Kinetic Analysis Research Articles

Hydrolysis of Nerve Agent Simulants Accelerated by Stimuli-Responsive Dinuclear Catalysts.

The ability to control the catalytic activity of enzymes in chemical transformations is essential for the design and development of artificial catalysts. Herein, we report the synthesis and characterization of functional ligands featuring two 1,4,7,10-tetraazacyclododecane units linked by an azobenzene group and their corresponding dinuclear Zn(II) complexes. We show that the configuration switching (E/Z) of the azobenzene spacer in the ligands and their dinuclear Zn(II) complexes is reversibly controlled by irradiation with UV and visible light. The Zn(II)-metal complexes are light-responsive catalysts for the hydrolytic cleavage of nerve agent simulants, i.e., p-nitrophenyl diphenyl phosphate and methyl paraoxon. The catalytic activity of the Z-isomers of the dinuclear Zn(II) complexes outperformed that of the E-counterparts. Moreover, combining the less active E-isomers with gold nanoparticles induced an enhancement in the hydrolysis rate of p-nitrophenyl diphenyl phosphate. Kinetic analysis has shown that the catalytic site appears to involve a single metal ion. We explain our results by considering the different desolvation effects occurring in the catalyst's configurations in the solution and the catalytic systems involving gold nanoparticles.

Molecular Cloning, Expression and Enzymatic Characterization of Tetrahymena thermophila Glutathione-S-Transferase Mu 34.

Glutathione-S-transferase enzymes (GSTs) are essential components of the phase II detoxification system and protect organisms from oxidative stress induced by xenobiotics and harmful toxins such as 1-chloro-2,4-dinitrobenzene (CDNB). In Tetrahymena thermophila, the TtGSTm34 gene was previously reported to be one of the most responsive GST genes to CDNB treatment (LD50 = 0.079mM). This study aimed to determine the kinetic features of recombinantly expressed and purified TtGSTm34 with CDNB and glutathione (GSH). TtGSTm34-8xHis was recombinantly produced in T. thermophila as a 25-kDa protein after the cloning of the 660-bp full-length ORF of TtGSTm34 into the pIGF-1 vector. A three-dimensional model of the TtGSTm34 protein constructed by the AlphaFold and PyMOL programs confirmed that it has structurally conserved and folded GST domains. The recombinant production of TtGSTm34-8xHis was confirmed by SDS‒PAGE and Western blot analysis. A dual-affinity chromatography strategy helped to purify TtGSTm34-8xHis approximately 3166-fold. The purified recombinant TtGSTm34-8xHis exhibited significantly high enzyme activity with CDNB (190µmol/min/mg) as substrate. Enzyme kinetic analysis revealed Km values of 0.68mM with GSH and 0.40mM with CDNB as substrates, confirming its expected high affinity for CDNB. The optimum pH and temperature were determined to be 7.0 and 25°C, respectively. Ethacrynic acid inhibited fully TtGSTm34-8xHis enzyme activity. These results imply that TtGSTm34 of T. thermophila plays a major role in the detoxification of xenobiotics, such as CDNB, as a first line of defense in aquatic protists against oxidative damage.

Mechanism of Z-Selective Allylic Functionalization via Thianthrenium Salts.

A detailed mechanistic study of the Z-selective allylic functionalization via thianthrenium salts is presented. Kinetic analyses, deuterium labeling experiments, and computational methods are used to rationalize the observed reactivity and selectivity. We find that the reaction proceeds via a rate-determining and stereodetermining allylic deprotonation of an alkenylthianthrenium species. The Z-configuration of the resultant allylic ylide is translated into the Z-allylic amine product through a sequence of subsequent fast and irreversible steps: protonation to form a Z-allylic thianthrenium electrophile and then regioselective substitution by the nucleophile. In the stereodetermining deprotonation step, computational studies identified a series of stabilizing nonbonding interactions in the Z-alkene-forming transition state that contribute to the stereoselectivity.

Glass transition and crystallization of Se95Te5 chalcogenide glassy semiconductor

The study is dedicated to the investigation of thermo-physical characteristics of Se95Te5 chalcogenide glassy semiconductor during its glass formation and crystallization processes, employing various scanning rates of 5, 10, 15 and 20 K/min in non-isothermal modes through DSC measurement. Analysis of the structural relaxation kinetics involves the Kissinger’s, Augis and Bennett's, as well as Matusita’s approaches. Experimental data yield contains the determination of crucial parameters such as glass transition (𝑇𝑇𝑔𝑔), crystallization(𝑇𝑇𝑐𝑐), and melting temperatures alongside factors like reduced temperature of glass transition (𝑇𝑇𝑟𝑟𝑟𝑟), Hruby’s parameter (𝐾𝐾𝑔𝑔𝑔𝑔), fragility index (𝐹𝐹𝑖𝑖), Avrami exponents (n, m), glass transition (140.24 kJ/mol) and crystallization (Ec = 95.11 kJ/mol) energies, respectively. The results confirm that Se95Te5 chalcogenide system as an efficient glass former. Matusita’s method reveals that the crystallization mechanism (n = 2.51, m = 1.9) corresponds to volumetric nucleation with two-dimensional growth.

Essential amino acid residues and catalytic mechanism of trans-epoxysuccinate hydrolase for production of meso-tartaric acid.

This study aimed to discuss the essential amino acid residues and catalytic mechanism of trans-epoxysuccinate hydrolase from Pseudomonas koreensis for the production of meso-tartaric acid. The optimum conditions of the enzyme were 45°C and pH 9.0, respectively. It was strongly inhibited by Zn2+, Mn2+ and SDS. Michaelis-Menten enzyme kinetics analysis gave a Km value of 3.50mM and a kcat of 99.75s-1, with an exceptional EE value exceeding 99.9%. Multiple sequence alignment and homology modeling revealed that the enzyme belonged to MhpC superfamily and possessed a typical α/β hydrolase folding structure. Site-directed mutagenesis indicated H34, D104, R105, R108, D128, Y147, H149, W150, Y211, and H272 were important catalytic residues. The 18O-labeling study suggested the enzyme acted via two-step catalytic mechanism. The structure and catalytic mechanism of trans-epoxysuccinate hydrolase were first reported. Ten residues were critical for its catalysis and a two-step mechanism by an Asp-His-Asp catalytic triad was proposed.

Non-isothermal Kinetic Analysis of High Temperature Oxidation of Additively Manufactured Ti-6Al-4V Alloy

Non-isothermal Kinetic Analysis of High Temperature Oxidation of Additively Manufactured Ti-6Al-4V Alloy

Influence of Ti-incorporated Zeolite Topology and Pore Condensation on Vapor Phase Propylene Epoxidation Kinetics with Gaseous H2O2.

Vapor-phase propylene (C3H6) epoxidation kinetics with hydrogen peroxide (H2O2) strongly reflects the physical properties of Ti-incorporated zeolite catalysts and the presence of spectating molecules ("solvent") near active sites even without a bulk liquid phase. Steady-state turnover rates of C3H6 epoxidation and product selectivities vary by orders of magnitudes, depending on the zeolite silanol ((SiOH)x) density, pore topology (MFI, *BEA, FAU), and the quantity of condensed acetonitrile (CH3CN) molecules nearby active sites, under identical reaction mechanisms sharing activated H2O2 intermediates on Ti surfaces. Individual kinetic analyses for propylene oxide (PO) ring-opening, homogeneous diol oxidative cleavage, and homogeneous aldehyde oxidation reveal that secondary reaction kinetics following C3H6 epoxidation responds more sensitively to the changes in zeolite physical properties and pore condensation with CH3CN. Thus, higher PO selectivities achieved in hydrophilic Ti-MFI at steady-state reflect the preferential stabilization of transition states for C3H6 epoxidation (a primary reaction) relative to PO ring-opening and oxidative cleavage (secondary reactions) that solvation effects that reflect interactions among condensed CH3CN within pores and the extended pore structure.

Influence of Ti‐incorporated Zeolite Topology and Pore Condensation on Vapor Phase Propylene Epoxidation Kinetics with Gaseous H2O2

Vapor‐phase propylene (C3H6) epoxidation kinetics with hydrogen peroxide (H2O2) strongly reflects the physical properties of Ti‐incorporated zeolite catalysts and the presence of spectating molecules (“solvent”) near active sites even without a bulk liquid phase. Steady‐state turnover rates of C3H6 epoxidation and product selectivities vary by orders of magnitudes, depending on the zeolite silanol ((SiOH)x) density, pore topology (MFI, *BEA, FAU), and the quantity of condensed acetonitrile (CH3CN) molecules nearby active sites, under identical reaction mechanisms sharing activated H2O2 intermediates on Ti surfaces. Individual kinetic analyses for propylene oxide (PO) ring‐opening, homogeneous diol oxidative cleavage, and homogeneous aldehyde oxidation reveal that secondary reaction kinetics following C3H6 epoxidation responds more sensitively to the changes in zeolite physical properties and pore condensation with CH3CN. Thus, higher PO selectivities achieved in hydrophilic Ti‐MFI at steady‐state reflect the preferential stabilization of transition states for C3H6 epoxidation (a primary reaction) relative to PO ring‐opening and oxidative cleavage (secondary reactions) that solvation effects that reflect interactions among condensed CH3CN within pores and the extended pore structure.

Aluminum Removal from Rare Earth Chloride Solution through Regulated Hydrolysis via Electrochemical Method

Due to the coexistence of Al3+ and RE3+ and their similar properties, the separation of aluminum from rare earths is difficult. In this study, selective precipitation was used to separate aluminum from rare earth chloride solution via electrochemical regulated hydrolysis. By controlling the current density and electrolytic time, the rate of hydroxyl ion production was regulated, and the selective separation of rare earth and aluminum was realized according to the different precipitation sequences. By altering the temperature, current density, pH value, and other parameters, the separation performance of aluminum from rare earth in mixed rare earth chloride systems was systematically investigated. The removal rate of aluminum reached 88.35%, and the loss rate of rare earth was only 5.99% under optimized conditions. Compared with traditional neutralization hydrolysis, the new process showed higher efficiency and lower rare earth loss rate. Furthermore, a kinetic analysis of aluminum precipitation revealed that the reaction adhered to pseudo-first order kinetics. Additionally, the precipitate obtained via separation and filtration was amorphous alumina hydroxide with a small amount of rare earth attached. No reagent was consumed for the new process, which was more efficient and cleaner, providing a new idea for removing aluminum impurities from rare earth solutions.

Integrated Metabolomic and Transcriptomic Analysis Reveals the Underlying Antibacterial Mechanisms of the Phytonutrient Quercetin-Induced Fatty Acids Alteration in Staphylococcus aureus ATCC 27217

The utilization of natural products in food preservation represents a promising strategy for the dual benefits of controlling foodborne pathogens and enhancing the nutritional properties of foods. Among the phytonutrients, flavonoids have been shown to exert antibacterial effects by disrupting bacterial cell membrane functionality; however, the underlying molecular mechanisms remain elusive. In this study, we investigated the effect of quercetin on the cell membrane permeability of Staphylococcus aureus ATCC 27217. A combined metabolomic and transcriptomic approach was adopted to examine the regulatory mechanism of quercetin with respect to the fatty acid composition and associated genes. Kinetic analysis and molecular docking simulations were conducted to assess quercetin’s inhibition of β-ketoacyl-acyl carrier protein reductase (FabG), a potential target in the bacterial fatty acid biosynthesis pathway. Metabolomic and transcriptomic results showed that quercetin increased the ratio of unsaturated to saturated fatty acids and the levels of membrane phospholipids. The bacteria reacted to quercetin-induced stress by attempting to enhance fatty acid biosynthesis; however, quercetin directly inhibited FabG activity, thereby disrupting bacterial fatty acid biosynthesis. These findings provide new insights into the mechanism of quercetin’s effects on bacterial cell membranes and suggest potential applications for quercetin in bacterial inhibition.

A high-throughput lysosome trafficking assay guides ligand selection and elucidates differences in CD22-targeted nano-delivery

ABSTRACT Targeted nanoparticles offer potential to selectively deliver therapeutics to cells, however, their subcellular fate following endocytosis must be understood to properly design mechanisms of drug release. Here we describe a nanoparticle platform and associated cell-based assay to observe lysosome trafficking of targeted nanoparticles in live cells. The nanoparticle platform utilizes two fluorescent dyes loaded onto PEG-poly(glutamic acid) and PEG-poly(Lysine) block co-polymers that also comprise azide reactive handles on PEG termini to attach antibody-based targeting ligands. Fluorophores were selected to be pH-sensitive (pHrodo Red) or pH-insensitive (Alexafluor 488) to report when nanoparticles enter low pH lysosomes. Dye-labelled block co-polymers were further assembled into polyion complex micelle nanoparticles and crosslinked through amide bond formation to form stable nano-scaffolds for ligand attachment. Cell binding and lysosome trafficking was determined in live cells by fluorescence imaging in 96-well plates and quantification of red- and green-fluorescence signals over time. The platform and assay was validated for selection of optimal antibody-derived targeting ligands directed towards CD22 for nanoparticle delivery. Kinetic analysis of uptake and lysosome trafficking indicated differences between ligand types and the ligand with the highest lysosome trafficking efficiency translated into effective DNA delivery with nanoparticles bearing the optimal ligand.

CO-assisted partial oxidation of methane and selective C1 oxygenate formation using iridium-ZSM-5 catalyst

Abstract The direct partial oxidation of methane to oxygenates remains challenging. Here, CO-assisted methane conversion was investigated using an Ir-ZSM-5 catalyst, and it achieved higher C1 selectivity compared with that achieved using a model Rh-ZSM-5 catalyst. A plausible reaction sequence is proposed via kinetic analysis, and the differences between the two catalysts were revealed.

Preparation and Adsorption Performance of Boron Adsorbents Derived from Modified Waste Feathers

This research focuses on modifying discarded feathers by grafting glycidyl methacrylate (GMA) onto their surface through thiolation, followed by an epoxy ring-opening reaction with N-methyl-D-glucamine (NMDG) to synthesize feather-based boron adsorbents. Optimization of the adsorbent preparation conditions was achieved through single-factor experiments, varying temperature, time, GMA concentration, and initiator dosage. The synthesized adsorbent (F-g-GMA-NMDG) underwent characterization using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and X-ray diffraction (XRD). The adsorption behavior of the adsorbent was studied, and its boron adsorption capacity at different temperatures was determined through static adsorption kinetic curves. Analysis of adsorption isotherms, kinetics, and thermodynamics was conducted. Results indicate that the boron adsorption process by F-g-GMA-NMDG follows a pseudo-second-order model. The adsorption process is endothermic, with higher temperatures promoting adsorption efficiency. Gibbs free energy (ΔG) confirms the spontaneity of the adsorption process. Enhanced adsorption efficacy was observed under neutral and acidic pH conditions. After four cycles, the adsorbent maintained its adsorption efficiency, demonstrating its stability and potential for reuse. This study provides novel insights into both the treatment of discarded feathers and the development of boron adsorbents.

Electropolymerization of a Carbonyl-Modified Dihydropyrazine Derivative for Aqueous Zinc Batteries with Ultrahigh Cycling Stability.

The design of aqueous zinc-ion batteries (ZIBs) that have high specific capacity and long-term stability is essential for future large-scale energy storage systems. Cathode materials with extended π-conjugation and abundant active sites are desirable to enhance the charge storage performance and the cycling stability of the aqueous ZIB. Based on this concept, 6,9-dihydropyrazino[2,3-g]quinoxaline-2,3,7,8(1H,4H)-tetrone was chosen as the monomer to be electropolymerized onto carbon cloth (PDHPQ-Tetrone/CC). When used as the cathode material for aqueous ZIBs, an exceptional cycling life (>20,000 cycles) at a current density of 10 A g-1 was achieved, with the specific capacity maintained at 82.8% and with the Coulombic efficiency at around 100% throughout cycling. At the charge-discharge current density of 0.1 A g-1, the ZIB with PDHPQ-Tetrone/CC achieved a high specific capacity of 248 mAh g-1. Kinetic analyses showed that both surface-capacitive-controlled processes and semi-infinite diffusion-controlled processes contribute to the stored charge. The charge storage mechanism was investigated with ex situ characterizations and involves the redox processes of carbonyl/hydroxyl and amino/imino groups coupled with insertion and extraction of both Zn2+ and H+.

Novel chitosan-modified biochar prepared from a Chinese herb residue for multiple heavy metals removal: Characterization, performance and mechanism

In this study, the sorption properties of Cr(VI), As(III), and Pb(II) on chitosan-modified magnetic biochar (CMBC) derived from residues of Ligusticum chuanxiong Hort. were investigated. CMBC was found to be a valuable material for removing three heavy metals from water simultaneously. Kinetic analysis suggested Cr(VI), As(III), and Pb(II) were chemisorbed onto CMBC, while isotherm data conformed well to Langmuir model, the maximum adsorption capacity of CMBC was found to be 65.74 mg/g for Cr(VI), 49.32 mg/g for As(III), and 69.45 mg/g for Pb(II). Experiments, characterization, and density functional theory (DFT) calculations were employed to explore the mechanisms. Furthermore, CMBC demonstrated excellent removal rates of over 95% for Cr(VI), 99% for As(III) and Pb(II) from contaminated water bodies. This work shows that CMBC holds significant potential for wastewater treatment of heavy metals and provides an effective solution for the utilization of Chinese herb residues in environmental remediation.

Kinetics Parameters Estimation for the Coupled Neutron-Photon Point Kinetics Model in Monte Carlo Eigenvalue Calculations

The delayed photoneutron effect should be considered in the point kinetics equation (PKE) applied to D2O and beryllium-moderated or -reflected systems because of its importance on reactor kinetics. This paper proposes neutron-photon-coupled PKE with a clear definition of adjoint-weighted kinetics parameters after providing the mathematical derivation from the neutron and photon transport and precursor equations. The Monte Carlo algorithms to estimate the kinetics parameters are induced from their definition and implemented in the eigenvalue calculation module of McCARD. They are verified through homogeneous infinite-medium problems with few-group neutron and photon cross sections by comparing with analytic solutions. The proposed PKE and kinetics parameters estimation methods are applied for the kinetics analyses of the artificial control rod drop transient problem in the RB reactor. Photonuclear physics is also implemented in a time-dependent Monte Carlo simulation to calculate the reference data of neutron amplitude in the core to be compared with the PKE results. As good agreement is shown in the neutron amplitude, it is validated that the developed PKE is capable of predicting the reactor kinetics considering photoneutrons.

Drying kinetic, thermodynamic and quality analyses of infrared drying of truffle slices.

Kinetic and thermodynamic parameters are the most important part for making a suitable tool for drying agricultural products. Moreover, calculation of the energy required for the drying of product, the properties of the rehydration ratio, the food appearance changes, and the evaluation of the microstructure of food are crucial. Since the thermodynamic properties of truffle slices have not yet been reported, this study aims to establish a mathematical model to describe drying process of agriculture product, evaluate the effective moisture diffusion coefficient (Deff), determining the activation energy (Ea) to elucidate the thermodynamic characteristics, measure color characteristics, and rehydration ratio (RR) during the drying process of truffle slices. Truffle slices were dried in an infrared (IR) dryer at four temperatures of 50-80°C and two thicknesses of 0.5 and 1cm. The best model to describe the drying process of truffle slices was Midilli etal.'s model. The value of Deff, SEC, and RR were in the range of 3.06 × 10-8 to 2.48 × 10-7 m2/s, 79.68-191.271kWh/kg, and 5.99-7.49, respectively. The Deff of truffle slices increased with the above-mentioned parameters of the samples. The Ea obtained was 26.62-27.43kJ/mol. The results indicated that enthalpy and entropy decreased with increasing drying temperature, while Gibbs free energy improved. The enthalpy, entropy, and Gibbs free energy values changed between 24.48-25.28kJ/mol, -130.47 to -122.63 J/mol °K, and 63.97-70.17kJ/mol, respectively. In addition, the results of color attributes decreased with increasing temperature, while chroma oppositely increased.

Harnessing cardiac power: Heart kinetic motion analysis for energy harvesters

Accurately estimating the complex motion of the heart can unlock enormous potential for kinetic energy harvesting. This paper presents a foundational dataset for heart kinetic motion through in-vivo tests and investigates the most influential factors in heart kinetic motion. In-vivo tests on a living pig's heart, with signal processing, were carried out to study the heart movement by heart beating and respiration motions. A network of nine points on the heart was employed for in vivo measurements. These measurements illustrated the kinetic energy signals in displacement, velocity, and acceleration. The results indicated that the motion level varies in distinct locations over epicardium. The statistical features and autocorrelations were reported for these points, illustrating the highest displacement and acceleration. Each heartbeat generated an energy of 14.35 mJ and a power of 1.03 W. However, this available energy is not uniformly distributed. The results illustrated that not only is cardiac movement location-dependent, but the speed of cardiac displacement cycles is also location-dependent. The right atrium has the highest cardiac kinetic movement with an amplitude of 16.19 mm displacement and 16.3 m/s2 acceleration. To evaluate the energy harvesting possibility from the heart's motion, a piezoelectric energy harvester was simulated by the finite element method, implying that the energy harvesting level significantly depends on implant location over epicardium. The results of this study open the potential of designing novel energy harvesters based on accurate heart movements and provide a foundation for future investigations of energy harvesting for leadless pacemaker energy systems.

Increased Prolylcarboxypeptidase Expression Can Serve as a Biomarker of Senescence in Culture

Prolylcarboxypeptidase (PRCP, PCP, Lysosomal Pro-X-carboxypeptidase, Angiotensinase C) controls angiotensin- and kinin-induced cell signaling. Elevation of PRCP appears to be activated in chronic inflammatory diseases [cardiovascular disease (CVD), diabetes] in proportion to severity. Vascular endothelial cell senescence and mitochondrial dysfunction have consistently been shown in models of CVD in aging. Cellular senescence, a driver of age-related dysfunction, can differentially alter the expression of lysosomal enzymes due to lysosomal membrane permeability. There is a lack of data demonstrating the effect of age-related dysfunction on the expression and function of PRCP. To explore the changes in PRCP, the PRCP-dependent prekallikrein (PK) pathway was characterized in early- and late-passage human pulmonary artery endothelial cells (HPAECs). Detailed kinetic analysis of cells treated with high molecular weight kininogen (HK), a precursor of bradykinin (BK), and PK revealed a mechanism by which senescent HPAECs activate the generation of kallikrein upon the assembly of the HK–PK complex on HPAECs in parallel with an upregulation of PRCP and endothelial nitric oxide (NO) synthase (eNOS) and NO formation. The NO production and expression of both PRCP and eNOS increased in early-passage HPAECs and decreased in late-passage HPAECs. Low activity of PRCP in late-passage HPAECs was associated with rapid decreased telomerase reverse transcriptase mRNA levels. We also found that, with an increase in the passage number of HPAECs, reduced PRCP altered the respiration rate. These results indicated that aging dysregulates PRCP protein expression, and further studies will shed light into the complexity of the PRCP-dependent signaling pathway in aging.

Comprehensive Wheat Straw Processing with Deep Eutectic Solvent to Deliver Reducing Sugar

AbstractPretreatment is one of the bottlenecks in the cost and energy-efficient biomass valorization. Deep eutectic solvents are potential candidates for being used to address these challenges. In this work, the deep eutectic solvent composed of choline chloride, and acetic acid was studied for its use in wheat straw fractionation. The pretreated biomass was assessed concerning the lignin and glucan content. Under optimized time and temperature conditions, defined using Doehlert matrix chemometric tool, of 3 h 47 min and 139.6 °C, the processed wheat straw contained as much as 42.5 ± 0.42 wt.% and 38.59 ± 1.26 wt.% of glucan and lignin contents, respectively. The need for biomass washing after the pretreatment with deep eutectic solvents and before the enzymatic hydrolysis step was also evaluated. The obtained enzymatic hydrolysis results, i.e., glucan to glucose yield of 27.13 ± 0.25 vs. 25.73 ± 0.08 for washed or unwashed biomass correspondingly, are equally good substrates. Fractal kinetic analysis of the data showed similar values of k and h for both glucose and xylose reactions between washed and unwashed biomass. This confirmed that biomass washing is an unnecessary step, which in turn opens room for biomass processing intensification.