Chemically Research Articles

How Solvation Alters the Thermodynamics of Asymmetric Bond-Breaking: Quantum Simulation of NaK+ in Liquid Tetrahydrofuran.

Gas-phase potential energy surfaces (PESs) are often used to provide an intuitive understanding of molecular chemical reactivity. Most chemical reactions, however, take place in solution, and it is unclear whether gas-phase PESs accurately represent chemical processes in solvent environments. In this work we use quantum simulations to investigate the dissociation energetics of NaK+ in liquid tetrahydrofuran (THF) to understand the degree to which solvent interactions alter the gas-phase picture. Using umbrella sampling and thermodynamic integration techniques, we construct condensed-phase free energy surfaces of NaK+ on THF in both the ground and electronic excited states. We find that solvation by THF completely alters the nature of the NaK+ bond by reordering the thermodynamic dissociation products. Reaching the thermodynamic dissociation limit in THF also requires a long-range charge transfer process that has no counterpart in the gas phase. Gas-phase PESs, even with perturbations, cannot adequately describe the reactivity of simple asymmetric molecules in solution.

Assessment of the Aryl Hydrocarbon Receptor-Mediated Effects of Aromatic Sensitizers in Paper Recycling Effluent Employing Zebrafish Embryos and in Silico Docking.

Aromatic sensitizers and related substances (SRCs), which are crucial in the paper industry for facilitating color-forming and color-developing chemical reactions, inadvertently contaminate effluents during paper recycling. Owing to their structural resemblance to endocrine-disrupting aromatic organic compounds, concerns have arisen about potential adverse effects on aquatic organisms. We focused on SRC effects via the aryl hydrocarbon receptor (AHR), employing molecular docking simulations and zebrafish (Danio rerio) embryo exposure assessments. Molecular docking revealed heightened binding affinities between certain SRCs in the paper recycling effluents and zebrafish Ahr2 and human AHR, which are pivotal components in the SRC toxicity mechanism. Fertilized zebrafish eggs were exposed to SRCs for up to 96 h post fertilization; among these substances, benzyl 2-naphthyl ether (BNE) caused morphological abnormalities, such as pericardial edema and shortened body length, at relatively low concentrations (1 μM) during embryogenesis. Gene expression of cytochrome P450 1A (cyp1a) and ahr2 was also significantly increased by BNE. Co-exposure to the AHR antagonist CH-223191 only partially mitigated BNE's phenotypic effects, despite the effects of 2,3,7,8-tetrachlorodibenzo-p-dioxin being relatively well restored by CH-223191, indicating BNE's AHR-independent toxic mechanisms. Furthermore, some SRCs, including BNE, exhibited in silico binding affinity to the estrogen receptor and upregulation of cyp19a1b gene expression. Therefore, additional insights into the toxicity of SRCs and their mechanisms are essential. The present results provide important information on SRCs and other papermaking chemicals that could help minimize the environmental impact of the paper industry. Environ Toxicol Chem 2024;00:1-13. © 2024 SETAC.

Organocatalytic Synthesis of (Hetero)arylidene Malononitriles Using a More Sustainable, Greener, and Scalable Strategy.

The establishment of a green and sustainable Knoevenagel condensation reaction in organic chemistry is still crucial. This work aimed to provide a newly developed metal-free and halogen-free catalytic methodology for the synthesis of CS and (hetero-) arylidene malononitriles in the laboratory and industrial scale. The Knoevenagel condensation reaction of various carbonyl groups with malononitrile was investigated in ethanol, an ecofriendly medium, in the presence of seven nitrogen-based organocatalysts. A comparative study was conducted using two as-obtained and four commercially available nitrogen-based organocatalysts in Knoevenagel condensation reactions. The synthesis of CS gas (2-chlorobenzylidene malononitrile) using a closed catalytic system was optimized based on their efficiency and greener approach. The conversion of 100% and excellent yields were obtained in a short time. The products could be crystallized directly from the reaction mixture. After separating pure products, the residue solution was employed directly in the next run without any concentration, activation, purification, or separation. Furthermore, the synthesis of 2-chlorobenzylidenemahmonitrile (CS) was carried out on a large scale using imidazole as a selected nitrogen-based catalyst, afforded crystalline products with 95 ± 2% yield in five consecutive runs. Energy efficiency, cost saving, greener conditions, using only 5 mol% of organocatalyst, high recyclability of catalyst, prevention of waste, recycling extractant by a rotary evaporator for non-crystallized products, demonstrated the potential commercial production of CS using imidazole in ethanol as an efficient and highly recyclable catalytic system.

Green Chemistry and In silico Techniques for Synthesis of Novel Pyranopyrazole and Pyrazolo-pyrano-pyrimidine Derivatives as Promising Antifungal Agents.

Every year Invasive Fungal Infections (IFI) are globally affecting millions of people. Candida albicans and Aspergillus niger have been reported as the most infectious and mortality-inducing fungal strains among all pathogenic fungi. To tackle this problem in the current study Pyranopyrazoles and Pyrazolopyrano- pyrimidine derivatives were developed using molecular hybridization, green chemistry and one-pot multicomponent reaction. In the present work, New Chemical entities (NCE's) were developed on the basis of Structure activity relationship. All designed NCE's were screened for ADMET studies using the QikProp module of Schrodinger software. NCE's with zero violations were further docked on the crystal structure of 14α demethylase, cytochrome P450 and thymidine synthase (PDB ID: 5V5Z, 7SHI, 1BID). Selected molecules were synthesized using green chemistry techniques and evaluated for in vitro antifungal activity against Candida albicans and Aspergillus niger. Designed NCE's (B1-12 and C1-11) showed favorable results in ADMET studies. In the docking study six compounds from series-B and five molecules from series- C showed good dock score and binding interaction when compared with the standard drugs. Compounds B-3 and C-4 showed the highest zone of inhibition activity against Candida albicans, where as B-1 and C-3 had shown highest zone of inhibition activity against Aspergillus niger. Bicyclic ring (series B) showed better activity as compare to fused tricyclic ring (series C).

Localization and Orientation of Dye Molecules at the Surface of a Levitated Microdroplet in Air Revealed by Whispering Gallery Mode Resonances.

Microdroplets offer unique environments that accelerate chemical reactions; however, the mechanisms behind these processes remain debated. The localization and orientation of solute molecules near the droplet surface have been proposed as factors for this acceleration. Since significant reaction acceleration has been observed for electrospray- and sonic-spray-generated aerosol droplets, the analysis of microdroplets in air has become essential. Here, we utilized whispering gallery mode (WGM) resonances to investigate the localization and orientation of dissolved rhodamine B (RhB) in a levitated microdroplet (∼3 μm in diameter) in air. Fluorescence enhancement upon resonance with the WGMs revealed the localization and orientation of RhB near the droplet surface. Numerical modeling using Mie theory quantified the RhB orientation at 68° to the surface normal, with a small fraction randomly oriented inside the droplet. Additionally, low RhB concentrations increased surface localization. These results support the significance of surface reactions in the acceleration of microdroplet reactions.

Pyrolysis characterization and kinetic analysis of typical coals in western China: effects of coal type, particle size and heating rate

ABSTRACT The three typical coals selected in this study (Shuangyi coal (SY), Hengsheng coal (HS) and Ningxia anthracite (NX)) are widely used in western China, but their pyrolysis characteristics have been less studied. In this study, based on the simultaneous thermal analysis-Fourier transform infrared spectroscopy (STA-FTIR) technique, the effects of different coal types, particle sizes and heating rates on the pyrolysis characteristics of coal powder were investigated. The results showed that the weight loss behaviors of different types of coals with different particle sizes varied, as influenced by the type of coal and heat transfer. When the particle size increased from 170 μm to 380 μm, the weight loss rate decreased by 2.95% and 24.45% for SY and NX coals while increased by 4.81% for HS coals; whereas for the maximum decomposition rate, both SY and HS coals showed an increasing tendency (increased by 2.76% and 9.32%), while NX coals decreased by 21.43%. The R2 of the three coal DTG curves fitted by subcurves was all 0.999, which proved that the nature of coal weight loss was the coupling effect of certain types of chemical reactions or covalent bond breakage. Real-time infrared spectroscopy was combined with covalent bonding to explore the major gas products and their influence by particle size. The activation energies at different temperatures were calculated by the Coats-Redfern method, in which the activation energies of the fast pyrolysis stage of HS coal were 1.68 and 2.75 times higher than those of the other two stages, 1.79 and 3.03 times higher than those of SY coal, and 1.99 and 1.11 times higher than those of NX coal, respectively.

Reactions of Hydroperoxyl Radicals (HO2) with Oxygenated Aromatic Bio-oil Model Compounds

During thermal utilization of biomass, a complex array of reactions ensues in the oxidative environment between fragments of the biomass and reactive species. In the low-temperature window, hydroperoxyl (HO2) radicals assume a central role prior to the establishment of the O/H radical pool. Anisole, cresol, guaiacol and vanillin are often utilized as representative model compounds to comprehend the combustion chemistry of the phenolic entities in biomass and oxygen-containing derived bio-oil. This paper reports thermo-kinetic parameters for the reactions of HO2 radicals with anisole, cresol, guaiacol and vanillin. Computed activation enthalpies entail facile values for H abstraction from the side-chain functional groups in the investigated compounds. H abstraction from the hydroxyl groups incurs lower activation energies in reference to methyl sites in cresol and guaiacol. Hence, H abstraction from the OH sites in these two molecules proceeds at a faster reaction rate constant when compared to abstraction from the methyl site. In the vanillin molecule, abstraction from the aldehydic and hydroxyl sites portrays comparable importance. The effect of scaling vibrational frequencies and the type of applied quantum tunneling on the computed reaction rate constants were thoroughly explored. Analysis of entropies of activation indicates that the transition states exhibit a product-like character. While ignition delay times of fuels often exhibit a profound sensitivity towards initial H abstraction reactions by HO2, we found that ignition delay times of the four title molecules remain almost unchanged when updating literature kinetics models with new reaction rate constants calculated herein. It is anticipated that reported outcomes from this study aid in formulating a better understanding of the complex chemical reactions that dictate oxidative decomposition of oxygenated bio-oil model compounds.

Atomic Electrostatic Potential as a Descriptor of Aminolysis of Phenyl and Thiophenyl Acetates and Hydrolysis of Acetanilides

Abstract: Hydrolysis of acetanilides and aminolysis of phenyl and thiophenyl acetates are related reactions since these are processes of nucleophilic substitution on the carbonyl carbon. Current views of chemical reactivity based on the DFT theory rely upon reactivity indices that are descriptors of both the reaction center and the molecule as a whole, and have not been applied to the given processes before. One of such descriptors is an atomic electrostatic potential. The given parameter was calculated by the DFT theory M06/6-311+G (non-specific solvation, MeCN, SMD, and full optimization) for the structures of substituted phenyl acetates XPhO-C(O)Me, acetanilides XPhNHC(O)Me, thiophenyl acetates ZPhSC(=O)Me, and benzyl amines XPhСH2NH2 (X, Z substituents). It has been found that all relationships between the atomic electrostatic potential, the charge on the reaction center in the Hirshfeld scheme, and logK are symbatic. Consequently, in all of the cases, the rate is determined by the nucleophilic attack on the reaction center, with the activity/selectivity relationship being observed. The fact that the reaction rate is limited by the nucleophilic attack of the reagent is not inconsistent with the views of the reaction being concerted, since it is known that such reactions may be quite concerted though not quite synchronous.

A Cytochrome P450 TxtE Model System with Mechanistic and Theoretical Evidence for a Heme Peroxynitrite Active Species.

The cytochrome P450 homolog, TxtE, efficiently catalyzes the direct and regioselective aromatic nitration of the indolyl moiety of L-tryptophan to 4-nitro-L-tryptophan, using nitric oxideand dioxygenas co-substrates. Pathways for such direct and selective nitration of heteroaromatic motifs present platforms for engineering new nitration biocatalysts for pharmacologically beneficial targets, among a medley of other pivotal industrial applications. Precise mechanistic details concerning this pathway are only weakly understood, albeit a heme iron(III)-peroxynitrite active species has been postulated. To shed light on this unique reaction landscape, we investigated the indole nitration pathway of a series of biomimetic ferric heme superoxide mimics, [(Por)FeIII(O2-•)], in the presence of NO. Therein, our model systems gave rise to three distinct nitroindole products, including 4-nitroindole, the product analogous to that obtained with TxtE. Moreover, 15N and 18O isotope labeling studies, along with meticulously designed control experiments lend credence to a heme peroxynitrite active nitrating agent, drawing close similarities to the tryptophan nitration mechanism of TxtE. All organic and inorganic reaction components have been fully characterized using spectroscopic methods. Theoretical investigation into several mechanistic possibilities deem a unique indolyl radical based reaction pathway as the most energetically favorable, products of which, are in excellent agreement with experimental findings.

Groot Aub groundwater quality and its suitability for domestic purposes, Namibia

The Groot Aub (GA) settlement depends entirely on groundwater for domestic purposes and other development activities. Development activities are mainly agriculture, such as animal husbandry, chicken farming and crop farming using irrigation. However, these activities have the potential to contaminate the groundwater system. A total of 87 groundwater samples were collected from the boreholes in the study area during the dry and wet season. Water quality parameters (pH, salinity, total dissolved solids (TDS), electrical conductivity (EC) and hydrochemistry (Na+ > Ca2+ > Mg2+ > K+, and HCO3− > SO42− > Cl−) of 5 boreholes and 1 reservoir tank were analysed. The dominant cations were attributed to cation exchange processes as a coupled exchange of Na+ + K+ replacing Ca2+; and Na+ replacing Mg2+ ions in the rock–water interactions. The HCO3− anion is attributed to underlying rich carbonate rocks in the study area and chemical reactions between groundwater and silicate minerals. TDS ranged from 639.01 to 1 998.96 mg/L. The microbial levels as indicated by heterotrophic plate count (HPC) values exceed the limits imposed by the local Namibian and WHO drinking water regulations. The Piper diagrams showed a mixed water type of mainly HCO3− and SO42− anions and Na+ and Ca2+ > Mg2+ cations. The study shows that the elemental composition of the groundwater is impacted significantly by primarily anthropogenic activities and secondarily geogenic processes. Based on the results of this study it is recommended that a buffer zone be created between human activities and production boreholes to avoid further groundwater contamination.

Effect of chemical absorption on Jeffery Fluid Flow in saturated Porous Media with variable thermal conductivity

This study investigates the impact of species absorption of Jeffery fluid flow through a saturated permeable medium with variable thermal conductivity. The dimensional partial nonlinear derivative model controlling the chemical reacting fluid flow is transformed to invariant form. The resulting flow equations are computed numerically using an approximated finite implicit Crack-Nicolson. A chemical absorption of fluid reactant occurs in a boundless vertical device. Computations are performed for different parameters to examine their sensitivity under isothermal temperature conditions. The computed results are offered graphically for qualitative and quantitative insights into the flow behaviour. The obtained outcomes revealed that the fluid flow rate rises with an increasing values of the parameters and, and it damps with upsurge in the values of the parameters, and. The heat transfer field is reduced with enhancing values of the thermal source, viscous dissipation and time, but declines for a boosted value of the terms suction and Prandtl number. Also, the mass transfer field is higher when mass absorption and time are increased, and diminish with an elevate in the values of Schmidt number and chemical reactions.

Factors Affecting Non-Enzymatic Protein Acylation by trans-3-Methylglutaconyl Coenzyme A

The leucine catabolism pathway intermediate, trans-3-methylglutaconyl (3MGC) CoA, is considered to be the precursor of 3MGC acid, a urinary organic acid associated with specific inborn errors of metabolism (IEM). trans-3MGC CoA is an unstable molecule that can undergo a sequence of non-enzymatic chemical reactions that lead to either 3MGC acid or protein 3MGCylation. Herein, the susceptibility of trans-3MGC CoA to protein 3MGCylation was investigated. trans-3MGC CoA was generated through the activity of recombinant 3-methylcrotonyl CoA carboxylase (3MCCCase). Following enzyme incubations, reaction mixtures were spin-filtered to remove 3MCCCase. The recovered filtrates, containing trans-3MGC CoA, were then incubated in the presence of bovine serum albumin (BSA). Following this, sample aliquots were subjected to α-3MGC IgG immunoblot analysis to probe for 3MGCylated BSA. Experiments revealed a positive correlation between trans-3MGC CoA incubation temperature and 3MGCylated BSA immunoblot signal intensity. A similar correlation was observed between incubation time and 3MGCylated BSA immunoblot signal intensity. When trans-3MGC CoA hydratase (AUH) was included in incubations containing trans-3MGC CoA and BSA, 3MGCylated BSA immunoblot signal intensity decreased. Evidence that protein 3MGCylation occurs in vivo was obtained in studies with liver-specific 3-hydroxy-3-methylglutaryl (HMG) CoA lyase knockout mice. Therefore, trans-3MGC CoA is a reactive, potentially toxic metabolite, and under normal physiological conditions, lowering trans-3MGC CoA levels via AUH-mediated hydration to HMG CoA protects against aberrant non-enzymatic chemical reactions that lead to protein 3MGCylation and 3MGC acid production.

Hydrogen production from iron sulphate photolysis using mark-5 cycle

ABSTRACT Hydrogen production was carried out in a photochemical device in a Mark-5 cycle. The photolysis of iron sulphate solution was carried out in a close periodic system. The reaction mixture was 8.5 g iron sulphate compound (FeSO4•7 H2O), 2.5 g I2 and 1.0 g HI in 100 mL water. Fifty millilitres of this solution was filled into a quartz reactor and connected to cycle system. The optimisation of hydrogen production was achieved by temperature, flow rate and radiation irradiation. The maximum hydrogen generated was 50.0 × 1016 molecules per minute at 120 °C temperature, 0.08 mL/sec. Pump speed, pressure 0.30 MPas, and Hg-vapour λmax = 365 nm. Eact. = 14.92 kC/mol caused bimolecular reactions to occur at low temperatures by photochemical action. Quantum yield of hydrogen depended on the absorbed of 0.5 × 1015 kvant/s. The energy of the quantum above T ≥ 100°C temperatures was φ ≥ 1. The dependence of the hydrogen generation rate (W) increased from 0.001 to 0.0038 × 1016 molecules/sec at 10-90 minutes, respectively.

Computer-Aided Synthesis Planning (CASP) and Machine Learning: Optimizing Chemical Reaction Conditions.

Computer-aided synthesis planning (CASP) has garnered increasing attention in light of recent advancements in machine learning models. While the focus is on reverse synthesis or forward outcome prediction, optimizing reaction conditions remains a significant challenge. For datasets with multiple variables, the choice of descriptors and models is pivotal. This selection dictates the effective extraction of conditional features and the achievement of higher prediction accuracy. This review delineates the origins of data in conditional optimization, the criteria for descriptor selection, the response models, and the metrics for outcome evaluation, aiming to acquaint readers with the latest research trends and facilitate more informed research in this domain.

Three-Dimensional Radiative Rotating MHD Nanofluid Flow of Over a Stretched Sheet with Homogeneous-Heterogeneous Chemical Reactions

CNTs are employed in energy storage, device modelling, automobile parts, water filters, thin-film electronics, coating, and more. The continuous three-dimensional (3D) magnetohydrodynamics (MHD) rotational flow of water-based nanofluid comprising SWCNT and MWCNT past a stretching/shrinking sheet under magnetic field and homogeneous-heterogeneous chemical processes is examined in this study. Heat transport is also examined with thermal radiation and heat source/sink. The governing partial differential equations (PDEs) are transformed to non-linear ODEs using proper similarity transformations and solved numerically using MATLAB's bvp4c package. Graphs and tables show how magnetic field, rotational, suction/injection, thermal radiation, heat source/sink parameters, nanoparticle (NP) volume fraction, and homogeneous and heterogeneous reactions affect velocity, temperature, concentration, skin friction coefficient, and Nusselt number. For larger rotational parameters, the main velocity declines and the second velocity increases, and MWCNTs flow more than SWCNTs.

Numerical Study on Chemical Kinetic Characteristics of Counterflow Diffusion Flame Extinction of Methane/Ammonia/Air Flame under High Pressure or Air Preheating Temperature

Green ammonia has become an increasingly popular fuel in recent years because of its combustion process without carbon oxide release. Adding ammonia to methane fuel for co-combustion has become one of the important research topics in the current combustion field. In the present study, the CH4/NH3/Air counterflow diffusion flame was taken as the research object, and Chemkin-2019 R3 software was used to explore and analyze the flame extinction limit and chemical kinetics characteristics under different ammonia mixing ratios, initial pressures, and air preheating temperatures. It was obtained that the flame extinction stretch rate was decreased by increasing the NH3 mole fraction in the CH4/NH3 mixed fuel. The increase in pressure or air preheating temperature would accelerate the chemical reaction rate of each component in the combustion process, increase the flame extinction limit, and counteract the “stretching effect” of the flame, thus restraining the flame extinguishing phenomenon. The results of a path analysis show that the formation and consumption of OH had an important influence on flame extinction in the chain reaction. The net reaction rate of OH increases with increasing the initial pressure or air preheating temperature, which leads to an increase in flame intensity, combustion stability, and the extinction limit. Furthermore, the function curve between the reaction influences the RIF factor and the stretch rate of the first-to-ten reactions, affected by the heat release of flame combustion, was drawn and quantitatively analyzed. Eventually, a sensitivity analysis of the flame under different working conditions was completed, which found that promoting the forward reaction R39 H + O2<=>O + OH also promotes the positive combustion as a whole when the flame was near extinction. The sensitivity coefficient of R39 in the CH4/NH3/Air flame increases with the growing initial pressure. The increasing air preheating temperature was capable of switching the reaction of R248 NH2 + OH<=>NH + H2O in the CH4/NH3/Air flame from an inhibiting reaction to a promoting reaction, while decreasing the sensitivity coefficient of inhibiting the forward reaction R10 O + CH3<=>H + CH2O, R88 OH + HO2<=>O2 + H2O, and R271 H + NO + M<=>HNO + M. Thus, the inhibition effect of flame extinction was weakened, and the positive progress of combustion was promoted.

PCA-based synthetic sensitivity coefficients for chemical reaction network in cancer

Chemical reaction networks are powerful tools for modeling cell signaling and its disruptions in diseases like cancer. Realistic chemical reaction networks involve hundreds of proteins and reactions, resulting in a model depending on a consistently large number of kinetic parameters. Since finely calibrating all the parameters would require an unrealistic amount of data, proper sensitivity analysis is required to identify a subset of parameters for which fine tuning is needed and thus provide a fundamental tool for the qualitative analysis of the network. We present a multidisciplinary approach for computing a set of synthetic sensitivity indices. These indices rank the kinetic parameters, based on the impact that errors in their values would have on the protein concentration profile at equilibrium. Our tests on a chemical reaction network devised for colorectal cells demonstrate the effectiveness of the considered sensitivity indices in different scenarios including in-silico drug dosage and novel therapeutic target discovery. The Matlab code for computing the synthetic sensitivity indices and the data concerning the network for colorectal cells are available at https://github.com/theMIDAgroup/CRN_sensitivity.

Indirect Voltammetry Detection of Non-Electroactive Neurotransmitters Using Glassy Carbon Microelectrodes: The Case of Glutamate

Glassy carbon (GC) microelectrodes have been successfully used for the detection of electroactive neurotransmitters such as dopamine and serotonin through voltammetry. However, non-electroactive neurotransmitters such as glutamate, lactate, and gamma-aminobutyric acid (GABA) are inherently unsuitable for detection through voltammetry techniques without functionalizing the surface of the microelectrodes. To this end, we present here the immobilization of the L-glutamate oxidase (GluOx) enzyme on the surface of GC microelectrodes to enable the catalysis of a chemical reaction between L-glutamate, oxygen, and water to produce H2O2, an electroactive byproduct that is readily detectable through voltammetry. This immobilization of GluOx on the surface of bare GC microelectrodes and the subsequent catalytic reduction in H2O2 through fast-scan cyclic voltammetry (FSCV) helped demonstrate the indirect in vitro detection of glutamate, a non-electroactive molecule, at concentrations as low as 10 nM. The functionalized microelectrodes formed part of a four-channel array of microelectrodes (30 μm × 60 μm) on a 1.6 cm long neural probe that was supported on a flexible polymer, with potential for in vivo applications. The types and strengths of the bond between the GC microelectrode surface and its functional groups, on one hand, and glutamate and the immobilized functionalization matrix, on the other hand, were investigated through molecular dynamic (MD) modeling and Fourier transform infrared spectroscopy (FTIR). Both MD modeling and FTIR demonstrated the presence of several covalent bonds in the form of C-O (carbon–oxygen polar covalent bond), C=O (carbonyl), C-H (alkenyl), N-H (hydrogen bond), C-N (carbon–nitrogen single bond), and C≡N (triple carbon–nitrogen bond). Further, penetration tests on an agarose hydrogel model confirmed that the probes are mechanically robust, with their penetrating forces being much lower than the fracture force of the probe material.

Mechanism of methanol-to-olefin (MTO) reaction

The full name of MTO is methanol to olefin, which is a new chemical reaction process to gain an important chemistry industry raw material. In this paper, we mainly talk about several general reaction process as well as the mechanism of the reaction. The use of molecular sieve catalytic process is a key point where the new MTO process different form the original simple petroleum cracking in order to again olefin. In this work we mainly discuss how the MTO process could happen with the assist of the molecular sieve catalyst. There are direct mechanism Carbene mechanism and Methane-formaldehyde mechanism. The effect of the direct mechanism is to gain some simple and short Carbon-Carbon product. And then the indirect mechanism will take on to control the rate of the reacting process and the ration of different products. By studying on the mechanism of the MTO reaction, we can figure out how a powerful catalyst, molecular sieve catalyst, works in the reaction. Also, the MTO process is a meaningful way to take place of the origin cracking process to gain olefin, as the storage of petroleum is decreasing fast recently.

Performance of flexible CeO2 composite abrasive in force rheological polishing of fused silica glass

Polishing is critical for obtaining high-quality surfaces on fused silica glass components, which are used extensively in numerous civil and military applications. The abrasive used in conventional polishing processes is typically on the microscale or nanoscale. This study prepared a millimeter-scale flexible composite abrasive consisting of a natural rubber (NR) core coated with CeO2 for use in force rheological polishing (FRP), aiming to improve efficiency and material removal selectivity without compromising surface quality. An analysis of the synthesized abrasive indicated that the CeO2 exhibited excellent adhesion to the surface of the rubber core. The results of polishing experiments conducted on fused silica glass workpieces using the proposed composite abrasive indicated that following 20 min of FRP, the surface roughness (Sa) of the workpiece was reduced from 464.2 nm to 2.2 nm and a high material removal rate (MRR) of 337.2 nm/min was achieved with negligible damage to the surface. The utilization of the composite abrasive for FRP effectively promoted the chemical reaction between CeO2 and silica glass to achieve rapid material removal. Furthermore, the material removal selectivity characteristics of the composite abrasive were investigated by polishing micro-grooved surfaces. The resulting groove contours and morphologies revealed that the composite abrasive played a crucial role in selectively removing material from the edges and bottoms of the micro-grooves such that elevated points experienced more extensive material removal, realizing a flatter surface. However, the effectiveness of selective removal diminished as the micro-groove width increased. The results of this study furnish compelling theoretical and experimental evidence supporting the utilization of millimeter-scale flexible composite abrasives in FRP.