation reactions are exothermic, and that the entropic contribution is the driving force of the processes.Formation constants of pregabalin (L) with Zn2+, Cu2+, Ca2+, and Mg2+ were determined in NaCl(aq) at different ionic strength values, at 298.15 K. Different speciation models were proposed for the various metal/Pregabalin systems: ZnHL2+, ZnLOH0(aq), CuL+, CuL20(aq), CaL+, CaHL2+, and MgL+, depending on the different acid-base properties of the metals and the possible formation of sparingly soluble species. The modelling of the thermodynamic formation parameters respect to the temperature and ionic strength variation was carried out by using both the Specific Ion Interaction Theory (SIT) and an extended Debye-Hückel type equation.Being Pregabalin an emerging contaminant, it was interesting to investigate its distribution in presence of the investigated metal cations in aqueous solution simulating both biological fluid (urine) and natural water (seawater).

Periodate-driven efficient degradation of diverse pharmaceuticals with iodine-doped MnO2

This research investigated the development of a novel catalyst for contaminant remediation. The strategy involved enhancing the catalytic effectiveness of MnO2 by strategically incorporating iodine, resulting in I-MnO2. Electron paramagnetic resonance (EPR) spectroscopy confirmed an augmentation in oxygen vacancies upon iodine inclusion, leading to increased catalytic activity. I-MnO2 was evaluated as an efficient catalyst within an advanced oxidation process for ciprofloxacin removal through periodate activation. The system achieved a 91.2 % degradation of 20 ppm ciprofloxacin within 9 min, demonstrating a strong correlation between catalyst and oxidant dosages. The I-MnO2/IO4¯ system exhibited remarkable stability across a broad pH range and minimal susceptibility to ionic strength variations, water anions, and humic acid presence. Quenching experiments coupled with EPR analysis suggested the involvement of singlet oxygen (1O2) and iodate radicals (IO3•) generated from the interaction of the metastable Mn(IV)-O-IO3 species with ciprofloxacin. X-ray photoelectron spectroscopy analysis of Mn 2p and O 1s orbitals, performed before and after reactions, further corroborated the role of I-MnO2 in facilitating periodate activation by promoting the conversion of Mn(II) and Mn(III) to Mn(IV) species. This innovative catalyst demonstrates exceptional efficiency in eliminating high concentrations of organic pollutants, suggesting its potential for practical and cost-effective applications in wastewater treatment.

A Study of Micellar Catalyses on Oxidation of Glycine by QDC in the Presence of Sodium Dodecyl Sulphate (SDS) in Aqueous Perchloric Acid Medium

Aims: To study the micellar effect of SDS on the oxidation of glycine by Quinolinium Dichromate (QDC) in perchloric acid medium. Background: Among the amino acids, glycine plays a major role in multiple metabolic reactions, such as glutathione synthesis and one-carbon metabolism. The oxidation of glycine has received importance because it is the major neurotransmitter inhibitor in the spinal cord and brainstem. In the oxidation process of amino acids, highly toxic chromium (VI) compounds are converted into non-toxic chromium (III) by quinolinium dichromate (QDC) oxidant in an appropriate pH value medium. Objective: 1. To study the catalytic role of anionic surfactant (SDS) on the oxidation of glycine by QDC through micellization, evaluation of critical micelles concentration (CMC) in the presence and absence of glycine and other surface properties along with thermodynamic quantities. 2. Determination of rate constant and order of reaction with respect to QDC, glycine, acid and surfactant which will help to study the kinetics of the reaction 3. Analysis of oxidation product by FT-IR and calculation of activation parameters. 4. Synthesis of oxidant (QDC) and its characterization by UV-Visible spectrophotometer and NMR spectroscopy. Results: First-order kinetics was observed with respect to oxidant, glycine and hydrogen ions. The rate of reaction increased remarkably with an increase in the concentration of surfactant (SDS). The kinetic results show that the ionic strength variation does not have any significant effect on the rate whereas the increase in the dielectric constant of the medium shows a remarkable effect on the rate constant. From stoichiometry study, it was found that 2 moles of oxidant (QDC) consumed 3 moles of glycine to produce aldehyde (Formaldehyde). Conclusion: The observed negative value of (ΔS) entropy of activation and positive (ΔH) enthalpy of activation suggests a more ordered activated complex formation and highly solvated transition state. The kinetics of the reaction in a perchloric acid medium is found to be accelerated in the presence of surfactant (SDS). The kinetics of the reaction follow pseudo first-order decay of Cr(VI) species (QDC), a unity dependence of rate on glycine and perchloric acid. The oxidation product formaldehyde was identified by FTIR. NMR spectrum analysis of synthesized QDC shows a resemblance with pure QDC.

Microwave Synthesis of Fluorescent Carbon Quantum dots from Araucaria Heterophylla Gum: Application in Drug Detection.

This study employed a green microwave synthesis technique to produce carbon quantum dots (CQDs) from araucaria heterophylla gum extract. The produced CQDs emit a distinct blue fluorescent light, contributing a remarkable quantum yield of 14.69%. Their average particle size measures at 1.62 ± 0.39nm. Furthermore, these CQDs demonstrate excellent water solubility and maintain high fluorescence stability despite ionic strength, pH and time variations. Moreover, we present here for the first time that the synthesized CQDs demonstrate a rapid, exceptionally sensitive, and discerning fluorescence quenching phenomenon (IFE) concerning Cefprozil (CPR). The fluorescent probe was sensitive and specific with good linear relationships for CPR in the 0-18 µM range. The limit of detection for relationships for CPR was 2.51 µM. This study provides novel opportunities for producing high-quality luminescent CQDs that meet the requirements for various biological and environmental applications.

Multiphysics Modeling of Electrode Dissolution Under Hydrodynamic Conditions in Low Conductivity Water

Efficient plug-flow electrochemical reactors are characterized by their ability to effectively convert species with significant ionic strength and/or with the assistance of a well-behaved electrolyte. Because of the classic electroconductivity requirement, electrochemical reactors are not particularly attractive options for applications with low-conductivity conditions, especially for low-pressure feeds. However, these reactors can still find application in dedicated processes such as ultra-clean water conditioning and biological-coupled separation systems. Consequently, a multi-physics model was developed using COMSOL Multiphysics to characterize different reactor-design conditions based on the Tertiary Current Distribution which accounts for the effects of expected variations in electrolyte composition and ionic strength on the electrochemical process, as well as solution resistance and electrode kinetics. The modelling framework presented here employs single-phase laminar fluid flow, the Nernst-Planck equation, the water-based electroneutrality condition, and concentration-dependent overpotentials. This investigation particularly explores the electrolysis process of “anodic dissolution,” in which elemental species dissociate from the solid matrix of the electrode and enter the liquid phase of the electrolyte as soluble ions. The reactor configuration of interest has a rectangular parallel-electrode design and is operated galvanostatically. A series of parametric studies are carried out to inspect the response of the system when hydrodynamic, kinetic, and geometric conditions are changed. The parametric sweep resulted in variable effluent concentrations and system voltage, which reveal underlaying optimization patterns for electrode dissolution in low conductivity water.

A practical process for effective thickening of silica shells formed onto spherical cores by considering the variation in ionic strength during sol-gel reaction

A novel process for coating spherical silica cores with a thick, mesoporous shell to obtain core-shell type mesoporous silica particles (C-MSPs) was developed. The solution pH during the sol-gel reaction in the presence of cetyltrimethylammonium bromide (CTAB), which was used for micelle templates, was measured to model the concentrations of ionic species. Silicate ions were of particular interest because their concentration rapidly increased by the hydrolysis of tetraethyl orthosilicate (TEOS) at high concentrations. The silicate ions present in the reaction mixture were determined by rate equations for the hydrolysis of TEOS and the condensation of silica. Estimating the ionic strength based on the modeled concentrations of ionic species in the solution allowed us to design an appropriate process of coating particles with a mesoporous silica shell. Mesoporous shells were effectively thickened by the continuous addition of TEOS at controlled feeding rates, where the concentration of silicate ions was kept lower than the solubility of silica, which helped suppressing the generation of secondary particles (by-products). Micron-sized C-MSPs with a mesoporous shell around a submicron-sized silica core were successfully obtained by the co-addition of TEOS and CTAB. An approximately 400 nm thick mesoporous shell with a porosity similar to that of conventional thin shells was formed onto 460 nm spherical cores. The concept of controlling the ionic strength of the reaction solution can also be applied to other cores, which offers a practical approach to synthesize core-shell type mesoporous particles required in various future applications.

Self-Assembly of Ultrasmall 3D Architectures of (l)-Acyclic Threoninol Nucleic Acids with High Thermal and Serum Stability.

The primary challenge of implementing DNA nanostructures in biomedical applications lies in their vulnerability to nuclease degradation and variations in ionic strength. Furthermore, the size minimization of DNA and RNA nanostructures is limited by the stability of the DNA and RNA duplexes. This study presents a solution to these problems through the use of acyclic (l)-threoninol nucleic acid (aTNA), an artificial acyclic nucleic acid, which offers enhanced resilience under physiological conditions. The high stability of homo aTNA duplexes enables the design of durable nanostructures with dimensions below 5 nm, previously unattainable due to the inherent instability of DNA structures. The assembly of a stable aTNA-based 3D cube and pyramid that involves an i-motif formation is demonstrated. In particular, the cube outperforms its DNA-based counterparts in terms of stability. We furthermore demonstrate the successful attachment of a nanobody to the aTNA cube using the favorable triplex formation of aTNA with ssDNA. The selective in vitro binding capability to human epidermal growth factor receptor 2 is demonstrated. The presented research presents the use of aTNA for the creation of smaller durable nanostructures for future medical applications. It also introduces a new method for attaching payloads to these structures, enhancing their utility in targeted therapies.

Adsorption performance of 1,4-dioxane by MCM-22 and Beta zeolites and their bio-zeolite composite system in the presence of co-contaminants

Addressing the significant challenge of efficiently separating 1,4-dioxane from aquatic environments using traditional adsorbents is crucial. In this study, we evaluated the adsorption performance of MCM-22 and Beta zeolites. Both were identified as highly effective adsorbents. Equilibrium adsorption of 1,4-dioxane was achieved within 20 min for an initial concentration of 500 mg L-1 on both MCM-22 and Beta zeolites. At 288 K, the maximum adsorption capacities fitted by Langmuir isotherm were 79.66 mg g−1 for MCM-22 and 121.66 mg g−1 for Beta zeolite. Fixed-bed column studies demonstrated that the Yan model properly predicted the behavior of both zeolites under varying flow rates. Additionally, MCM-22 exhibited a wider pore size distribution compared to Beta zeolite, while Beta zeolite demonstrated a higher volume of ultra-micropores (<1 nm) than MCM-22. This highlights the importance of pore volume filling in facilitating excellent adsorption of 1,4-dioxane by both zeolites. Further analysis via FTIR and 1H NMR confirmed the significance of Brønsted acid sites in 1,4-dioxane adsorption. The adsorption performance of both zeolites remained unaffected by initial pH values ranging from 2 to 11, as well as variations in ionic strength or the presence of natural organic matter (NOM) for both zeolites. However, the co-existence of 1,1-dichloroethene (1,1-DCE) resulted in competitive adsorption with 1,4-dioxane, leading to a notable decrease in adsorption capacity of 1,4-dioxane. In contrast, the presence of metal ions Cu2+ and Ag+ did not compete for adsorption sites with 1,4-dioxane. Our study demonstrated the effectiveness of the bio-zeolite system in regenerating spent adsorbents, surpassing water and solvent regeneration methods in efficiency and recyclability. Although addressing the persistence of 1,1-DCE remains a challenge, bio-zeolites emerge as versatile tools for mitigating the bio-inhibition of heavy metals, such as Cu2+ and Ag+, while offering a sustainable solution for 1,4-dioxane bioremediation.

Formation of the calpain-1/calpastatin complex promotes activation of calpain-1 under oxidizing conditions.

Calpains are cysteine proteinases responsible for many biological roles in muscle, including protein degradation, muscle growth, and myoblast fusion. Calpains are inhibited by calpastatin, an endogenous inhibitor. Other factors, such as variations in pH, ionic strength, and oxidation influence calpain activity. This study aimed to determine the extent to which oxidation influences calpastatin inhibition of calpain-1. A series of order of addition assays were used to determine calpain-1 calcium activation and autolysis after exposure to an oxidizing agent (n-ethylmaleimide [NEM] or hydrogen peroxide [H2O2]. In the first series, purified calpastatin was added to the assay before or after oxidizing exposure at 165mM NaCl, pH 6.5. In the second series, incubation buffer ionic strength (165mM or 295mM NaCl) was evaluated. The inhibitory activities of purified porcine calpastatin, purified human calpastatin domain I, or a subdomain B inhibitor peptide were evaluated in the third series. In the fourth series, a maleimide-polyethylene glycol molecule (MAL-PEG; MW = 5,000 Dalton) was used to evaluate the accessibility of free sulfhydryl groups and tagging of calpain-1 under each condition through a molecular weight shift assay. Results from this study indicate that autolysis of calpain-1, when used as an indicator of activation, occurred when the calpain-1/calpastatin complex was exposed to an oxidant or cysteine modifier such as NEM. However, when calpain-1 was exposed to the cysteine modifier before calpastatin, autolysis of calpain-1 did not occur or was significantly decreased (P < 0.05). Irreversible modification of cysteine residues by NEM prevented activation of calpain-1 in the absence of calpastatin, but if the cysteine modification is potentially reversible (H2O2), calpain-1 activity can be recovered. Results from this study indicate that when calpastatin is bound to calpain-1, calpain-1 activation can occur even after being exposed to a cysteine modifier (NEM) or hydrogen peroxide (H2O2). Calpain-1 is not tagged with maleimide-polyethylene glycol (MAL-PEG) in the presence of calpastatin, indicating that calpastatin blocks or covers free cysteines on calpain-1 from modification. Moreover, exposure to calpain-1/calpastatin complex with a cysteine modifier allows activation of calpain-1, indicating that the inhibitory action of calpastatin is compromised. These results indicate a regulatory role for calpastatin that is not inhibitory but protective for calpain-1.

KCD: A prediction web server of knowledge-based circular dichroism.

We present a web server that predicts the far-UV circular dichroism (CD) spectra of proteins by utilizing their three-dimensional (3D) structures from the Protein Data Bank (PDB). The main algorithm is based on the classical theory of optical activity together with a set of atomic complex polarizabilities, which are obtained from the analysis of a series of synchrotron radiation CD spectra and their related 3D structures from the PDB. The results of our knowledge-based CD method (KCD) are in good agreement with measured spectra that could include the effect of D-amino acids. Our method also delivers some of the most accurate predictions, in comparison with the calculated spectra from well-established models. Specifically, using a metric of closeness based on normalized absolute deviations between experimental and calculated spectra, the mean values for a series of 57 test proteins give the following figures for such models: 0.26 KCD, 0.27 PDBMD2CD, 0.30 SESCA, and 0.47 DichroCalc. From another point of view, it is worth mentioning the remarkable capabilities of the recent approaches based on artificial intelligence, which can precisely predict the native structure of proteins. The structure of proteins, however, is flexible and can be modified by a diversity of environmental factors such as interactions with other molecules, mechanical stresses, variations of temperature, pH, or ionic strength. Experimental CD spectra together with reliable predictions can be utilized to assess eventual secondary structural changes. A similar kind of evaluation can be done for the case of an incomplete protein structure that has been reconstructed by using different approaches. The KCD method can be freely accessed from: https://kcd.cinvestav.mx/.

Extended ADM1 model to study trace metal speciation and its effects on anaerobic digestion

Trace metals (TM) are often added to anaerobic digestors (AD) to improve digestor performance and methane yield. Though numerous experimental studies are done to study TM effects, a model based on ADM1 will help plant operators in case of metal deprivation as there are analytical limitations in quantifying metal speciation which controls TM effects on AD. This study developed a complete dynamic model based on ADM1 with least and unavoidable model input information to study TM speciation and its influence on AD. In addition to the biochemical and gas stripping processes described in ADM1, the model introduced new physicochemical processes with effects of operational conditions like pH, temperature and ionic strength. The biogeochemical processes influencing TM speciation include microbial uptake, precipitation (sulphides, phosphates, carbonates), adsorption (onto biomass, soluble inerts and precipitates), inorganic complexation and organic complexation (with EDTA, VFAs, amino acids (AAs)). The model was tested under different scenarios: variable EDTA concentration and dosing form, variable substrate and variable ionic strength. Complexation of TMs with EDTA and AAs influences metal bioavailability and methane yield. Supplementing EDTA reduces TM dosing and dosing EDTA as metal-EDTA complex is more effective than supplementing metals and EDTA separately. TM-AA complexation depends on substrates as amino acid compounds vary with substrates. Ionic strength influences TM adsorption and precipitation processes and hence is an important operational parameter controlling the system like pH and temperature. The model has been compared to experimental data obtained from this study and has been successfully applied to predict cobalt deprivation in an anaerobic digestor.

Transport and retention of silica nanoparticles in glass-bead columns: effects of particle size, type, and concentration of ionic species

Silica nanoparticles (SiO2 NPs) have garnered substantial attention as versatile additives in saline fluids, finding application in areas like environmental remediation, wastewater treatment, enhanced oil recovery, and carbon geo-sequestration. Despite their potential, the intricate interaction between electrolyzed nanoparticles and porous media remains inadequately researched in these contexts. This study delves into the pivotal yet underexplored aspect of silica nanoparticle absorption behavior within porous media, a key determinant of their practical effectiveness. The research focuses on silica particles with dimensions of 10 nm and 50 nm, synthesized via hydrolysis and condensation of tetraethyl orthosilicate (TEOS) in methanol. Employing packed glass bead columns as a surrogate for porous media, the study unravels the complex mechanisms governing nanoparticle transport and deposition. Comprehensive investigations encompass variations in particle sizes, ionic strength, and ionic species, resulting in the examination of 48 distinct flooding scenarios. UV/Vis spectrophotometry is used to quantify nanoparticle concentrations in effluents, elucidating their transport behavior within the porous media. Concurrently, pressure drop alterations across the media serve as indicators of particle plugging and changes in permeability. Intriguingly, specific conditions involving a nanofluid comprising 50 nm silica nanoparticles and 10,000 ppm of magnesium chloride exhibit pronounced permeability reduction, offering potential insights for optimizing applications. Particularly noteworthy is the unique reduction in silica particle retention on glass bead surfaces as salinity increases, especially in the presence of magnesium sulfate. A concentration of 5000 ppm magnesium sulfate induces a log-jamming mechanism, resulting in an amplified final-to-intermediate permeability ratio. Experimental outcomes align with observations from scanning electron microscopy, improving understanding of porous media retention mechanisms. This study contributes to a deeper understanding of interactions between nanoparticles and porous media, paving the way for enhanced application strategies.

Interlayer confinement mediated oxidation of americium by sodium bismuthate and stability of its higher redox states in acidic solution.

Mutual separation of trans-plutonium actinides (Ans) from lanthanides (Lns) or adjacent Ans is challenging as they exhibit great chemical similarity. Selective Am oxidation-based Am-Lns or Am-Cm separation strategies give very high separation factors. There exist several reports on different aspects of Am3+ oxidation by NaBiO3·xH2O (x = 2-3), which suggests that the oxidation mechanism is still not well understood. We, therefore, carefully performed several experiments taking advantage of the difference in the redox chemistry of Eu3+ and Am3+. The ion exchange of Eu3+ with the interlayer Na+ in NaBiO3 was confirmed by an ionic strength variation experiment. The shift in the 001 peak of NaBiO3 in XRD and the appearance of peaks corresponding to the trivalent Ln ions in XRF after Ln3+ loading give direct evidence for Na+ exchange with Ln3+. The stability of the higher oxidation state of Am was monitored spectrophotometrically. The experimental investigations also suggested the role of Am3+ → AmO22+ transformation in NaBiO3·xH2O (x = 2-3) dissolution even at pH ∼ 1, which otherwise is difficult to achieve even with >1 M HNO3. The role of colloidal NaBiO3 particles and dissolved BiO3- in controlling or stabilizing different oxidation states of Am was also discussed.

Unintended Cation Crossover in CO2 Conversion MEA Cells: Causes and Effects

Membrane electrode assemblies in gas diffusion cells enable CO2 reduction at industrially relevant rates, yet their long-term operational stability is often limited by the formation of solid precipitates (e.g. K2CO3) in the cathode pores. This is a consequence of a combination of 1) local alkalization due to the electrochemical reaction, 2) generation of (bi)carbonate by chemical reaction of CO2 with the alkaline electrolyte, and 3) the presence of alkali metal cations. In catholyte-free, zero-gap cells using anion exchange membranes, the presence of electrolyte cations at the cathode is the result of unintended crossover from the anolyte, and a detailed understanding of the factors enabling this crossover is lacking. Here we show that the anolyte concentration governs the flux of cation migration through the membrane, and this substantially influences the behaviors of copper catalysts in catholyte-free CO2 electrolysers. Systematic variation of the anolyte ionic strength (using aqueous KOH or KHCO3) correlated with drastic changes in the observed product selectivity – most notably, at low ionic strength, Cu catalysts produced predominantly CO, in contrast to the mixture of C2+ products typically observed on Cu. In this talk, we examine the factors influencing ion crossover and the resulting effects on catalyst structure and activity, under conditions of both CO2 and CO reduction. Operando X-ray absorption spectroscopy and quasi in situ X-ray photoelectron spectroscopy were used to study how the catalyst is affected by operation conditions. Our results show that even in catholyte-free cells, cation effects (including unintended ones) can significantly influence reaction pathways, and this must be considered in future development of catalysts and devices.El-Nagar, G. A., Haun, F., Gupta, S., Stojkovikj, S. & Mayer, M. T. Unintended cation crossover influences CO2 reduction activity in Cu-based zero-gap electrolysers. Nature Communications14, 2062 (2023) doi: doi.org/10.1038/s41467-023-37520-x Figure 1

Exothermic binding and structural alteration of the carrier protein lysozyme induced by Yohimbine: A spectroscopic, calorimetric and cheminformatic insight

The crucial function of bioactive ligands in the interaction with diverse proteins has garnered significant attention in the fields of pharmacokinetics and pharmacodynamics, hence generating considerable interest in the discipline of medicinal chemistry. To better comprehend its molecular mechanism, we implored a detailed biophysical analyses (using multi-spectroscopic, calorimetric, and computational tools) of the carrier protein Lysozyme, Lyz (also known as “Muramidase”) with Yohimbine (Yoh). The binding constant (K) of the Lyz-Yoh complex was estimated to be 105 M−1, exhibiting a progressive decline as temperature increased. The thermodynamic-profiling indicated the binding to be associated with an exothermic interaction driven by entropy. The confirmation of spontaneous binding is evidenced by the observed decrease in free energy. The variation in ionic strength indicated that non-polyelectrolytic forces were involved in the association. In addition, it was investigated how different metal ions affected the Lyz-Yoh binding. Calorimetric studies revealed the binding to be exothermic in nature, which also aligns with spectroscopic data. Results from circular dichroism (CD) experiments, demonstrated the structural alterations brought about in Lyz by Yoh. The likely binding sites and protein residuals to the ligand (Yoh) were illustrated using theoretical techniques, viz., molecular docking and molecular dynamic (MD) simulation. In clinical and pharmaceutical assessments, these metrics are especially relevant for rational drug development.

Synthesis and Characterization of Stimuli-Responsive Polymer Brushes in Nanofluidic Channels.

Nanochannels with controllable gating behavior are attractive features in a wide range of nanofluidic applications including viral detection, particle sorting, and flow regulation. Here, we use selective sidewall functionalization of nanochannels with a polyelectrolyte brush to investigate the channel gating response to variations in solution pH and ionic strength. The conformational and structural changes of the interfacial brush layer within the channels are interrogated by specular and off-specular neutron reflectometry. Simultaneous fits of the specular and off-specular signals, using a dynamical theory model and a fitting optimization protocol, enable detailed characterization of the brush conformations and corresponding channel geometry under different solution conditions. Our results indicate a collapsed brush state under basic pH, equivalent to an open gate, and an expanded brush state representing a partially closed gate upon decreasing the pH and salt concentration. These findings open new possibilities in noninvasive in situ characterization of tunable nanofluidics and lab-on-chip devices with advanced designs and improved functionality.

The Smallest Infectious Substructure Encoding the Prion Strain Structural Determinant Revealed by Spontaneous Dissociation of Misfolded Prion Protein Assemblies

It is commonly accepted that the prion replicative propensity and strain structural determinant (SSD) are encoded in the fold of PrPSc amyloid fibril assemblies. By exploring the quaternary structure dynamicity of several prion strains, we revealed that all mammalian prion assemblies exhibit the generic property of spontaneously generating two sets of discreet infectious tetrameric and dimeric species differing significantly by their specific infectivity. By using perturbation approaches such as dilution and ionic strength variation, we demonstrated that these two oligomeric species were highly dynamic and evolved differently in the presence of chaotropic agents. In general, our observations of seven different prion strains from three distinct species highlight the high dynamicity of PrPSc assemblies as a common and intrinsic property of mammalian prions. The existence of such small infectious PrPSc species harboring the SSD indicates that the prion infectivity and the SSD are not restricted only to the amyloid fold but can also be encoded in other alternative quaternary structures. Such diversity in the quaternary structure of prion assemblies tends to indicate that the structure of PrPSc can be divided into two independent folding domains: a domain encoding the strain structural determinant and a second domain whose fold determines the type of quaternary structure that could adopt PrPSc assemblies.