Probing electrolyte influence on CO2 reduction in aprotic solvents

Selective CO2 capture and electrochemical conversion is an important tool in the fight against climate change. Industrially, CO2 is captured using a variety of aprotic solvents due to their high CO2 solubility. However, most research efforts on electrochemical CO2 conversion use aqueous media and are plagued by competing hydrogen evolution reaction (HER) from water breakdown. Fortunately, aprotic solvents can circumvent HER; making it important to develop strategies that enable integrated CO2 capture and conversion in an aprotic solvent. However, the influence of ion solvation and solvent selection within nonaqueous electrolytes for efficient and selective CO2 reduction is unclear. In this work, we show that bulk solvation behavior within the nonaqueous electrolyte can control the CO2 reduction reaction and product distribution occurring at the catalyst-electrolyte interface. We study different TBA (tetrabutylammonium) salts in two electrolyte systems with glyme-ethers (e.g., 1,2 dimethoxyethane or DME) and dimethylsulfoxide (DMSO) as a low and high dielectric constant medium, respectively. Using spectroscopic tools, we quantify the fraction of ion pairs that form within the electrolyte and show how ion-pair formation is prevalent in DME electrolytes and is dependent on anion type. More importantly, we show as ion-pair formation decreases within the electrolyte, CO2 current densities increases, and a higher CO Faradaic efficiency is observed at low overpotentials. Meanwhile, in an electrolyte medium where ion-pair fraction does not change with anion type (such as in DMSO), a smaller influence of solvation was observed on CO2 current densities and product distribution. By directly coupling bulk solvation to interfacial reactions and product distribution, we showcase the importance and utility of controlling the reaction microenvironment in tuning electrocatalytic reaction pathways. Insights gained from this work will enable novel electrolyte design for efficient and selective CO2 conversion to desired fuels and chemicals

Conductometric studies of 1, 3, 5 –triazinothiocarbamide at different concentration and temperature

Conductivity plays vital role in drug diffusion. Thermodynamic parameters affected by substituents of drug. Thermodynamic parameters of 1, 3, 5 –triazinothiocarbamide (1a) have been investigated by using conductometrically carried out at different molar concentrations. This work highlights investigation of G, K and µ values. The thermodynamic parameters viz. ΔH, ΔS and ∆G for ion pair formation determine from the value of ion association constant. This technique is suitable and accurate to study of pharmokinetics and pharmodynamics parameters.

Pb Mineral Precipitation in Solutions of Sulfate, Carbonate and Phosphate: Measured and Modeled Pb Solubility and Pb2+ Activity

Lead (Pb) solubility is commonly limited by dissolution–precipitation reactions of secondary mineral phases in contaminated soils and water. In the research described here, Pb solubility and free Pb2+ ion activities were measured following the precipitation of Pb minerals from aqueous solutions containing sulfate or carbonate in a 1:5 mole ratio in the absence and presence of phosphate over the pH range 4.0–9.0. Using X-ray diffraction and Fourier-transform infrared spectroscopic analysis, we identified anglesite formed in sulfate-containing solutions at low pH. At higher pH, Pb carbonate and carbonate-sulfate minerals, hydrocerussite and leadhillite, were formed in preference to anglesite. Precipitates formed in the Pb-carbonate systems over the pH range of 6 to 9 were composed of cerussite and hydrocerussite, with the latter favored only at the highest pH investigated. The addition of phosphate into the Pb-sulfate and Pb-carbonate systems resulted in the precipitation of Pb3(PO4)2 and structurally related pyromorphite minerals and prevented Pb sulfate and carbonate mineral formation. Phosphate increased the efficiency of Pb removal from solution and decreased free Pb2+ ion activity, causing over 99.9% of Pb to be precipitated. Free Pb2+ ion activities measured using the ion-selective electrode revealed lower values than predicted from thermodynamic constants, indicating that the precipitated minerals may have lower KSP values than generally reported in thermodynamic databases. Conversely, dissolved Pb was frequently greater than predicted based on a speciation model using accepted thermodynamic constants for Pb ion-pair formation in solution. The tendency of the thermodynamic models to underestimate Pb solubility while overestimating free Pb2+ activity in these systems, at least in the higher pH range, indicates that soluble Pb ion-pair formation constants and KSP values need correction in the models.

Structural determinants of voltage-gating properties in calcium channels

Voltage-gated calcium channels control key functions of excitable cells, like synaptic transmission in neurons and the contraction of heart and skeletal muscles. To accomplish such diverse functions, different calcium channels activate at different voltages and with distinct kinetics. To identify the molecular mechanisms governing specific voltage-sensing properties we combined structure modeling, mutagenesis, and electrophysiology to analyze the structures, free energy, and transition kinetics of the activated and resting states of two functionally distinct voltage-sensing domains (VSDs) of the eukaryotic calcium channel CaV1.1. Both VSDs displayed the typical features of the sliding helix model; however, they greatly differed in ion-pair formation of the outer gating charges. Specifically, stabilization of the activated state enhanced the voltage-dependence of activation, while stabilization of resting states slowed the kinetics. This mechanism provides a mechanistic model explaining how specific ion-pair formation in separate VSDs can realize the characteristic gating properties of voltage-gated cation channels.

An Eco-Concerned Development of a Fast, Precise and Economical Spectrophotometric Assay for the Antiviral Drug Simeprevir based on Ion-Pair Formation

Simeprevir sodium (SMV) is one of the antiviral drugs used for the treatment of virus C. The current strategy develops and validates a new eco-concerned tool for its quantification in the pure and pharmaceutical formulations. Sulfonephthalein acid dyes were used for this purpose, applying visible analyses based on ion-pair formation. A linear relation between the absorbed signal and the drug concentration is obtained up to 67.0 μg mL-1 with r2 of 0.9989-0.9999. The measurement is carried out at 410, 415, 410, and 403 nm for bromocresol green, bromoxelenol blue, bromothymol blue, and bromocresol purple, respectively, in dichloromethane as a solvent. The drug structure was confirmed utilizing different tools; mass spectrometry, FT-IR, 1H NMR, and thermal analysis. Association, formation constants, molar absorptivity, and free energy change for SMV-ion-pairs were calculated. The limit of detection reaches 50.0 ng mL-1 with a quantification limit of 180.0 ng mL-1. The recovery values are 96.44-104.39%, with a relative standard deviation 0.15-1.37%. For confirmation of the obtained results, they were statistically compared with a previously published HPLC method utilizing t- and F- tests.