Determination Of Rate Constants Research Articles

Moment analysis method for determination of rate constants of solute permeation across interface of spherical molecular aggregates by means of high-performance liquid chromatography

A moment analysis method was developed for the study of solute permeation at the interface of spherical molecular aggregates. At first, new moment equations were developed for determining the partition equilibrium constant (Kp) and permeation rate constants (kin and kout) of solutes from the first absolute (μ1A) and second central (μ2C) moments of elution peaks measured by using high-performance liquid chromatography (HPLC). Then, the method was applied to the analysis of mass transfer phenomena of three solutes, i.e., hydroquinone, resorcinol, and catechol, at the interface of sodium dodecylsulfate (SDS) micelles. HPLC data were measured by using an ODS column and an aqueous phosphate buffer solution (pH = 7.0) as the mobile phase solvent. Pulse response experiments were conducted while changing SDS concentration (5 - 20 mmol dm−3) in the mobile phase under the conditions that the surface of ODS stationary phase was dynamically coated by SDS monomers. In order to demonstrate the effectiveness of the moment analysis method using HPLC, the values of Kp, kin, and kout were determined for the three solutes as 35 - 69, 2.4 × 10−8 - 1.4 × 10−6 m s−1, and 7.0 × 10−10 - 2.1 × 10−8 m s−1, respectively. Their values increase with an increase in the hydrophobicity of the solutes. The method has some advantages for the study of interfacial solute permeation of molecular aggregates. For example, neither immobilization nor chemical modification of both solute molecules and molecular aggregates is required when elution peaks are measured by using HPLC. Interfacial solute permeation takes place in the mobile phase without any chemical reaction or physical action on molecular aggregates. The values of Kp, kin, and kout were analytically determined from those of μ1A and μ2C by using the moment equations. The results of this study must contribute to the dissemination of an opportunity for studying the interfacial solute permeation of molecular aggregates to many researchers because of extremely high versatility of HPLC.

Moment Analysis Method for Determination of Rate Constants of Solute Permeation across Interface of Spherical Molecular Aggregates by Means of High-Performance Liquid Chromatography

A moment analysis method was developed for the study of solute permeation at the interface of spherical molecular aggregates. At first, new moment equations were developed for determining the partition equilibrium constant (Kp) and permeation rate constants (kin and kout) of solutes from the first absolute (μ1A) and second central (μ2C) moments of elution peaks measured by using high-performance liquid chromatography (HPLC). Then, the method was applied to the analysis of mass transfer phenomena of three solutes, i.e., hydroquinone, resorcinol, and catechol, at the interface of sodium dodecylsulfate (SDS) micelles. HPLC data were measured by using an ODS column and an aqueous phosphate buffer solution (pH = 7.0) as the mobile phase solvent. Pulse response experiments were conducted while changing SDS concentration (5 - 20 mmol dm−3) in the mobile phase under the conditions that the surface of ODS stationary phase was dynamically coated by SDS monomers. In order to demonstrate the effectiveness of the moment analysis method using HPLC, the values of Kp, kin, and kout were determined for the three solutes as 35 - 69, 2.4 × 10−8 - 1.4 × 10−6 m s−1, and 7.0 × 10−10 - 2.1 × 10−8 m s−1, respectively. Their values increase with an increase in the hydrophobicity of the solutes. The method has some advantages for the study of interfacial solute permeation of molecular aggregates. For example, neither immobilization nor chemical modification of both solute molecules and molecular aggregates is required when elution peaks are measured by using HPLC. Interfacial solute permeation takes place in the mobile phase without any chemical reaction or physical action on molecular aggregates. The values of Kp, kin, and kout were analytically determined from those of μ1A and μ2C by using the moment equations. The results of this study must contribute to the dissemination of an opportunity for studying the interfacial solute permeation of molecular aggregates to many researchers because of extremely high versatility of HPLC.

Charge Transfer Kinetics in Halide Perovskites: On the Constraints of Time-Resolved Spectroscopy Measurements.

Understanding photophysical processes in lead halide perovskites is an important aspect of optimizing the performance of optoelectronic devices. The determination of exact charge carrier extraction rate constants remains elusive, as there is a large and persistent discrepancy in the reported absolute values. In this review, we concentrate on experimental procedures adopted in the literature to obtain kinetic estimates of charge transfer processes and limitations imposed by the spectroscopy technique employed. Time-resolved techniques (e.g., transient absorption-reflection and time-resolved photoluminescence spectroscopy) are commonly employed to probe charge transfer at perovskite/transport layer interfaces. The variation in sample preparation and measurement conditions can produce a wide dispersion of the measured kinetic parameters. The selected time window and the kinetic fitting model employed introduce additional uncertainty. We discuss here evaluation strategies that rely on multiexponential fitting protocols (regular or stretched) and show how the dispersion in the reported values for carrier transfer rate constants can be resolved.

Theoretical studies on the kinetics and mechanism of hydroxyl radical reaction with quinclorac and quinmerac herbicides in aqueous media

AbstractThe kinetic and mechanistic studies for the reaction of hydroxyl radical with two quinoline based herbicides, namely, quinclorac and quinmerac has been performed using various computational methods in aqueous media. Geometry optimizations were performed using Density Functional Theory (DFT) methods including water as the solvent. Local reactivity parameters of these herbicides towards the •OH radical are predicted using condensed Fukui function. Single point energies of various species were calculated using double hybrid method, namely, B2PLYP–D for better accuracy. The pKa values for these acid based herbicides allow them to exist in deprotonated form in aqueous condition. Hence, the calculations are also performed for the deprotonated or the anionic form apart from the neutral species. Individual rate coefficients for •OH radical addition reaction with each carbon atoms were evaluated using conventional transition state theory using one–dimensional tunneling corrections. The solvent effect on reaction is implemented through Collins–Kimball formulations. Both the approaches, namely, the Fukui index and individual rate constant determination confirms that the most reactive site for the •OH radical addition in these two herbicide is the carbon atom attached to the COOH group. The total rate constant for the •OH radical reaction with both neutral and anionic forms of these two herbicides are relatively high and equal to its diffusion‐limit value. Evaluation of the ecotoxicities of the parent herbicides and their OH adducts is estimated using the structure–activity relationship concept.

Performance evaluation of Bi/Zn‐impregnated commercial TiO2 nanoparticles for photocatalytic nitrobenzene decomposition

AbstractBACKGROUNDCommercial TiO2 nanoparticles were subjected to modification through Bi and Zn metal doping. The resulting catalysts were comprehensively characterized, and their performance was then reviewed for removal of model pollutant nitrobenzene in water.RESULTSAmidst the synthesized catalysts, the co‐doping of Bi/Zn (0.25:0.75 wt%) demonstrated the best photocatalytic degradation activity, achieving 95% degradation within 90 min of reaction time, with 2.99 × 10−2 min−1 rate constant value. The involvement of different radicals during the degradation process was elucidated by employing appropriate radical scavengers. Furthermore, the degradation results were investigated applying the first‐order kinetic model, leading to the determination of reaction rate constants and initial rates of the degradation process.CONCLUSIONAn improved photocatalytic activity was observed with metal doping due to the synergistic effect of doped metals with commercial TiO2 and profound charge transfer among them. It was observed that performance was increased with temperature rise in the practical range of application, that is, 5–20 °C. This behavior was due to high rate of movement of charge carriers. Further, involvement and functioning of various radical species such as h+, OH− and O2− in nitrobenzene degradation were successfully established using appropriate radical scavengers. © 2024 Society of Chemical Industry (SCI).

Millistructured Coiled Flow Inverter for Biphasic Continuous Flow 5‐Chloromethylfurfural Synthesis

AbstractSyntheses of alternative platform chemicals, such as 5‐chloromethylfurfural (CMF), from bio‐based starting materials are often associated with complicated kinetic schemes and mass transfer processes. Millistructured flow reactor concepts can help to elucidate kinetic schemes and determine rate constants which are of crucial importance for the design of respective technical processes. For the first time, the influence of proton concentration on the rate constants involved in the biphasic synthesis of CMF is systematically investigated. Results are discussed in terms of green chemistry metrics.

Ultrasonic monitoring of enzymatic hydrolysis of proteins. 2. Relaxation effects

The paper investigates the occurrence of relaxation processes in enzymatic hydrolysis of whey proteins in phosphate buffer using high-resolution ultrasonic spectroscopy. The hydrolysis produces a frequency-dependent evolution of ultrasonic velocity and attenuation originated by the proton transfer between the terminal group of protein hydrolysates and the phosphate ions. Such frequency dependence is absent in other systems, e.g., Tris buffer. Real-time profiles of ultrasonic velocity and attenuation measured during the hydrolysis of β–lactoglobulin, α–lactalbumin and bovine serum albumin by α–chymotrypsin were employed in quantitative analysis of the relaxation mechanisms, relaxation times, determination of the proton transfer rate constants and the reaction volume. The proton transfer is characterised by the rate constant 9.4 x 107 L mol-1 s-1 and the adiabatic reaction volume 24 x 10-6 m3 mol-1. The obtained reaction volume agrees well with thermodynamic data for ionisation volumes and enthalpies of the terminal amino group and phosphate. The described methodology for estimating the relaxation contribution to ultrasonic characteristics allows for precision real-time ultrasonic measurements of the concentration of peptide bonds cleaved during protein hydrolysis in a broad range of environmental conditions.

Machine Learning for Experimental Reactivity of a Set of Metal Clusters toward C-H Activation.

Understanding the mechanisms of C-H activation of alkanes is a very important research topic. The reactions of metal clusters with alkanes have been extensively studied to reveal the electronic features governing C-H activation, while the experimental cluster reactivity was qualitatively interpreted case by case in the literature. Herein, we prepared and mass-selected over 100 rhodium-based clusters (RhxVyOz- and RhxCoyOz-) to react with light alkanes, enabling the determination of reaction rate constants spanning six orders of magnitude. A satisfactory model being able to quantitatively describe the rate data in terms of multiple cluster electronic features (average electron occupancy of valence s orbitals, the minimum natural charge on the metal atom, cluster polarizability, and energy gap involved in the agostic interaction) has been constructed through a machine learning approach. This study demonstrates that the general mechanisms governing the very important process of C-H activation by diverse metal centers can be discovered by interpreting experimental data with artificial intelligence.

A DFT study of the antioxidant potency of α-tocopherol and its derivatives: PMHC, Trolox, and α-CEHC

In this research, antioxidant potency (in terms of peroxyl radical scavenging and catalytic iron ions sequestration) of α-tocopherol and its analogues, has been theoretically investigated. A DFT based kinetic estimation of HOO• radical scavenging potency of PMHC (lipophilic α-TOH derivative) and Trolox (hydrophilic α-TOH derivative) was performed in eight solvents of different polarity. Calculations employing M06-2X functional, accompanied by 6-311++G(d,p) basis set and SMD solvation model, were found as more accurate in reproducing experimentally determined rate constants than M05-2X functional. Rate constant of Trolox in pentyl ethanoate also was estimated by using Snelgrove−Ingold equation and Abraham’s β2H solvent parameter. Scavenging of CH3OO• and HOO• radicals, which is influenced by location, orientation, and dynamics of α-TOH and its derivatives in the membrane lipid bilayer, was estimated by using M06-2X functional. Position of α-TOH phenolic OH group is opposite to that of its metabolite α-CEHC: α-TOH’s OH group is located at the membrane-water interface, and α-CEHC’s OH group is deeply buried into the bilayer. In the aqueous phase both fHAT and SET were investigated, and inside the bilayer only fHAT was considered as feasible. The spontaneous disproportionation of HOO•/O2•− in aqueous solutions should be taken into account to predict potency of antioxidant in scavenging of HOO• radicals. Iron chelating ability of α-TOH and α-CEHC was also investigated. Obtained results indicate α-CEHC, α-tocopherol final catabolite, as more potent scavenger of CH3OO• and HOO• radicals and iron ions chelator than the parent molecule.

A fundamental study on cyclic voltammetry at porous carbon thin-film electrodes

Porous carbons represent an important group of electrode materials for electrochemical applications due to their high specific surface area, good conductivity, and intrinsic porosity. However, the often-neglected influence of the electrode porosity on the electrochemical results may lead to wrong interpretation of data. The aim of this work is therefore to provide comprehensive understanding of the effects of electrode porosity on cyclic voltammetry (CV) – a technique which is frequently used for initial characterization of novel electrode materials. Our approach consists of simulating experimental results, observed for the redox-reactions of [Fe(CN)6]3-/4− at porous CNT thin-film electrodes, with a mathematical model. The results demonstrate that the main difference between planar and porous electrode is the additional charge transferred in the porous electrode domain, which has the decisive contribution to the overall faradaic current at high scan rates. To further verify the applied model, the porosity of the porous CNT film is varied on purpose by changing the Nafion-Carbon-ratio (NCR). We are able to determine the electrochemically available pore volume (ECPV) of the electrode, which is strongly affected by the NCR, and correlate changes in the ECPV with changes in the scan-rate dependent CV. Moreover, we implement an approach for determination of reaction rate constants at porous electrodes, which was verified by simulated CV data. Evaluation of the experimental results shows that the reaction rate constant of the porous CNT material actually has the same order of magnitude as the planar glassy carbon substrate.

Shine-Dalgarno Accessibility Governs Ribosome Binding to the Adenine Riboswitch.

Translational riboswitches located in the 5' UTR of the messenger RNA (mRNA) regulate translation through variation of the accessibility of the ribosome binding site (RBS). These are the result of conformational changes in the riboswitch RNA governed by ligand binding. Here, we use a combination of single-molecule colocalization techniques (Single-Molecule Kinetic Analysis of RNA Transient Structure (SiM-KARTS) and Single-Molecule Kinetic Analysis of Ribosome Binding (SiM-KARB)) and microscale thermophoresis (MST) to investigate the adenine-sensing riboswitch in Vibrio vulnificus, focusing on the changes of accessibility between the ligand-free and ligand-bound states. We show that both methods faithfully report on the accessibility of the RBS within the riboswitch and that both methods identify an increase in accessibility upon adenine binding. Expanding on the regulatory context, we show the impact of the ribosomal protein S1 on the unwinding of the RNA secondary structure, thereby favoring ribosome binding even for the apo state. The determined rate constants suggest that binding of the ribosome is faster than the time required to change from the ON state to the OFF state, a prerequisite for efficient regulation decision.

Corrigendum: Time‐Resolved CIDNP as a Tool for Determination of Rate Constants of Triplet Quenching Using the Example of Photo‐Induced Oxidation of Histidine‐Containing Compounds

Corrigendum: Time‐Resolved CIDNP as a Tool for Determination of Rate Constants of Triplet Quenching Using the Example of Photo‐Induced Oxidation of Histidine‐Containing Compounds

Boosted photocatalytic accomplishment of 3D/2D hierarchical structured Bi4O5I2/g-C3N4 p-n type direct Z-scheme heterojunction towards synchronous elimination of Cr(VI) and tetracycline

The threats posed by heavy metal ions and antibiotics present in natural aqueous environments have been a serious cause of concern across the globe. The synchronous elimination of these contaminants through visible light responsive semiconductor mediated photocatalysis is a suitable strategy to solve this problem. However, designing proficient photocatalysts for the said purpose is a crucial task. Herein, hierarchical 3D/2D architectures of Bi4O5I2/g-C3N4 p-n type direct Z-scheme heterojunction photocatalysts (BOCNs) were fabricated by a two-step solvothermal-calcination approach. The characterisation of BOCNs by XRD, FTIR, XPS, SEM, TEM, HRTEM, LSV and MS techniques corroborated the robust heterojunction formation between Bi4O5I2 and g-C3N4. The presence of g-C3N4 and application of high treatment temperature (400 °C) assisted the formation of BiOC bond which is responsible for the development of an intimate interfacial interaction in BOCN. The heterostructured photocatalyst (BOCN3) demonstrated higher rate constant (kCr(VI)/synchronous) of 0.068 min−1 for Cr(VI) detoxification and that (kTCH/synchronous) of 0.075 min−1 for TCH degradation synchronously with respect to the reported values. The determined rate constants are about 1.8 folds greater than those were observed in isolated systems. The expedited photocatalytic activity can be ascribed to its wide visible light response, minimum charge recombination rate and increased redox ability. These are resulted from the synergistic effect of hierarchical 3D/2D architecture construction, existence of strong BiOC interfacial bond, p-n heterojunction formation and prevalence of direct Z-scheme charge transfer principle. The synchronous elimination of Cr(VI) and TCH over BOCN3 up to the fifth consecutive cycle without any appreciable change in photoactivity signified its enhanced stability and reusability. The plausible mechanism for the spectacular photocatalytic performance of BOCN3 was proposed.

NIR phosphorescence from decatungstate anions allows the conclusive characterization of its elusive excited triplet behaviour and kinetics.

The characterization of the triplet state of decatungstate (3DT*) and its NIR phosphorescence with lifetimes ∼100 ns in acetonitrile allow the easy determination of rate constants that are key to understanding its role in catalysis. The absence of oxygen quenching can now be understood as the excitation energy of 3DT* is lower than the energy of singlet oxygen.

Quantitative structure-activity relationships for the reaction kinetics of trace organic contaminants with one-electron oxidants.

Understanding the reactivity between trace organic contaminants (TrOCs) and radicals involved in advanced oxidation processes (AOPs) is necessary for a good process design, but the experimentally determined rate constants (k values) are not sufficient for numerous artificial TrOCs. Thus, the development of quantitative structure-activity relationships (QSARs) for predicting k values may be an effective way to address this limitation. In this work, we developed QSARs for the reactions of TrOCs with AOP-related one-electron oxidants. Specifically, 15 QSARs using Hammett constants and 8 cross-correlations were developed based on the k values of over 400 reactions between TrOCs (most contain electron-rich moieties, such as phenol, aniline, and alkoxy benzene) and 5 one-electron oxidants (SO4˙-, Br˙, Br2˙-, Cl2˙-, and CO3˙-). Overall, the developed QSARs show a good predictive performance with 94% (237/251, for Hammett constant-based QSARs) and 80% (218/274, for cross-correlations) of the k values predicted within a factor of 3. All the Hammett constant-based QSARs show negative slope values and all cross-correlations show positive relationships, suggesting all 5 one-electron oxidants mainly share similar electrophilic mechanisms with the TrOCs highlighted in this work. Previous QSAR studies on the k values of one-electron oxidants were compared and integrated into their model analysis. Furthermore, k values predicted herein from the QSARs were used to evaluate the degradation of TrOCs during UV/persulfate and UV/chlorine treatment in multiple wastewater matrices, which were demonstrated to be useful. Finally, remarks on the use of the developed QSARs were presented.

Understanding heterogeneous growth mechanisms at graphene edges: a theoretical study on acetylene deposition and mechanistic analysis

DFT and CI-NEB are used to investigate potential energy surfaces and determine rate constants of C2H2 deposition on graphene edges. Chemical lumping enables implementation of the proposed rate constants in pyrocarbon deposition kinetic models.

Kinetic features of solvent extraction by N,O-donor ligands of f-elements: a comparative study of diamides based on 1,10-phenanthroline and 2,2'-bipyridine.

A variant of microfluidic setup design for the study of extraction kinetics has been proposed. Mass transfer constants for Am(III) and Eu(III) and observed rate constants were obtained for N-,O-donor ligands featuring phenanthroline and bipyridyl cores. The possibility of determining rate constants for cations independently of each other makes it possible to observe the kinetic effect of separation. The extraction rate was found to be lower for the bipyridyl ligand, compared to phenanthroline. The values of the rotation barriers for the ligands were calculated using the DFT method. The values correlate with the obtained low extraction rate for the bipyridyl ligand. Also, crystallographic data showing anti-conformation for the bipyridyl ligand align with the kinetic data. Surface tension was also determined for the systems with the studied ligands. It is shown that at equal ligand concentrations, the value of surface tension agrees with the extraction rate. Furthermore, it is shown that for the bipyridyl ligand, prior contact of the organic phase with nitric acid significantly affects the surface tension.

Kinetic study of the hydrolysis of ester with mineral acid by spectrophotometer at different temperature

To determine the kinetic parameters and activation energy of the hydrolysis of ethyl acetate with hydrochloric acid monitored by spectrophotometry. The first order fits were automatically drawn and the values of the first order rate constants (k) were calculated using standard equations as part of the program. Acidic hydrolysis of ethyl acetate is essentially an irreversible and first order reaction whereas alkaline hydrolysis is an irreversible and second order reaction. Rate of reaction is the change in the number of molecules of reacting species per unit volume per unit time. In this hydrolysis of ethyl acetate with hydrochloric acid to accelerate the reaction mixture. A simple and sensitive kinetic spectrophotometric method presented for the determination of rate constant, order of reaction and activation energy. This method based on a kinetic investigation of ethyl acetate and hydrochloric acid at 35°C and 45°C temperature. The reaction followed spectrophotometrically by measuring the absorbance at 500 nm as a function of time. The initial rate and fixed time methods utilized for construction of calibration graphs successfully for the determination of rate constant, order of reaction and activation energy. The rate constant after calculation from the graphs was approximately k1 ≈ 0.00260 Sec-1 k2 ≈ 0.00322 Sec-1 by titration and spectrophotometric method respectively, order of reaction found to be first order and the activation energy for this reaction is 17.44 kJ/mol. One factor that influences the absorbance of a sample is the concentration (c). As the concentration increases, more radiation is absorbed and the absorbance increase. Therefore, the absorbance is directly proportional to the concentration.

Scavenging of Cation Radicals of the Visual Cycle Retinoids by Lutein, Zeaxanthin, Taurine, and Melanin.

In the retina, retinoids involved in vision are under constant threat of oxidation, and their oxidation products exhibit deleterious properties. Using pulse radiolysis, this study determined that the bimolecular rate constants of scavenging cation radicals of retinoids by taurine are smaller than 2 × 107 M-1s-1 whereas lutein scavenges cation radicals of all three retinoids with the bimolecular rate constants approach the diffusion-controlled limits, while zeaxanthin is only 1.4-1.6-fold less effective. Despite that lutein exhibits greater scavenging rate constants of retinoid cation radicals than other antioxidants, the greater concentrations of ascorbate in the retina suggest that ascorbate may be the main protectant of all visual cycle retinoids from oxidative degradation, while α-tocopherol may play a substantial role in the protection of retinaldehyde but is relatively inefficient in the protection of retinol or retinyl palmitate. While the protection of retinoids by lutein and zeaxanthin appears inefficient in the retinal periphery, it can be quite substantial in the macula. Although the determined rate constants of scavenging the cation radicals of retinol and retinaldehyde by dopa-melanin are relatively small, the high concentration of melanin in the RPE melanosomes suggests they can be scavenged if they are in proximity to melanin-containing pigment granules.

Quantitative Analysis of 2D EXSY NMR Spectra of Strongly Coupled Spin Systems in Transmembrane Exchange.

Solute translocation by membrane transport proteins is a vital biological process that can be tracked, on the sub-second timescale, using nuclear magnetic resonance (NMR). Fluorinated substrate analogues facilitate such studies because of high sensitivity of 19 F NMR and absence of background signals. Accurate extraction of translocation rate constants requires precise quantification of NMR signal intensities. This becomes complicated in the presence of J-couplings, cross-correlations, and nuclear Overhauser effects (NOE) that alter signal integrals through mechanisms unrelated to translocation. Geminal difluorinated motifs introduce strong and hard-to-quantify contributions from non-exchange effects, the nuanced nature of which makes them hard to integrate into data analysis methodologies. With analytical expressions not being available, numerical least squares fitting of theoretical models to 2D spectra emerges as the preferred quantification approach. For large spin systems with simultaneous coherent evolution, cross-relaxation, cross-correlation, conformational exchange, and membrane translocation between compartments with different viscosities, the only available simulation framework is Spinach. In this study, we demonstrate GLUT-1 dependent membrane transport of two model sugars featuring CF2 and CF2 CF2 fluorination motifs, with precise determination of translocation rate constants enabled by numerical fitting of 2D EXSY spectra. For spin systems and kinetic networks of this complexity, this was not previously tractable.