Chemically Research Articles

Spiers Memorial Lecture: Engineering biocatalysts.

Enzymes are being engineered to catalyze chemical reactions for many practical applications in chemistry and biotechnology. The approaches used are surveyed in this short review, emphasizing methods for accessing reactivities not expressed by native protein scaffolds. The successful generation of completely de novo enzymes that rival the rates and selectivities of their natural counterparts highlights the potential role that designer enzymes may play in the coming years in research, industry, and medicine. Some challenges that need to be addressed to realize this ambitious dream are considered together with possible solutions.

Precision Measurement of the Electron Affinity of Chlorine via High-Resolution Photoelectron Spectroscopy.

Chlorine (Cl2) is a diatomic molecule used as an important industrial gas. However, the electron affinity (EA) of Cl2, a fundamental parameter for understanding chemical reactions, has no accurate experimental result available. The latest result of the EA value of Cl2 is 2.50(20) eV reported in 1983. In the present work, we report the precision measurement of the EA of Cl2 with the successive difference method via the high-resolution photoelectron spectroscopy of cryogenically cold chlorine anions Cl2-. The EA of Cl2 is determined to be 19432(9) cm-1 or 2.4093(11) eV.

Influence of steel slag content on the mechanical and hydraulic properties of compacted silt-bentonite mixtures

ABSTRACT The reuse of by-products has become increasingly important as a means of minimising the consumption of natural resources and reducing waste disposal. This study examines the potential reuse of steel slag for soil stabilisation, with benefits such as conserving natural resources and mitigating the greenhouse gas emissions associated with the production of conventional stabilising agents. It focuses on evaluating the effect of pozzolanic reactions on the strength and stiffness of both loess silt and silt-bentonite mixtures. The experimental tests included the physical characterisation of granular materials, reactivity tests of the pozzolanicity of soil mixtures, compaction tests, unconfined compression tests, and hydraulic conductivity tests. The impact of the curing period was also analysed to quantify the effects of natural cementation and the development of hydrogels within soil pores on the compacted soil properties. The findings suggest that adding steel slag can significantly increase the strength and the stiffness of compacted loess silts by over 300% and 500%, respectively, after 56 days of curing, substantially reducing the hydraulic conductivity of granular materials, such as the tested silt, as hydrogels partially occupy the pores available for liquid flow. It should be noted that the chemical reactions during hydrogel formation may hinder the free expansion of clay mixtures and release Ca2+ ions, thereby counteracting the expected reduction in hydraulic conductivity when bentonite is added to compacted earthen barriers.

Gold nanoparticle microemulsion films with tunable surface plasmon resonance signal

Composite films were prepared by the dip-coating method. An organosol of Au nanoparticles (6.3±0.4nm) was used as the reaction mixture. The nanoparticles were stabilized with sodium bis(2-ethylhexyl) sulfosuccinate (AOT). The prepared films were formed of an AOT layer with encapsulated Au nanoparticles (i.e. Au@AOT films). The films demonstrated a stable plasmon effect. The variation of the immersion number of the glass substrate from 1 to 10 allowed the adjustment of the plasmonic properties. The absorption intensity and maximum wavelength of the surface plasmon resonance were found to change from 0.183 to 0.245 and from 529±2 to 539±2nm, respectively. The plasmonic properties were found to correlate with the film thickness, roughness, and morphology. An increase in the concentration of Au nanoparticles improves the film’s mechanical strength and wettability.

Cold atmospheric plasma-activated medium for potential ovarian cancer therapy.

Cold atmospheric plasma (CAP) has emerged as an innovative tool with broad medical applications, including ovarian cancer (OC) treatment. By bringing CAP in close proximity to liquids such as water or cell culture media, solutions containing reactive oxygen species (ROS) and reactive nitrogen species (RNS) are generated, called plasma-activated media (PAM). In this systematic review, we conduct an in-depth analysis of studies focusing on PAM interactions with biological substrates. We elucidate the diverse mechanisms involved in the activation of different media and the complex network of chemical reactions underlying the generation and consumption of the prominent reactive species. Furthermore, we highlight the promises of PAM in advancing biomedical applications, such as its stability for extended periods under appropriate storage conditions. We also examine the application of PAM as an anti-cancer and anti-metastatic treatment for OC, with a particular emphasis on its ability to induce apoptosis via distinct signaling pathways, inhibit cell growth, suppress cell motility, and enhance the therapeutic effects of chemotherapy. Finally, the future outlook of PAM therapy in biomedical applications is speculated, with emphasis on the safety issues relevant to clinical translation.

Two-dimensional model in a laminar flow slit photoreactor for the determination of surface kinetic constants considering the presence of diffusion limitations

Narrow slit reactors are widely used in laboratory testing of photocatalytic materials, as well as for the determination of kinetic coefficients in surface photocatalyzed reactions. In this work, the behavior of a continuous laminar flow slit reactor was described by a two-dimensional model, addressing the advection–diffusion problem in the fluid phase, coupled with a first-order chemical reaction on the reactor walls. The concentration profile of the reactant, in the transverse and longitudinal directions of the reactor, depends on two parameters that characterize the system; the Péclet number and the Damköhler number, in addition to the geometry of the reactor. Once a short distance from the reactor’s entrance has been surpassed, the relationship between the transversally averaged reactant concentration and the concentration existing on the catalytic surface becomes essentially constant, thus defining an (external) effectiveness factor. The simulations carried out for a wide range of values of the parameters characterizing the model showed that the effectiveness factor only depends on the Damköhler number, being independent of the value of the Péclet number and of the relationship between the reactor length and the distance separating the plates. An analytical expression for the effectiveness factor as a function of the Damköhler number was proposed, which allows to determine the value of the kinetic coefficient for the surface reaction (ks), even in the presence of important limitations to mass transfer. The methodology proposed was illustrated performing experiments of photocatalytic oxidation of toluene in air (with Péclet numbers ranging from 20 to 40), employing a paint formulated with carbon-doped TiO2 in a continuous laboratory photoreactor of flat parallel plates. The observed toluene conversions were in the range of 13 to 26 %, consequently, the calculated Damköhler number was Da = 0.0307 and the surface kinetic coefficient thus determined (for 50 % of relative humidity and 42.3 W/m2 of irradiance flux) was ks = 1.262 10-4 m/s. The significance of this work lies in the development of a comprehensive model that can be used to know the surface kinetics in photocatalytic reactions, applicable to scenarios where there are considerable mass transfer limitations or not

Electrooxidation of gaseous volatile organic compounds based on deep eutectic solvent modified Ni/SnOx-Sb nanocomposites

Volatile organic compounds (VOCs) are one of the main sources of atmospheric haze and pose a threat to human health. Electrocatalysis is a technique that catalyzes chemical reactions by applying an electrical potential, which offers mild reaction conditions and environmental friendliness, making it highly promising for the treatment of VOCs. In this research, a series of deep eutectic solvent (DES) modified Ni/SnOx nanosheets doped with different Sb doping amounts (Ni/SnOx-Sb-DES) have been prepared and applied to the electrooxidation of toluene. In the process of electrochemical gas–solid interface catalysis, the content of reactive oxygen species released on Ni/SnOx-Sb-DES electrodes are affected by the specific surface area and the number of oxygen vacancies. Electrochemical characterization discovered that there are significant differences in overpotential among catalysts of different ratios, thus affecting catalytic activity of Ni/SnOx-Sb-DES. Among them, the Ni/SnOx-Sb-DES with best ratio removal rate of toluene reached 83.07%, while the selectivity of CO2 was greater than 95%. This study proposes a method for removing VOCs at ambient temperatures, aiming to provide a new avenue for commercial applications in environmental-related fields.

Mathematical modeling and machine learning-based optimization for enhancing biofiltration efficiency of volatile organic compounds

Biofiltration is a method of pollution management that utilizes a bioreactor containing live material to absorb and destroy pollutants biologically. In this paper, we investigate mathematical models of biofiltration for mixing volatile organic compounds (VOCs) for instance hydrophilic (methanol) and hydrophobic (α\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha$$\\end{document}-pinene). The system of nonlinear diffusion equations describes the Michaelis-Menten kinetics of the enzymic chemical reaction. These models represent the chemical oxidation in the gas phase and mass transmission within the air-biofilm junction. Furthermore, for the numerical study of the saturation of α\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha$$\\end{document}-pinene and methanol in the biofilm and gas state, we have developed an efficient supervised machine learning algorithm based on the architecture of Elman neural networks (ENN). Moreover, the Levenberg-Marquardt (LM) optimization paradigm is used to find the parameters/ neurons involved in the ENN architecture. The approximation to a solutions found by the ENN-LM technique for methanol saturation and α\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha$$\\end{document}-pinene under variations in different physical parameters are allegorized with the numerical results computed by state-of-the-art techniques. The graphical and statistical illustration of indications of performance relative to the terms of absolute errors, mean absolute deviations, computational complexity, and mean square error validates that our results perfectly describe the real-life situation and can further be used for problems arising in chemical engineering.

Investigating the Metal-TiO2 Influence for Highly Selective Photocatalytic Oxidation of Methane to Methanol.

Methane conversion to valuable chemicals is a highly challenging and desirable reaction. Photocatalysis is a clean pathway to drive this chemical reaction, avoiding the high temperature and pressure of the syngas process. Titanium dioxide, being the most used photocatalyst, presents challenges in controlling the oxidation process, which is believed to depend on the metal sites on its surface that function as heterojunctions. Herein, we supported different metals on TiO2 and evaluated their activity in methane photooxidation reactions. We showed that Ni-TiO2 is the best photocatalyst for selective methane conversion, producing impressively high amounts of methanol (1.600 μmol·g-1) using H2O2 as an oxidant, with minimal CO2 evolution. This performance is attributed to the high efficiency of nickel species to produce hydroxyl radicals and enhance H2O2 utilization as well as to induce carrier traps (Ti3+ and SETOVs sites) on TiO2, which are crucial for C-H activation. This study sheds light on the role of catalyst structure in the proper control of CH4 photoconversion.

Do Molecular Geometries Change Under Vibrational Strong Coupling?

As pioneering experiments have shown, strong coupling between molecular vibrations and light modes in an optical cavity can significantly alter molecular properties and even affect chemical reactivity. However, the current theoretical description is limited and far from complete. To explore the origin of this exciting observation, we investigate how the molecular structure changes under strong light-matter coupling using an ab initio method based on the cavity Born-Oppenheimer Hartree-Fock ansatz. By optimizing H2O and H2O2 resonantly coupled to cavity modes, we study the importance of reorientation and geometric relaxation. In addition, we show that the inclusion of one or two cavity modes can change the observed results. On the basis of our findings, we derive a simple concept to estimate the effect of the cavity interaction on the molecular geometry using the molecular polarizability and the dipole moments.

Alkaloid extract of seed Citrullus colocynthis as novel green inhibitor for mild steel corrosion in one molar HCl acid solution: DFT and MC/MD approaches

The study was designed to explore the corrosion prevention capabilities of Citrullus colocynthis seeds alkaloid-rich extract (CSEA) on MS in a 1 M HCl environment by use of electrochemical and theoretical methods. Notably, Electrochemical Impedance Spectroscopy (EIS) and potentiodynamic polarization were used to probe the impact of immersion time and temperature. Energy-dispersive X-ray spectroscopy (EDX) and spanning electron microscopy (SEM) were used to confirm the presence of a protective layer on the substrate surface. Density functional theory (DFT) method was used to optimize the investigated species by use of B3LYP/6–31 + G(d, p) level of theory. The global and local quantum chemical reactivity descriptors were calculated to explore the inhibition corrosion efficiency and to identify the most favorable sites for electrophilic and nucleophilic attacks. Monte Carlo (MC) and molecular dynamics simulation (MDS) methods were used to study the interactions between corrosion inhibitor and metal surface. Noteworthy, results showed that CSEA exhibited an impressive inhibition efficiency, which reached 94.3% with a concentration of 2 g/L at 298 K. Potentiodynamic polarization revealed that the extract acted as a mixed-type inhibitor. Nyquist graphs showed that charge-transfer resistance and dæouble-layer capacitance both rised with increasing CSEA concentration, suggesting better inhibition efficiency. Notably, the Langmuir adsorption isotherm is well-aligned with the adsorption of inhibitor compounds. Importantly, all aforementioned theoretical methods were in agreement with the experimental findings. The outcome of the present work supported using Citrullus colocynthis seeds alkaloid-rich extract as ecofriendly agents to prevent corrosion.

Mixed convective magneto flow of nanofluid for the Sutterby fluid containing micro-sized selfpropelled microorganisms with chemical reaction: Keller Box Analysis

Abstract The current work aims to scrutinize the bioconvection Sutterby nanofluid flow of the Cattaneo-Christov heat and mass flux over a rotating disk. The effects of thermophoresis and Brownian motion receive considerable consideration. The process of analyzing heat and mass transfer phenomena involves taking into account the impacts of thermal radiation and chemical reactions that are susceptible to convective boundary conditions. Firstly, we reduce the PDEs of the physical model to ODEs through alter transformation and then numerically solved the transformed ODEs using Keller Box technique. An analysis of numerical data follows to ascertain the role of numerous flow variables on the flow profiles. Based on the findings, it is evident that an increase in the fluid variable Δ and the porous variable K leads a decrease in the, radial F'(ζ), axial F(ζ) and tangential G(ζ) velocities. Furthermore, we find that the growing values of the thermal radiation Rd variable and the thermal Biot number B_T greatly aid in raising the fluid's temperature. Concentration profile shows decreasing behavior for rising values of Schmidt number Sc but upsurge for solutal Biot number B_C. The microorganism is decayed with greater Lewis number Lb and Peclet number Pe.

Nonequilibrium Membrane Dynamics Induced by Active Protein Interactions and Chemical Reactions: A Review

Biomembranes wrapping cells and organelles are not only the partitions that separate the insides but also dynamic fields for biological functions accompanied by membrane shape changes. In this review, we discuss the spatiotemporal patterns and fluctuations of membranes under nonequilibrium conditions. In particular, we focus on theoretical analyses and simulations. Protein active forces enhance or suppress the membrane fluctuations; the membrane height spectra are deviated from the thermal spectra. Protein binding or unbinding to the membrane is activated or inhibited by other proteins and chemical reactions, such as ATP hydrolysis. Such active binding processes can induce traveling waves, Turing patterns, and membrane morphological changes. They can be represented by the continuum reaction‐diffusion equations and discrete lattice/particle models with state flips. The effects of structural changes in amphiphilic molecules on the molecular‐assembly structures are also discussed.

A Globally Accurate Neural Network Potential Energy Surface and Quantum Dynamics Studies on Be+(2S) + H2/D2 → BeH+/BeD+ + H/D Reactions

Chemical reactions between Be+ ions and H2 molecules have significance in the fields of ultracold chemistry and astrophysics, but the corresponding dynamics studies on the ground-state reaction have not been reported because of the lack of a global potential energy surface (PES). Herein, a globally accurate ground-state BeH2+ PES is constructed using the neural network model based on 18,657 ab initio points calculated by the multi-reference configuration interaction method with the aug-cc-PVQZ basis set. On the newly constructed PES, the state-to-state quantum dynamics calculations of the Be+(2S) + H2(v0 = 0; j0 = 0) and Be+(2S) + D2(v0 = 0; j0 = 0) reactions are performed using the time-dependent wave packet method. The calculated results suggest that the two reactions are dominated by the complex-forming mechanism and the direct abstraction process at relatively low and high collision energies, respectively, and the isotope substitution has little effect on the reaction dynamics characteristics. The new PES can be used to further study the reaction dynamics of the BeH2+ system, such as the effects of rovibrational excitations and alignment of reactant molecules, and the present dynamics data could provide an important reference for further experimental studies at a finer level.

Photodissociation spectra of single trapped CaOH+ molecular ions.

Molecular ions that are generated by chemical reactions with trapped atomic ions can serve as an accessible testbed for developing molecular quantum technologies. On the other hand, they are also a hindrance to scaling up quantum computers based on atomic ions, as unavoidable reactions with background gases destroy the information carriers. Here, we investigate the single- and two-photon dissociation processes of single CaOH+ molecular ions co-trapped in Ca+ ion crystals using a femtosecond laser system. We report the photodissociation cross section spectra of CaOH+ for single-photon processes at λ = 245-275 nm and for two-photon processes at λ = 500-540 nm. Measurements are interpreted with quantum-chemical calculations, which predict the photodissociation threshold for CaOH+ → Ca+ + OH at 265nm. This result can serve as a basis for dissociation-based spectroscopy for studying the internal structure of CaOH+. The result also gives a prescription for recycling Ca+ ions in large-scale trapped Ca+ quantum experiments from undesired CaOH+ ions formed in the presence of background water vapor.

Profiles of volatile sulfur compounds in various vegetables consumed in Korea using HS-SPME-GC/MS technique

Volatile sulfur compounds (VSCs) are not only important for their therapeutic potential but also significantly influence the flavor profiles of agricultural products. VSCs exhibit various chemical structures due to their stability and volatility, and they may form or be altered as a result of enzymatic and chemical reactions during storage and cooking. This study has focused on profiles of VSCs in 58 different vegetable samples by using HS-SPME-GC/MS technique and chemometric analyses. The validation was carried out using cabbage juice as a vegetable matrix for VSCs analysis, showing satisfactory repeatability (RSD 8.07% ~ 9.45%), reproducibility (RSD 4.22% ~ 7.71%), accuracy and specificity. The established method was utilized on various vegetables, revealing that 21 VSCs such as sulfides, disulfides, trisulfides, isothiocyanates, sulfhydryls, and thiophenes were successfully identified and quantified. These compounds were found in a range of vegetables including Allium species, Cruciferae, Capsicum species, green leafy vegetables, and mushrooms. In particular, isocyanate and allyl groups were abundant in Cruciferae and Allium vegetables, respectively. Cooking conditions were shown to reduce the levels of certain sulfur compounds such as dimethyl sulfide and dimethyl trisulfide in vegetables like broccoli and cabbage, suggesting that heat treatment can lead to the volatilization and reduction of these compounds. The present study provides reliable insights into the compositions of VSCs in various vegetables and examines the changes induced by different cooking methods.

Development of 1400°C(2552°F) class Ceramic Matrix Composite Turbine Shroud and Demonstration Test with JAXA F7 Aircraft Engine

Abstract The Authors developed 1400°C(2552°F) class CMC material system which consist of SiC fibers and SiC matrix and ytterbium silicate base matrix, aiming for higher temperature capability. Then they designed and manufactured high pressure turbine shrouds for aircraft engines using that 1400°C class material system, and they conducted strength tests and thermal cycle tests for turbine shroud components. After that they conducted engine tests for the CMC turbine shrouds demonstration in the actual engine environment jointly with the Japan Aerospace Exploration Agency (JAXA) in 2021. The engine test was conducted for over 75 hours including over 35 hour hot time. After the test teardown inspection was conducted. No spallation of EBC, no recession and no wear on CMC turbine shrouds were found. As the result of the microstructure observation for cut faces of CMC turbine shrouds, no oxidation in SiC fibers, no chemical reaction in matrix, and no microcrack in matrix were found, but, some oxidation in fiber interface coating and microcrack in EBC were found. Bending strength tests with specimens cut out from CMC turbine shrouds were conducted in order to survey the degradation of material. As the result of bending test, the strength of the specimens cut out from engine tested shrouds were equivalent to the strength of the specimens cut out from unused shrouds. The CMC turbine shrouds after engine test were determined to be serviceable, therefore the developed 1400°C class CMC shrouds was proven to be sound in an actual engine environment.

Synthesis of Enamides through Hydro‐Functionalization of Ynamides

Most of the methods for the synthesis of functionalized enamides from ynamides were developed in the last two decades showing the contemporary interest in the exploration of ynamide chemistry. The utilization of the intrinsic reactivity of the ynamide triple bond through keteniminium intermediacy, coordination with metals, and as a radical acceptor toward the development of strategies for the synthesis of functionalized enamides reflect the constant strive and creativity in the design and execution of synthetic methods. The present review summarizes the synthetic strategies developed during the last two decades and is divided into the sections depending on the type of hydrofunctionalization reaction. It may be predicted that this field of chemistry will continue to grow exponentially in the coming years and the ready availability of a wide range of ynamides now provides an excellent opportunity to further enrich mainstream synthetic methodologies.

Solution of state transfer matrix based on DNA strand displacement circuits

Abstract In recent years, DNA strand displacement (DSD) circuits have been developed in leaps and bounds. The high storage and parallelism of DNA give it an inherent advantage in the field of DNA computations. DSD is widely used in analog computations and neural network computations. However, there are few studies on solving state transfer matrix using DSD circuits. Aiming at the above problems, a scheme for solution of state transfer matrix based on DSD circuits is proposed. In this paper, the summation, subtraction, multiplication, division and exponential reaction modules are built by the DSD reactions. Based on the reaction modules, DNA chemical reaction networks of state transfer matrix are constructed. DSD circuits are built by cascading the DNA chemical reaction networks. The solution of the state transfer matrix is implemented through the DSD circuits. The Visual DSD is used to verify the practicality of DSD circuits. This scheme may provide a reference to analog computations based on DSD circuits.

Detection and Differentiation of Amines and N‐Heterocycles via Recognition Enabled Chromatographic 19F NMR

AbstractIn this study, we successfully employed a 19F‐labeled cyclopalladium probe to achieve simultaneous differentiation and detection of various amines and N‐heterocyclic compounds. This method features a broad detection window, facilitating the discrimination and multi‐component analysis of structural analogs and isomers through the generation of characteristic 19F NMR signals with distinct chemical shifts. The utility of this approach is demonstrated in monitoring chemical reactions and identifying components in food, beverages, and cosmetics.