Reaction Processes Research Articles

COMPARATIVE STUDY USING CFD OF COUNTER-CURRENT AND CO-CURRENT HYDROTREATING REACTORS USING JATROPHA CURCAS L VEGETABLE OIL

In this work, mathematical modeling and CFD simulation of two countercurrent and cocurrent hydrotreatment reactors were carried out, validating the results with a drained bed reactor (TBR), a commercial CoMo/γ-Al2O3 catalyst was used, the material the raw material was Jatropha Curcas L vegetable oil. The operating conditions were temperature 380 ° C, pressure 8 MPag. The kinetic model that was used considered 13 reactions that involve processes of decarboxylation, decarbonization, hydrodeoxygenation and hydrocracking reactions for triolein and tristearin triglycerides. The CFD simulation was carried out in Fluent 18.2 in a transient state and in 3D, considering the standard κ - ε turbulence models, Eulerian multiphase model and porous medium model, it was shown that the countercurrent reactor has less pressure drop than the countercurrent, the conversion the countercurrent reactor has a greater conversion of reactants of 99%, the generation of products from the countercurrent reactor has higher concentrations than the cocurrent reactor, this is because it has more contact areas between phases in the reactor.

The effect of glass sealing stabilization on LSM–YSZ cathode poisoning and oxygen reduction reaction processes in solid oxide fuel cell

AbstractThe perovskite structure and electrochemical activity of (La0.80Sr0.20)0.95MnO3−x–(Y2O3)0.08(ZrO2)0.92 (LSM–YSZ) composite cathode can be significantly affected by volatile boron species originated from sealing glass–ceramics. Herein, we investigate the impact of doping the varying Er2O3 content (ranging from 0 to 4%) into an aluminoborosilicate glass to mitigate boron volatilization, its interaction with the LSM–YSZ cathode and consequent effects on its electrochemical performance. The results reveal that the volatility of boron species can be significantly suppressed by introducing Er oxide into the glass network by enhancing the conversion of [BO3] to [BO4] units, thereby increasing the binding energy of boron and strengthening of the glass structure. Moreover, the electrocatalytic performance for the O2 reduction reaction on the LSM–YSZ/8YSZ/LSM–YSZ symmetric cells is studied under open‐circuit conditions in the presence and absence of glass sealants. The analyses utilizing electrochemical impedance spectroscopy (EIS) and distribution of the relaxation times (DRT) analysis indicate that the electrocatalytic performance of LSM–YSZ cathodes can be enhanced in the presence of glass with 4% Er2O3 (GE4). This enhancement in the electrocatalytic activity of the LSM–YSZ electrode for the oxygen reduction reaction (ORR) is attributed to formation of the thin layer on the electrode surface, leading to a notable reduction in the polarization resistance (Rp) from 0.81 Ω cm2 in the glass absence to 0.45 Ω cm2 in the presence of GE4. However, DRT analysis demonstrates that the prolonged exposure of the cathode to GE4 causes a deterioration in cell performance primarily due to the blocking the cathode active sites, which impedes dominant cathode processes of oxygen dissociative adsorption/desorption and charge transfer and consequently reducing kinetics of the ORR.

Detection of Impedance Inhomogeneity in Lithium-Ion Battery Packs Based on Local Outlier Factor

The inhomogeneity between cells is the main cause of failure and thermal runaway in Lithium-ion battery packs. Electrochemical Impedance Spectroscopy (EIS) is a non-destructive testing technique that can map the complex reaction processes inside the battery. It can detect and characterise battery anomalies and inconsistencies. This study proposes a method for detecting impedance inconsistencies in Lithium-ion batteries. The method involves conducting a battery EIS test and Distribution of Relaxation Times (DRT) analysis to extract characteristic frequency points in the full frequency band. These points are less affected by the State of Charge (SOC) and have a strong correlation with temperature, charge/discharge rate, and cycles. An anomaly detection characteristic impedance frequency of 136.2644 Hz was determined for a cell in a Lithium-ion battery pack. Single-frequency point impedance acquisition solves the problem of lengthy measurements and identification of anomalies throughout the frequency band. The experiment demonstrates a significant reduction in impedance measurement time, from 1.05 h to just 54 s. The LOF was used to identify anomalies in the EIS data at this characteristic frequency. The detection results were consistent with the actual conditions of the battery pack in the laboratory, which verifies the feasibility of this detection method. The LOF algorithm was chosen due to its superior performance in terms of FAR (False Alarm Rate), MAR (Missing Alarm Rate), and its fast anomaly identification time of only 0.1518 ms. The method does not involve complex mathematical models or parameter identification. This helps to achieve efficient anomaly identification and timely warning of single cells in the battery pack.

Mechanisms underlying drying shrinkage in ASM-based geopolymer: Capillary tensile stress and its prediction method

A pivotal limitation in the widespread adoption of geopolymer stems from their notable and substantial drying shrinkage properties, which significantly constrain their potential applications. The complex reaction processes and amorphous gel structures make it difficult to quantitatively calculate the drying shrinkage rate. In this study, alkali-activated slag-metakaolin-based geopolymer was used to develop a method for predicting drying shrinkage. By analyzing the internal relative humidity changes, contact angles on the structure surface at different ratios, and the surface tension of pore solutions, the capillary tensile stress within the structure was calculated. This analysis was combined with measurements of drying shrinkage, elastic modulus, and porosity to establish a predictive method for the drying shrinkage of alkali-activated slag-metakaolin-based geopolymer. The results indicated that as the system's relative humidity decreased, the surface tension of the pore solution increased, the interface contact angle reduced, and the capillary tensile stress, as calculated using the Young-Laplace equation, increased. These changes intensified the microstructural shrinkage and, consequently, increased the geopolymer's overall shrinkage rate. At the same time, the larger the porosity of the geopolymer system, the smaller the elastic modulus, the larger the dry shrinkage rate of the geopolymer. At a porosity of 29.0 %, an elastic modulus of 1.83 GPa, and a capillary tensile stress of 3.6 MPa, the dry shrinkage of the geopolymer is only 0.899 %. By adjusting the porosity and elastic modulus to 38.3 % and 1.60 GPa, respectively, and increasing the capillary tensile stress to 10.84 MPa, the dry shrinkage of the geopolymer reaches a maximum of 1.942 %. The prediction method for geopolymer drying shrinkage, established based on these factors, has a correlation coefficient of 0.97, effectively predicting the trend of geopolymer drying shrinkage rate characteristics. The current study provides a theoretical basis for methods to reduce shrinkage in geopolymers and their application in engineering.

Evaluation of Processing Parameters in the Solvothermal Synthesis of Cu-Rich Tetrahedrites for Potential Application as Thermoelectric Materials

The major issue associated with thermoelectric performance is the low efficiency of power conversion. The main challenge is achieving a combination of high Seebeck coefficient, high electrical conductivity, and low thermal conductivity for a significantly improved figure of merit (ZT). Developing strategies include the production of tetrahedrites with an intrinsically low thermal conductivity through the solvothermal method, using a low reaction time and processing temperature. Here, we report on the preparation of Cu-rich tetrahedrites through the solvothermal technique at low temperature, providing a promising strategy for the preparation of materials with potential applications in thermoelectricity. The influence of synthesis reaction time and temperature on the morphological, structural, and thermoelectrical properties of the samples was investigated through different characterization techniques. Tetrahedrite synthesized at 180 °C for 19 h yielded a favorable ZT value of >0.43 and a thermal conductivity of 0.2 Wm−1 K−1 (423 K), related to the Sb3+/Sb5+ and Cu+/Cu2+ ratio, as was observed by XPS. The cubic tetrahedrite phase attributed to the (222) plane was confirmed by XRD and TEM and the intense Raman mode observed at 351 cm−1. SEM images revealed that nanotetrahedral Cu-rich tetrahedrites efficiently assemble into spherical structures, resulting in an improvement in the Seebeck coefficient (437 µVK−1) and electrical conductivity.

Spent coffee to carbon: blending with manganese zinc ferrite as a plasmonic photocatalysis for degradation of organic dyes

ABSTRACT In this work, we introduce a new composite material consisting of Mn(1-x)ZnxFe2O4 (MZF) and wasted coffee grounds carbon (C). Crucially, the surface chemistry of the ‎composite, which lacks Zn2+ ions in octahedral locations, highlights its distinctive structural ‎characteristics. Before the integration of the carbon composite, the saturation magnetisation ‎of the sample was recorded as 53.073 emu/g. However, it decreased to 45.49 emu/g ‎after the composite was formed and the reaction processes occurred. UV-spectroscopy ‎enabled the measurement of band gap energies, which showed that the band gap energies for ‎ferrite were 2.93 eV and for the MZF/C composite were 2.12 eV. By utilising plasmonic ‎photocatalysis, the MZF/C composite has shown exceptional effectiveness as a high-temperature photocatalyst, specifically in the breakdown of methylene blue (MB) and Eosin (EO) dyes, ‎which are representative of basic and acidic dyes, respectively. The study demonstrated enhanced photocatalytic degradation kinetics under both visible light and sunlight, with sunlight showing superior performance. Over a 120-min period, the ferrite composite achieved a removal efficiency of 89% under sunlight, compared to 68% under artificial light. By utilising plasmonic photocatalysis principles, this work clarifies the structural and optical ‎properties of the MZF/C composite and emphasises its capacity to tackle environmental ‎issues through effective dye degradation mechanisms.‎

Preparation of CIP@Fe3O4 particles and their impact on the fenton reaction processing performance of single-crystal SiC

This study proposes the preparation of CIP@Fe3O4 composite magnetic particles, which maintain excellent magnetic properties while exhibiting superior Fenton reaction performance for the magnetorheological chemical polishing of single-crystal SiC. The CIP@Fe3O4 particles were prepared by coating a nanoscale layer of Fe3O4 onto micron-sized carbonyl iron powder (CIP) using the co-precipitation method. Their Fenton reaction performance and magnetic properties were characterized, and CIP@Fe3O4 was used as a solid-phase catalyst in Fenton reaction-induced etching, frictional wear, and polishing experiments on single-crystal SiC. The prepared CIP@Fe3O4 particles have a saturation magnetization of 184.3 emu/g, representing only an 8.7 % reduction compared to CIP, yet achieved a decolorization rate of 76.2 % for the methyl orange indicator (compared to only 17.2 % with CIP alone). The Fenton reaction using CIP@Fe3O4 resulted in a prominent corrosion layer on the surface of single-crystal SiC, with the oxygen atomic fraction reaching 22.15 %. The study examined material removal from SiC under Fenton reactions with different solid-phase catalysts: CIP, CIP@Fe3O4, and CIP + Fe3O4. Frictional wear results indicated that the maximum scratch cross-sectional removal area on the SiC surface under the Fenton reaction with CIP@Fe3O4 was 474.38 μm2, representing a 207.3 % increase compared to without the Fenton reaction. Additionally, Si-O compounds were identified in the debris. Polishing experiments showed that the material removal rate (MRR) with the Fenton reaction was 3295 nm/h, an increase of 220.2 % compared to without the Fenton reaction, and the surface roughness was reduced to Ra 0.895 nm, a 73.4 % reduction compared to without the Fenton reaction. This study provides additional evidence for the application of magnetorheological technology and the Fenton reaction in the polishing field of single-crystal SiC.

Valence-engineered catalysis-selectivity regulation of molybdenum oxide nanozyme for acute kidney injury therapy and post-cure assessment.

The optimization of the enzyme-like catalytic selectivity of nanozymes for specific reactive oxygen species (ROS)-related applications is significant, and meanwhile the real-time monitoring of ROS is really crucial for tracking the therapeutic process. Herein, we present a mild oxidation valence-engineering strategy to modulate the valence states of Mo in Pluronic F127-coated MoO3-x nanozymes (denoted as MF-x, x: oxidation time) in a controlled manner aiming to improve their specificity of H2O2-associated catalytic reactions for specific therapy and monitoring of ROS-related diseases. Experimentally, MF-0 (Mo average valence 4.64) and MF-10 (Mo average valence 5.68) exhibit exclusively optimal catalase (CAT)- or peroxidase (POD)-like activity, respectively. Density functional theory (DFT) calculations verify the most favorable reaction path for both MF-0- and MF-10-catalyzed reaction processes based on free energy diagram and electronic structure analysis, disclosing the mechanism of the H2O2 activation pathway on the Mo-based nanozymes. Furthermore, MF-0 poses a strong potential in acute kidney injury (AKI) treatment, achieving excellent therapeutic outcomes in vitro and in vivo. Notably, the ROS-responsive photoacoustic imaging (PAI) signal of MF-0 during treatment guarantees real-time monitoring of the therapeutic effect and post-cure assessment in vivo, providing a highly desirable non-invasive diagnostic approach for ROS-related diseases.

Edge-Hosted Graphitic Nitrogen Sites Carbocatalysts Mediated Electron Transfer Process for Powerful Fenton-Like Reactions

Edge-Hosted Graphitic Nitrogen Sites Carbocatalysts Mediated Electron Transfer Process for Powerful Fenton-Like Reactions

Colorimetric Oxygen Sensing by Analyzing Chromaticity Points for Polymer Cobalt Schiff Base in CIELAB

AbstractPolymer membranes of a copolymer ligand (L) coordinated to tetra‐coordinated N,N'‐ethylene bis(salicylideneiminato) cobalt(II) at the fifth coordinating site of the center cobalt(II), Co(II)S‐L, are prepared to measure colorimetrically the color changes in response to rapid reversible oxygen binding simultaneously with slow oxidation under moist conditions to yield Co(III)S‐L. The chromaticity point observed in CIELAB is the endpoint of the vector sum of the unit vectors for Co(II)S‐L, O2‐Co(II)S‐L, and Co(III)S‐L, scaled by their respective abundance ratios: (1 − m)(1 − n), m(1 − n), and n, where m is the ratio of O2‐Co(II)S‐L to the sum of Co(II)S‐L and O2‐Co(II)S‐L and n is the ratio of Co(III)S‐L to the total of the three cobalt complexes. The observed limited area in CIELAB as a stoichiometric Euclidean space is supported by the following two different reaction processes of the polymer membranes: an oxygen‐binding reaction under several different partial pressures of oxygen supplied to the membranes in a short period, during which oxidation of the cobalt(II) complexes is negligible, and an oxidation reaction over a long period at a constant partial pressure of oxygen. The chromaticity points in both processes progress linearly in three different two‐dimensional coordinates: a*b*, a*L*, and b*L*.

Tutorial Review on the Set-Up and Running of Quantum Mechanical Cluster Models for Enzymatic Reaction Mechanisms.

Enzymes turnover substrates into products with amazing efficiency and selectivity and as such have great potential for use in biotechnology and pharmaceutical applications. However, details of their catalytic cycles and the origins surrounding the regio- and chemoselectivity of enzymatic reaction processes remain unknown, which makes the engineering of enzymes and their use in biotechnology challenging. Computational modelling can assist experimental work in the field and establish the factors that influence the reaction rates and the product distributions. A popular approach in modelling is the use of quantum mechanical cluster models of enzymes that take the first- and second coordination sphere of the enzyme active site into consideration. These QM cluster models are widely applied but often the results obtained are dependent on model choice and model selection. Herein, we show that QM cluster models can give highly accurate results that reproduce experimental product distributions and free energies of activation within several kcal mol-1, regarded that large cluster models with >300 atoms are used that include key hydrogen bonding interactions and charged residues. In this tutorial review, we give general guidelines on the set-up and applications of the QM cluster method and discuss its accuracy and reproducibility. Finally, several representative QM cluster model examples on metal-containing enzymes are presented, which highlight the strength of the approach.

Carbohydrate Derived Value-added Products from Lignocelluloses

Abstract: Chemistry is confronted with the pressing issues of depleting non-renewable fossil resources and the imperative to combat environmental pollution, which is crucial for a sustainable future. Biomass stands out as the sole organic carbon source in nature among the array of sustainable resources available, positioning it as a prime substitute for fossil-derived chemicals and fuels. Extensive research has been conducted on the abundant lignocelluloses as a potential source for biofuels, bioenergy, and various valuable products, wherein, the incorporation of various processes in biomass fractionation to separate biopolymers (such as lignin, cellulose, and hemicellulose) has the potential to enhance the overall value of the process. However, industrial demonstration of biomass utilization for commercial products has been limited due to the challenges posed by the recalcitrance and complexity of biomass. Therefore, there is a need for efficient reaction processes to enable the production of bio-chemicals and fuels from renewable lignocellulose. This review focuses on the latest chemical methods developed for producing value-added chemicals from biomass-derived cellulose as a renewable feedstock.

Temperature-Dependent Oxidation Behavior of Silicon Carbide Surface: Reactive Molecular Dynamics Simulations.

The high-temperature oxidation mechanism of silicon carbide (SiC) is crucial for designing thermal protection systems in aircraft. This study explored the oxidative chemical reaction processes and mechanism on SiC surface and interfaces within the temperature range of 300-2300 K by using reactive molecular dynamics simulation. The oxygen impact on the silica (SiOx) growth of the SiC surface was analyzed, which shows a progressive increase of silica thickness. The simulation results indicated that the oxidation process of SiC was a typical passive oxidation mechanism. With the environmental temperature rising and oxygen impact, the increase of oxidation thickness on the SiC surface undergoes three oxidizing reaction processes: little chemical adsorption of oxygen molecules on the initial surface, rapid oxidation of silicon and carbon, and dramatic oxidation of the interface between the oxidation layer and SiC. Additionally, this work studied the mechanism of oxidation thickness growth and chemical diffusion of oxygen. The oxidation rate is weakened according to the oxygen atom diffusion barrier effect of silica repulsion. Moreover, the kinetic parameters were statistically calculated by fitting the growth of Si-O bonds and their reaction rate constants. Subsequently, the activation energy and pre-exponential factors were derived by using the Arrhenius equation to model the chemical reaction kinetics of the thermal oxidation process. The chemical reaction behaviors of the two stages could be concluded as follows: (i) in stage I, the initial oxidation is reaction rate limiting; (ii) in stage II, SiC oxidation is limited by both the oxidation reaction rate and the oxygen diffusion coefficient of the oxidation layer. The activation energy of stage II increased compared with stage I due to the oxygen atoms diffusion barrier between the oxidation layers. This study on the oxidation and ablation mechanism of the SiC surface at the atomic scale would provide insight into understanding thermal oxidation behavior and the design of ceramic materials.

Zirconium(IV) coordination-mediated rapid and versatile post-modification of polydopamine coating as stationary phase for open-tubular capillary electrochromatography

In recent years, mussel-inspired polydopamine (PDA)-based materials have attracted significant attention in the field of open-tubular capillary electrochromatography (OT-CEC) owing to their diverse and appealing properties. However, previously established functionalized PDA coating-based CEC stationary phases predominantly relied on the latent reactivity of PDA with amine/thiol-containing molecules, limiting the types of applicable modifiers and requiring time-consuming reaction processes. Herein, we presented a versatile and efficient method for the facile and rapid fabrication of diverse functionalized PDA coatings as OT-CEC stationary phases through a Zr(IV) coordination-mediated post-modification strategy. Different kinds of modifiers, including octadecylamine (ODA), lauric acid (LA), and perfluorooctanoic acid (PFOA), were rapidly and robustly grafted onto the PDA coating, verified through multiple characterization techniques. The influences of preparation parameters on the grafting efficiency of the functionalized PDA coating were systematically investigated. Utilizing the Zr(IV)-mediated ODA-, LA- and PFOA-functionalized PDA-based OT-CEC columns, we achieved high-efficiency baseline separation of a series of neutral analytes with excellent repeatability, good stability, and long lifetime. Given the strong universality of the Zr(IV) coordination-mediated post-modification approach, our study provides an effective pathway for advancing the development of a wider range of functional PDA-based chromatographic stationary phases.

Improving heat transfer prediction across catalytic SiC interface through a multiscale framework leveraging machine learning and data fusion techniques

Accurate aerothermal prediction under hypersonic flow conditions is crucial for any thermal protection materials design and engineering. The surface catalytic effect, where dissociated atoms recombine into their molecular forms at the air-solid interface, is an exothermic reaction and plays an important role in high-enthalpy aerodynamic environment prediction. Taking SiC, a widely recognized high-temperature thermal protection material as an example, a multiscale fusion approach for aerothermal prediction is proposed. The approach utilizes reactive molecular dynamics method to construct an interface catalysis model, and the Bayesian maximum entropy to integrate experimental and simulational data into an optimized database. Subsequently, using the radial basis function neural network algorithm, a machine learning-based reaction kinetics model with precise analysis of surface catalysis is trained. The obtained catalytic recombination efficiency is used as a boundary input for computational fluid dynamics simulation, enabling rapid and accurate prediction of hypersonic thermal environment. The result shows that the predicted surface heat flux by this novel approach is consistent with the benchmark studies, but comes with significantly reduced computation time. The stagantion heat flux predictions based on the assumptions of full catalytic wall, finite rate catalytic wall (from the proposed multiscale fusion method), and non-catalytic wall are determined to be 8.65×106 W/m2, 7.51×106 W/m2, and 4.02×106 W/m2, respectively. Comparing these with the wind tunnel benchmark value of 7.48×106 W/m2, the error from the proposed multiscale fusion method is 0.30 %, indicating significant enhancement in prediction accuracy through the proposed upscaling method. The new approach could not only reveal complex exothermic reaction processes at the interface, but also enhance the prediction accuracy at much higher computational efficiency, providing an alternative for multiscale modeling of complex flow and heat transfer at the interface.

Quantification of Synergistic Two-Color Covalent Bond Formation.

The emergence of highly wavelength resolved reactivity information for complex photochemical reaction processes allows the establishment of multi-color reaction modes. One particularly powerful mode is the synergistic two-color reaction, where two colors of light have to be present in the same volume element to either enable or enhance photochemical reactivity that leads to a specific photoproduct. Herein, we introduce a two-color synergistic photochemical reaction system based on a diaryl indenone epoxide (DIO) photoswitch and the cis-to-trans isomerization of a bridged ring-strained azobenzene (SA), which respond to ultraviolet (365 nm) and visible light (430 nm), respectively, with different rates, forming a well-defined heterocyclic photoadduct, DIOSA, that we structurally confirm via single crystal x-ray diffraction (SXRD). To quantitatively capture the effectiveness of the dual-color irradiation as a function of the reaction conditions such as light intensity and starting material ratio as a function of product yield, we introduce a parameter, the photochemical synergistic ratio. A reduced synergistic ratio- that extrapolates to conditions of infinitesimal conversions - allows to compare the efficiency of the synergistic photochemistry at varying reaction conditions.

Cauliflower-like Pd/MoC||Mo2C/C heterostructure as an efficient trifunctional catalyst for formic acid oxidation, hydrogen evolution, and oxygen reduction reactions

The use of Pd-based catalytic materials as electrocatalysts for formic acid oxidation reaction (FAO), hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) has been well-established for some time. The incorporation of a second phase can markedly enhance the electronic properties of the composites. The combination of different compounds with superior electronic properties is crucial for the design and preparation of catalysts with optimal catalytic activity and stability. In this study, a novel cauliflower-like Pd/MoC||Mo2C/C composite with heterostructure is synthesised, which exhibits excellent catalytic activity and long-term stability against FAO, HER, and ORR. The high-temperature treatment results in the formation of small-sized Mo₂C and MoC nanoparticles on the carbonaceous substrate, thereby exposing a greater number of Mo and Mo-C active sites. The formation of heterostructures between Mo₂C and MoC optimises the electronic structure of the composite, thereby facilitating enhanced reaction processes. In terms of FAO, the mass activity of Pd/MoC||Mo2C/C is 1.87A mgPd-1, which is 2.75 times higher than that of Pd/C (0.68A mgPd-1). As for the HER, a much lower overpotential of 28mV is required to achieve a current density of 10mAcm-2 compared to Pd/C (40mV). Fortunately, Pd/MoC||Mo2C/C also shows excellent ORR activity with a half-wave potential of 0.798V and the maximum current density of approximately 5.73mAcm-2 in alkaline electrolyte. These findings may contribute to the development of other noble metal-based materials loaded on intermetallic compounds with stable and effective electrocatalytic performance.

Effects of hexagonal boron nitride nanosheets on the biostabilization of recycled sands for geotechnical fill applications

Biostabilization techniques including plant enzyme induced calcite precipitation (EICP) and microbially induced calcite precipitation (MICP) represent promising and environmentally friendly methods for improving the engineering properties of recycled geomaterials for geotechnical fill applications. In this study, hexagonal boron nitride (h-BN) nanosheets were dispersed and utilized as nano-additives in the EICP and MICP reaction processes to facilitate the precipitation of calcium carbonate polymorphs (CaCO3) in washed recycled sands (RS) derived from construction and demolition (C&D) wastes for geotechnical fill applications. The investigation comprised a systematic range of biological and chemical microscopic and macroscopic experiments intending to stabilize the RS for geotechnical fill applications. The study results suggested that using h-BN nanosheets did not have a notable impact on bacterial growth or the functioning of bacterial and plant enzyme activity. In addition, it was observed that the optimal addition of h-BN nanosheet additives substantially increased CaCO3 precipitation by up to 34 % and 28 % in the EICP and MICP reaction processes respectively, which can be postulated to be due to the nanosheets acting as nucleation sites throughout the high surface area and negatively surface charge. Furthermore, the introduction of h-BN nanosheets led to a significant enhancement in the performance of unconfined compressive strength (UCS) of the stabilized RS through nanofillers and reinforcements, with improvements of up to 20 % and 13 % in the biostabilization of RS using the EICP and MICP after 10 treatment cycles. Detailed analyses, including Fourier-transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM) imaging, revealed that h-BN nanosheets, with a substantial surface area and effective chemical functional groups, interconnected with the CaCO3 mineral surface. Overall, the study suggests that integrating effective additives can improve the utilization of EICP and MICP in geotechnical fill applications, namely in road embankments and pavements, whilst providing both commercial viability and enhanced performance.

Quantification of Synergistic Two‐Color Covalent Bond Formation

The emergence of highly wavelength resolved reactivity information for complex photochemical reaction processes allows the establishment of multi‐color reaction modes. One particularly powerful mode is the synergistic two‐color reaction, where two colors of light have to be present in the same volume element to either enable or enhance photochemical reactivity that leads to a specific photoproduct. Herein, we introduce a two‐color synergistic photochemical reaction system based on a diaryl indenone epoxide (DIO) photoswitch and the cis‐to‐trans isomerization of a bridged ring‐strained azobenzene (SA), which respond to ultraviolet (365 nm) and visible light (430 nm), respectively, with different rates, forming a well‐defined heterocyclic photoadduct, DIOSA, that we structurally confirm via single crystal x‐ray diffraction (SXRD). To quantitatively capture the effectiveness of the dual‐color irradiation as a function of the reaction conditions such as light intensity and starting material ratio as a function of product yield, we introduce a parameter, the photochemical synergistic ratio. A reduced synergistic ratio – that extrapolates to conditions of infinitesimal conversions – allows to compare the efficiency of the synergistic photochemistry at varying reaction conditions.

Molecular mechanics studies of factors affecting overall rate in cascade reactions: Multi-enzyme colocalization and environment.

Millions of years of evolution have optimized many biosynthetic pathways by use of multi-step catalysis. In addition, multi-step metabolic pathways are commonly found in and on membrane-bound organelles in eukaryotic biochemistry. The fundamental mechanisms that facilitate these reaction processes provide strategies to bioengineer metabolic pathways in synthetic chemistry. Using Brownian dynamics simulations, here we modeled intermediate substrate transportation of colocalized yeast-ester biosynthesis enzymes on the membrane. The substrate acetate ion traveled from the pocket of aldehyde dehydrogenase to its target enzyme acetyl-CoA synthetase, then the substrate acetyl CoA diffused from Acs1 to the active site of the next enzyme, alcohol-O-acetyltransferase. Arranging two enzymes with the smallest inter-enzyme distance of 60 Å had the fastest average substrate association time as compared with anchoring enzymes with larger inter-enzyme distances. When the off-target side reactions were turned on, most substrates were lost, which suggests that native localization is necessary for efficient final product synthesis. We also evaluated the effects of intermolecular interactions, local substrate concentrations, and membrane environment to bring mechanistic insights into the colocalization pathways. The computation work demonstrates that creating spatially organized multi-enzymes on membranes can be an effective strategy to increase final product synthesis in bioengineering systems.