Kinetic Method Research Articles

Transient kinetics reveal the mechanism of competitive inhibition of the neutral amino acid transporter ASCT2

ASCT2 (alanine serine cysteine transporter 2), a member of the SLC1 (solute carrier 1) family, mediates Na+-dependent exchange of small neutral amino acids across cell membranes. ASCT2 was shown to be highly expressed in tumor cells, making it a promising target for anti-cancer therapies. In this study, we explored the binding mechanism of the high-affinity competitive inhibitor Lc-BPE with ASCT2, using electrophysiological and rapid kinetic methods. Our investigations reveal that Lc-BPE binding requires one or two Na+ ions initially bound to the apo-transporter with high affinity, with Na1 site occupancy being more critical for inhibitor binding. In contrast to the amino acid substrate bound form, the final, third Na+ ion cannot bind, due to distortion of its binding site (Na2), thus preventing the formation of a translocation-competent complex. Based on the rapid kinetic analysis, the application of Lc-BPE generated outward transient currents, indicating that, despite its net neutral nature, the binding of Lc-BPE in ASCT2 is weakly electrogenic, most likely because of asymmetric charge distribution within the amino acid moiety of the inhibitor. The pre-incubation with Lc-BPE also led to a decrease of the turnover rate of substrate exchange and a delay in the activation of substrate-induced anion current, indicating relatively slow Lc-BPE dissociation kinetics. Overall, our results provide new insight into the mechanism of binding of a prototypical competitive inhibitor to the ASCT transporters.

A reduced kinetic method for investigating non-local ion heat transport in ideal multi-species plasmas

A reduced kinetic method (RKM) with a first-principles collision operator is introduced in a 1D2V planar geometry and implemented in a computationally inexpensive code to investigate non-local ion heat transport in multi-species plasmas. The RKM successfully reproduces local results for multi-species ion systems and the important features expected to arise due to non-local effects on the heat flux are captured. In addition to this, novel features associated with multi-species, as opposed to single species, cases are found. Effects of non-locality on the heat flux are investigated in mass and charge symmetric and asymmetric ion mixtures with temperature, pressure, and concentration gradients. In particular, the enthalpy flux associated with diffusion is found to be insensitive to sharp pressure and concentration gradients, increasing its significance in comparison to the conductive heat flux driven by temperature gradients in non-local scenarios. The RKM code can be used for investigating other kinetic and non-local effects in a broader plasma physics context. Due to its relatively low computational cost it can also serve as a practical non-local ion heat flux closure in hydrodynamic simulations or as a training tool for machine learning surrogates.

Performance and Phase Change Kinetic Investigations on Capric-Myristic Acid Eutectic Mixtures for Energy-Saving Construction

In the present study, capric acid and myrisic acid were first selected to prepare a capric acid-myrisic acid eutectic mixture using a compounding method. Then, the thermal properties, structural stability and weight loss of capric acid-myrisic acid eutectic mixtures were analyzed using differential scanning calorimetry, Fourier transform infrared and thermogravimetry. Finally, the activation energy and reaction order of the capric acid-myrisic acid eutectic mixture during solid-liquid transformation were calculated using the phase change kinetic methods of Kissinger and Ozawa. The results indicate that capric acid-myrisic acid eutectic mixtures have good thermal cycle stability and stable energy storage in practical applications. The activation energies of capric acid-myrisic acid eutectic mixtures were calculated using the phase change kinetic methods of Kissinger and Ozawa, with values of 345.6 KJ/mol and 333.3 KJ/mol, respectively, indicating that both phase change kinetic methods have good accuracy.

Angiopoietin2 is associated with coagulation activation and tissue factor expression in extracellular vesicles in COVID-19.

Coagulation activation in immunothrombosis involves various pathways distinct from classical hemostasis, offering potential therapeutic targets to control inflammation-induced hypercoagulability while potentially sparing hemostasis. The Angiopoietin/Tie2 pathway, previously linked to embryonic angiogenesis and sepsis-related endothelial barrier regulation, was recently associated with coagulation activation in sepsis and COVID-19. This study explores the connection between key mediators of the Angiopoietin/Tie2 pathway and coagulation activation. The study included COVID-19 patients with hypoxia and healthy controls. Blood samples were processed to obtain platelet-free plasma, and frozen until analysis. Extracellular vesicles (EVs) in plasma were characterized and quantified using flow cytometry, and their tissue factor (TF) procoagulant activity was measured using a kinetic chromogenic method. Several markers of hemostasis were assessed. Levels of ANGPT1, ANGPT2, and soluble Tie2 correlated with markers of coagulation and platelet activation. EVs from platelets and endothelial cells were increased in COVID-19 patients, and a significant increase in TF+ EVs derived from endothelial cells was observed. In addition, ANGPT2 levels were associated with TF expression and activity in EVs. In conclusion, we provide further evidence for the involvement of the Angiopoietin/Tie2 pathway in the coagulopathy of COVID-19 mediated in part by release of EVs as a potential source of TF activity.

Technological Analysis of the Production of Nickel-Containing Composite Materials

The article presents the results of obtaining a composite material by sintering nickel-containing raw materials mixed with carbon-containing materials, namely using coke and semi-coke. The sintering process was performed at a charge layer height of 240 mm and the temperature of the lower layer was T = 1200 °C. The results of the sieve analysis showed (a fraction of 10 mm) that the yield of a suitable composite material using coke was 68.3% and with semi-coke 67.0%. The average nickel and chromium content in the composite materials was 1.42% and 3.07%, accordingly. As a result of determining the strength characteristics of the obtained composite materials with various reducing agents by dropping from a height of 2 m onto a steel pallet, it was found that the obtained composite materials have high mechanical properties in terms of strength of 81% and 89.2%. The results of the elemental composition at the studied points and the thermal analysis of the studied composite material are presented. The mineralogical composition of the composite material is presented in the form of serpentine and nontronite, and the empty rock is made of quartz and talc. The activation energy of thermal analysis by the method of non-isothermal kinetics were calculated. The results of experiments on the production of composite materials from nickel-containing raw materials will be recommended for obtaining the optimal composition of composite materials at the stage of pilot tests and industrial development of the developed technology for processing nickel ores of the Republic of Kazakhstan. For the processing of nickel-poor nickel ores, it is of great importance to obtain optimal technological and technical and economic indicators that ensure low cost of nickel in the resulting product.

Application of Model-Free and Model-Based Kinetic Methods in Evaluation of Reactions Complexity during Thermo-Oxidative Degradation Process: Case Study of [4-(Hydroxymethyl)phenoxymethyl] Polystyrene Resin

This work examined the possibilities and limitations of model-free and model-based methods related to decrypting the kinetic complexity of multi-step thermo-oxidative degradation processes (as a testing system, a [4-(hydroxymethyl)phenoxymethyl] polystyrene resin was used), monitored by thermal analysis (TGA-DTG-DTA) techniques. It was found that isoconversional methods could successfully determine the correct number of process stages and presence of multiple reactions based on derived Ea(α) profiles and identify the negative dependence of the rate constant on the temperature. These methods could not overcome the problem that arose due to mass transfer limitations. The model-based method overcame more successfully the problem associated with mass transfer because its calculation machinery had capabilities for the correct solution of the total mass balance equation. However, a perfect fit with the experimental data was not achieved due to the dependence on the thermal history of the contribution (ctb.) of a given reaction step inside a fitting procedure cycle. On the other hand, through this approach, it was possible to estimate the rate-controlling steps of the process regarding the influence of the heating rate. It was found that for consecutive reaction mechanisms, the production of benzaldehyde and gases in high yields was controlled by the heating rate, where low heating rates were strongly recommended (≤10 K/min). Also, it was shown that the transport phenomenon may be also the rate-determining step (within the set of “intrinsic” kinetic parameters). It was also established that external heat transfer controls the overall rate, where the “pure” kinetic control regime had not been reached but was approached when lowering the temperature and size of the resin particles.

Enantiodivergent kinetic resolution of 4-substituted 1,2,3,4-tetrahydroquinolines employing amine oxidase

Optically pure 1,2,3,4-tetrahydroquinolines (THQs) represent a class of important motifs in many natural products and pharmaceutical agents. While recent advances on redox biocatalysis have demonstrated the great potential of amine oxidases, all the transformations focused on 2-substituted THQs. The corresponding biocatalytic method for the preparation of chiral 4-substituted THQs is still challenging due to the poor activity and stereoselectivity of the available enzyme. Herein, we developed a biocatalytic kinetic resolution approach for enantiodivergent synthesis of 4-phenyl- or alkyl-substituted THQs. Through structure-guided protein engineering of cyclohexylamine oxidase derived from Brevibacterium oxidans IH-35 A (CHAO), the variant of CHAO (Y215H/Y214S) displayed improved specific activity toward model substrate 4-phenyl substituted THQ (0.14 U/mg, 13-fold higher than wild-type CHAO) with superior (R)-stereoselectivity (E > 200). Molecular dynamics simulations show that CHAO Y215H/Y214S allows a suitable substrate positioning in the expanded binding pocket to be facilely accessed, enabling enhanced activity and stereoselectivity. Furthermore, a series of 4-alkyl-substituted THQs can be transformed by CHAO Y215H/Y214S, affording R-isomers with good yields (up to 50 %) and excellent enantioselectivity (up to ee > 99 %). Interestingly, the monoamine oxidase from Pseudomonas fluorescens Pf0–1 (PfMAO1) with opposite enantioselectivity was also mined. Together, this system enriches the kinetic resolution methods for the synthesis of chiral THQs.

Evaluation of beta glucan test using kinetic turbidimetric method on toxinometer MT-6500 for detection of invasive fungal infections in hospitalized patients

Evaluation of beta glucan test using kinetic turbidimetric method on toxinometer MT-6500 for detection of invasive fungal infections in hospitalized patients

Kinetics and molecular modeling studies on the inhibition mechanism of GH13 α-glycosidases by small molecule ligands

Alpha-glucosidase inhibitors play an important role in Diabetes Mellitus (DM) treatment since they prevent postprandial hyperglycemia. The Glycoside Hydrolase family 13 (GH13) is the major family of enzymes acting on substrates containing α-glucoside linkages, such as maltose and amylose/amylopectin chains in starch. Previously, our group identified glycoconjugate 1H-1,2,3-triazoles (GCTs) inhibiting two GH13 α-glycosidases: yeast maltase (MAL12) and porcine pancreatic amylase (PPA). Here, we combined kinetic studies and computational methods on nine GCTs to characterize their inhibitory mechanism. They all behaved as reversible inhibitors, and kinetic models encompassed noncompetitive and various mechanisms of mixed-type inhibition for both enzymes. Most potent inhibitors displayed Ki values of 30 μM for MAL12 (GPESB16) and 37 μM for PPA (GPESB15). Molecular dynamics and docking simulations indicated that on MAL12, GPESB15 and GPESB16 bind in a cavity adjacent to the active site, while on the PPA, GPESB15 was predicted to bind at the entrance of the catalytic site. Notably, despite its putative location within the active site, the binding of GPESB15 does not obstruct the substrate's access to the cleavage site. Our study contributes to paving the way for developing novel therapeutic strategies for managing DM-2 through GH13 α-glycosidases inhibition.

Neutrophil to lymphocyte ratio (NLR) as a surrogate marker of diabetic nephropathy

Background and objectives: Diabetic nephropathy and retinopathy are microvascular complications of diabetes. Nephropathy is clinically manifested as an increase in urine albumin excretion. Total white blood cell count is a crude but sensitive indicator of inflammation and studied in many cardiac and non-cardiac diseases as an inflammatory marker such as acute myocardial infarction, stroke, and heart failure. In this study, the association of neutrophil to lymphocyte ratio (NLR) with diabetic nephropathy and retinopathy. Methods: This was a prospective observational study performed on patients with diabetic nephropathy +/- retinopathy. A total of v104 subjects diagnosed with 3type 2 diabetes mellitus registered in this study. NLR was calculated by analyzing differential leukocyte count in complete blood picture. Spot Albuminuria was tested by immune turbidimetry method. Urine creatinine was tested by jaffe’s kinetic method by which spot urine microalbumin to creatinine ratio is calculated. ANOVA, Independent t-test, chi-square test, Karl Pearson correlation were applied to find significance. P<0.05 was considered as statistically significant. Results: Totally 104 diabetic subjects were registered, 52 subjects had DN and 52 had normal urine albumin. Mean±SD NLR for a normal group is 2.5±1.1 and in DN group is 3.4±1.4 which was highly significant (P =0.001). Conclusion: Our study showed that there was a significant relation between NLR and DN; and positive correlation between NLR and urine microalbumin to creatinine ratio. Therefore, NLR may be considered as a novel surrogate marker of DN.

Influences of Sulfur-Containing Components on the Key Phases of FeS Spontaneous Combustion Dynamics

ABSTRACT In petroleum storage tanks, sulfur-containing crude oil continues to corrode equipment, generating sulfur corrosion products such as FeS. These products exhibit rapid exothermic reactions upon contact with air, thereby increasing the risk of fires and explosions. Additionally, sulfur monomers precipitated from sulfur or other compounds present in crude oil can adhere to FeS, consequently altering its spontaneous combustion characteristics. To explore the impact of associated sulfur content on the spontaneous combustion characteristics of FeS during its formation, this research synthesized FeS and its sulfur mixtures with sulfur concentrations of 5%, 10%, 15%, and 20%. These mixtures were prepared using a liquid-phase method, which involved the synthesis of self-made active FeS followed by the addition of different sulfur components. Differences in the spontaneous combustion characteristics of the five groups of samples were investigated in stages by simultaneous thermal analysis. The trends of the characteristic parameters of spontaneous combustion of FeS with different percentages of sulfur-containing components were analyzed. Finally, the apparent activation energy values of FeS with FeS and its associated sulfur were calculated by using thermodynamic analysis in the room-temperature spontaneous combustion stage (RT-75℃) and high temperature combustion stage (160–250℃). The findings indicate that the presence of sulfur components enhances the reactivity of FeS, yet reduces its oxygen absorption saturation threshold, thus advancing the oxygen absorption endpoint and facilitating entry into the high-temperature combustion stage. Moreover, FeS and its associated sulfur exhibit prolonged sustained combustion times when the sulfur component percentage is below 10%, favorably influencing the combustion behavior of FeS. As the percentage of sulfur component increases (from 10% to 20%), the combustion duration temperature rises from 60°C to 95°C. Additionally, an increase in the percentage of sulfur component (from 10% to 20%) leads to a higher combustion temperature. The activation energies of the five samples were determined using the Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) kinetic methods. During the room temperature spontaneous combustion stage, the activation energy increases from 65.05 kJ/mol to 112.44 kJ/mol as the percentage of sulfur component rises from 0% to 20%. During the high temperature combustion stage, the activation energy increased from 108.32 kJ/mol to 214.49 kJ/mol with the increase in the percentage of sulfur component. FeS and its associated sulfur necessitate energy to propel the process due to heat absorption from the melting of sulfur monomers. As the reaction progresses into the high temperature stage, the required activation energy escalates accordingly.

DUGKS-GPU: An efficient parallel GPU code for 3D turbulent flow simulations using Discrete Unified Gas Kinetic Scheme

This paper presents a parallel implementation of the Discrete Unified Gas Kinetic Scheme (DUGKS) on the GPU system using the CUDA Fortran and CUDA C++ programming languages. Firstly, we conducted an extensive revision of our original CPU-based code, resulting in a threefold decrease in memory usage. This new implementation is also paired with a novel approach to compute cell face flux using trilinear interpolation. It is shown analytically that the interpolation-based approach to flux calculation is more accurate compared to the one used in the original DUGKS. The initial simulation results using this new approach suggest that trilinear interpolation can reduce numerical errors on a coarse mesh. For example, in the case of the decaying Taylor-Green vortex flow at a 1283 mesh resolution, the relative numerical error in the energy dissipation rate at t⁎=2, using the spectral simulation result as the benchmark, is approximately 30% lower than that of the original implementation. The improved GPU DUGKS method is applied to laminar and turbulent flows in periodic and wall-bounded boundary configurations. A performance comparison of the GPU implementation is also presented and compared to the previous CPU implementation. A maximum speedup of 7.64x was achieved on a desktop-level GPU compared to a 32-core CPU. The strong scaling test, conducted on an eight-GPU node, demonstrated the efficient utilization of available multiple GPU resources by the code. Program summaryProgram Title: DUGKS-GPUCPC Library link to program files:https://doi.org/10.17632/yykv5s9g2n.1Developer's repository link:https://github.com/kairzhan/DUGKS-GPUCode Ocean capsule:https://codeocean.com/capsule/3b1e4f74-cdd3-4781-8923-8514d5923dfb/Licensing provisions: GNU General Public License 3Programming language: CUDA C++, CUDA FortranSupplementary material:Nature of problem: DUGKS-GPU is an advanced numerical code designed to accelerate the simulation of turbulent fluid flows through the application of the kinetic method known as the Discrete Unified Gas Kinetic Scheme (DUGKS). This computational tool comprises a CUDA Fortran version, tailored for a single GPU, as well as a CUDA C++ version developed for multi-GPU platforms.Solution method: The code employs a second-order finite-volume discretization of the discrete velocity Boltzmann equation with the BGK collision model. It can be used to simulate small to medium-scale problems on modern multi-GPU platforms with CUDA architecture.

Bonding of ceramics to silver-coated titanium-A combined theoretical and experimental study.

It would be very beneficial to have a method for joining of ceramics to titanium reliably. Although several techniques have been developed and tested to prevent extensive interfacial chemical reactions in titanium-ceramic systems, the main problem of the inherent brittleness of interfaces was still unsolved. To overcome this problem also in dental applications, we decided to make use of an interlayer material that needs to meet the following requirements: First, it has to be biocompatible, second, it should not melt below the bonding temperatures, and third, it should not react too strongly with titanium, so that its plasticity will be maintained. Considering possible material options only the metals: gold, platinum, palladium, and silver, fulfill the first and second requirements. To find out-without an extensive experimental testing program-which of the four metals fulfills the third requirement best, the combined thermodynamic and reaction kinetic modeling was employed to evaluate how many and how thick reaction layers are formed between the interlayer metals and titanium. With the help of theoretical modeling, it was shown that silver fulfills the last requirement best. However, before starting to test experimentally the effect of the silver layer on the mechanical integrity of dental ceramic/Ag/Ti joints it was decided to make use of mechanical analysis of the three-point bending test, the result of which indicated that the silver layer increases significantly the bond strength of the joints. This result encouraged us to develop a new technique for plating silver on titanium. Subsequently, we executed numerous three-point bending tests, which demonstrated that silver-plated titanium-ceramic joints are much stronger than conventional titanium-ceramic joints. Hence, it can be concluded that the combined thermodynamic, reaction kinetic, and mechanical modeling method can also be a very valuable tool in medical research and development work.

Modeling of water gas shift reaction using neural network trained on detailed kinetic mechanisms

For the optimization of a chemical reactor or its control, computational fluid dynamics (CFD) that considers accurate reaction models is effective. Although detailed kinetic mechanisms can accurately predict gas-phase reactions, integrating them with CFD is too computationally expensive. In contrast, global reactions have lower computational costs but significantly reduced accuracy outside of tuned conditions. This study proposes a method for constructing a model using a neural network to predict the reaction rate of water gas shift reaction based on detailed kinetic mechanisms. It includes techniques to avoid unrealistic solutions inherent to detailed kinetic mechanisms and methods to minimize biases in training data. The neural network input was log-transformed concentrations and inverse temperatures, and the output was the logarithm of the absolute value of the reaction rate and direction, enabling the prediction of bidirectional reactions over a wide temperature range. The quality of the dataset significantly impacted the accuracy of the neural network. Using a dataset with less bias in chemical species concentrations, the model achieved accuracy similar to detailed models while facilitating an over 400 times faster computation. The study also discussed the impact of temperature change rate, showing that at about 72 K/min, the detailed kinetic mechanism's solution can be accurately replicated. Still, at 720 K/min, the radical concentration deviates from the quasi-steady state, leading to discrepancies. This study opens up new possibilities for computational methods in the prediction and optimization of chemical reactions.

Thermal Stability, Durability, and Service Life Estimation of Woven Flax-Carbon Hybrid Polyamide Biocomposites.

Woven flax-carbon hybrid polyamide biocomposites offer a blend of carbon fibers' mechanical strength and flax's environmental advantages, potentially developing material applications. This study investigated their thermal behavior, degradation kinetics, and durability to water uptake and relative humidity exposure and compared them with pure flax and carbon composites with the same matrix. The hybrid composite exhibited intermediate water/moisture absorption levels between pure flax and carbon composites, with 7.2% water absorption and 3.5% moisture absorption. It also displayed comparable thermal degradation resistance to the carbon composite, effectively maintaining its weight up to 300 °C. Further analysis revealed that the hybrid composite exhibited a decomposition energy of 268 kJ/mol, slightly lower than the carbon composite's value of 288.5 kJ/mol, indicating similar thermal stability. Isothermal lifetime estimation, employing the activation energy (Ed) and degree of conversion facilitated by the Model Free Kinetics method, indicated a 41% higher service life of the hybrid laminate at room temperature compared to the carbon laminate. These insights are crucial for understanding the industrial applications of these materials without compromising durability.

Comparative analysis of kinetic model-fitting methods and selection priority for horse manure pyrolysis

The diverse origins of biomass wastes provide a constraint on the practical application of pyrolysis, as it leads to uncertain chemical reactions, feedstock conversion, and energy consumption. Various model-fit methods are available to identify the decomposition kinetics, however, limited studies have compared the reliability and accuracy of those kinetic models. This work compared five different kinetic models, two based on model-fit methods (Coats–Redfern (CR), Kennedy-Clark (KC) and three based on the application forms of Criado Master Plots (CMP I, CMP II and CMP III). The mass loss data from the pyrolysis of horse manure (HM) through a thermogravimetric analyser was used as a biomass sample for evaluation. Results demonstrated that all five model-fit methods report different kinetics data. Although the model-fit methods (CR and KC) allow a direct determination of kinetic triplets, the accuracy of data is lower. The CMP-II and CMP-III methods (incorporating model-free data in the model-fit methods) showcase multi-step chemical kinetics and better describe the decomposition behavior of HM due to its multi-compositional properties. To obtain kinetic triplets with enhanced accuracy, it is recommended to incorporate model-free data into the model-fit method. Improved precision of the kinetics data is essential for developing experimental parameters and optimizing the process. Future research should include the selection criteria of model-fit methods shown in this study to improve the accuracy of kinetic data.

New perspectives of Pt–CeO2 system: stabilization on MWCNTs for boosting activity and water‐resistance in CO oxidation at ambient temperatures

The present study elucidates new perspectives regarding the Pt–CeO2 system for CO oxidation. The successful deposition of highly dispersed Pt–CeO2 species onto the surface of multiwalled carbon nanotubes (MWCNTs) led to the formation of abnormally active and water‐resistant catalysts. The catalysts were investigated by structural (XRD, TEM), spectral (XPS), and kinetic (TPR–CO+O2, TPR–CO, TPR–H2) methods. The application of TPR–CO+O2 revealed the remarkably high activity of all Pt–CeO2/MWCNTs catalysts at temperatures below 0 °C. The study of the catalysts at ambient temperature demonstrated high CO conversion in the presence of water vapor at a concentration of 100 ppm CO. The experimental findings suggest that active sites, comprising platinum structures stabilized directly on the surface of MWCNTs, play a pivotal role in the oxidation of CO under humid conditions. A dual–site approach was employed to develop a kinetic model that effectively describes the experimental data. This model provides valuable insights into the mechanism of wet CO oxidation.

Solidification process of ABO3-type perovskites: Kinetic two-phase growth method with optimized potential

The functional properties of ABO3-type perovskite materials have garnered extensive attention, yet their solidification properties have remained challenging to investigate due to high-temperature environments and characterization limitations. In this study, molecular dynamics simulations are employed to comprehensively explore the melting, quenching, and crystal growth processes of SrTiO3 (STO) structural evolution. Through iterative fitting and optimization of ion effective charge, a set of potential functions capable of accurately simulating the high-temperature melting of STO are derived. The melting point obtained for STO (2403 K) using the two-phase coexistence method closely corresponds to the empirical value (2333 K), affirming the precision of the optimized potential. Quenching the molten STO yields an amorphous structure characterized primarily by Ti-O six-fold coordination, which increased by 13.09% when reduced to 300 K at a cooling rate of 0.1 K/ps. Notably, the results for different cooling rates revealed that slower cooling rates and lower temperatures yielded more ordered amorphous structures. To circumvent the formation of amorphous states during crystal growth of perovskite materials, we have developed a kinetic two-phase growth (KTPG) method. This approach regulates the cooling rate within a solid-liquid two-phase system, maintaining constant low supercooling at the interface to mimic STO crystal growth kinetics. Cooling at 0.01 K/ps to 1760 K leads to a notable transformation, with the percentage of Ti-O six-fold coordination reaching 90%. This signifies substantial progress in achieving crystal growth through this method, highlighting its efficacy in facilitating crystal formation from the melt phase.

Surface Charge Effects for the Hydrogen Evolution Reaction on Pt(111) Using a Modified Grand-Canonical Potential Kinetics Method.

Surface charges of catalysts have important influences on the thermodynamics and kinetics of electrochemical reactions. Herein, we develop a modified version of the grand-canonical potential kinetics (GCP-K) method based on density functional theory (DFT) calculations to explore the effect of surface charges on reaction thermodynamics and kinetics. Using the hydrogen evolution reaction (HER) on the Pt(111) surface as an example, we show how to track the change of surface charge in a reaction and how to analyze its influence on the kinetics. Grand-canonical calculations demonstrate that the optimum hydrogen adsorption energy on Pt under the standard hydrogen electrode condition (SHE) is around -0.2 eV, rather than 0 eV established under the canonical ensemble, due to the high density of surface negative charges. By separating the surface charges that can freely exchange with the external electron reservoir, we obtain a Tafel barrier that is in good agreement with the experimental result. During the Tafel reaction, the net electron inflow into the catalyst leads to a stabilization of canonical energy and a destabilization of the charge-dependent grand-canonical component. This study provides a practical method for obtaining accurate grand-canonical reaction energetics and analyzing the surface charge induced changes.

C-H Bond Oxidation by MnIV-Oxo Complexes: Hydrogen-Atom Tunneling and Multistate Reactivity.

The reactivity of six MnIV-oxo complexes in C-H bond oxidation has been examined using a combination of kinetic experiments and computational methods. Variable-temperature studies of the oxidation of 9,10-dihydroanthracene (DHA) and ethylbenzene by these MnIV-oxo complexes yielded activation parameters suitable for evaluating electronic structure computations. Complementary kinetic experiments of the oxidation of deuterated DHA provided evidence for hydrogen-atom tunneling in C-H bond oxidation for all MnIV-oxo complexes. These results are in accordance with the Bell model, where tunneling occurs near the top of the transition-state barrier. Density functional theory (DFT) and DLPNO-CCSD(T1) computations were performed for three of the six MnIV-oxo complexes to probe a previously predicted multistate reactivity model. The DFT computations predicted a thermal crossing from the 4B1 ground state to a 4E state along the C-H bond oxidation reaction coordinate. DLPNO-CCSD(T1) calculations further confirm that the 4E transition state offers a lower energy barrier, reinforcing the multistate reactivity model for these complexes. We discuss how this multistate model can be reconciled with recent computations that revealed that the kinetics of C-H bond oxidation by this set of MnIV-oxo complexes can be well-predicted on the basis of the thermodynamic driving force for these reactions.