New insights in polydopamine formation via surface adsorption

Polydopamine is a biomimetic self-adherent polymer, which can be easily deposited on a wide variety of materials. Despite the rapidly increasing interest in polydopamine-based coatings, the polymerization mechanism and the key intermediate species formed during the deposition process are still controversial. Herein, we report a systematic investigation of polydopamine formation on halloysite nanotubes; the negative charge and high surface area of halloysite nanotubes favour the capture of intermediates that are involved in polydopamine formation and decelerate the kinetics of the process, to unravel the various polymerization steps. Data from X-ray photoelectron and solid-state nuclear magnetic resonance spectroscopies demonstrate that in the initial stage of polydopamine deposition, oxidative coupling reaction of the dopaminechrome molecules is the main reaction pathway that leads to formation of polycatecholamine oligomers as an intermediate and the post cyclization of the linear oligomers occurs subsequently. Furthermore, Tris molecules are incorporated into the initially formed oligomers.

An experimental study of the reactivity of terpinolene and β-caryophyllene with the nitrate radical

Biogenic volatile organic compounds (BVOCs) are subject to an intense emission by forests and crops into the atmosphere. They can rapidly react with the nitrate radical (NO3) during nighttime to form number of functionalized products. Among them, organic nitrates (ON) have been shown to behave as reservoirs of reactive nitrogen and consequently influence the ozone budget and secondary organic aerosols (SOA) which are known to have a direct and indirect effect on the radiative balance, and thus on climate. Nevertheless, BVOCs + NO3 reactions remain poorly understood. Thus, the primary purpose of the follow-up study is to furnish new kinetic and mechanistic data for one monoterpenes (C10H16), terpinolene, and one sesquiterpene (C15H24), β-caryophyllene, using simulation chamber experiments. These two compounds have been chosen in order to fill the lack of experimental data. Rate constants have been measured using both relative and absolute methods. They have been measured to be (5.5 ± 3.8) × 10−11 and (1.7 ± 1.4) × 10−11 cm3 molecule−1 s−1 for terpinolene and β-caryophyllene respectively. Mechanistic studies have also been conducted in order to identify and quantify the main reaction products. Total organic nitrates and SOA yields have been determined. Both terpenes appear to be major ON precursors both in gas and particle phase with formation yields of 69 % for terpinolene and 79 % for β-caryophyllene respectively. They also are major SOA precursor, with maximum SOA yields of around 60 % for both of the compounds. In order to support these observations, chemical analyses of the gas phase products were performed at the molecular scale using PTR-TOF-MS and FTIR. Detected products allowed proposing chemical mechanisms and providing explanations through peroxy and alkoxy reaction pathways.

Numerical Steady and Transient Evaluation of a Confined Swirl Stabilized Burner

Lean premixed combustion technology became state of the art in recent heavy-duty gas turbines and aeroengines. In combustion chambers operating under fuel-lean conditions, unsteady heat release can augment pressure amplitudes, resulting in component engine damages. In order to achieve deeper knowledge concerning combustion instabilities, it is necessary to analyze in detail combustion processes. The current study supports this by conducting a numerical investigation of combustion in a premixed swirl-stabilized methane burner with operating conditions taken from experimental data that were recently published. It is a follow-up of a previous paper from Farisco et al., 2019 where a different combustion configuration was studied. The commercial code ANSYS Fluent has been used with the aim to perform steady and transient calculations via Large Eddy Simulation (LES) of the current confined methane combustor. A validation of the numerical data has been performed against the available experiments. In this study, the numerical temperature profiles have been compared with the measurements. The heat release parameter has been experimentally and numerically estimated in order to point out the position of the main reaction zone. Several turbulence and combustion models have been investigated with the aim to come into accord with the experiments. The outcome showed that the combustion model Flamelet Generated Manifold (FGM) with the k-ω turbulence model was able to correctly simulate flame lift-off.

A computer-aided method for controlling chemical resistance of drugs using RRKM theory in the liquid phase

The chemical resistance of drugs against any change in their composition and studying the rate of multiwell-multichannel reactions in the liquid phase, respectively, are the important challenges of pharmacology and chemistry. In this article, we investigate two challenges together through studying drug stability against its unimolecular reactions in the liquid phase. Accordingly, multiwell-multichannel reactions based on 1,4-H shifts are designed for simplified drugs such as 3-hydroxyl-1H-pyrrol-2(5H)-one, 3-hydroxyfuran-2(5H)-one, and 3-hydroxythiophen-2(5H)-one. After that, the reverse and forward rate constants are calculated by using the Rice Ramsperger Kassel Marcus theory (RRKM) and Eckart tunneling correction over the 298–360 K temperature range. Eventually, using the obtained rate constants, we can judge drug resistance versus structural changes. To attain the goals, the potential energy surfaces of all reactions are computed by the complete basis set-quadratic Becke3 composite method, CBS-QB3, and the high-performance meta hybrid density functional method, M06-2X, along with the universal Solvation Model based on solute electron Density, SMD, due to providing more precise and efficient results for the barrier heights and thermodynamic studies. To find the main reaction pathway of the intramolecular 1,4-H shifts in the target molecules, all possible reaction pathways are considered mechanistically in the liquid phase. Also, the direct dynamics calculations that carry out by RRKM theory on the modeled pathways are used to distinguish the main reaction pathway. As the main finding of this research, the results of quantum chemical calculations accompanied by the RRKM/Eckart rate constants are used to predict the stability of drugs. This study proposes a new way to examine drug stability by the computer-aided reaction design of target drugs. Our results show that 3-hydroxyfuran-2(5H)-one based drugs are the most stable and 3-hydroxythiophen-2(5H)-one based drugs are more stable than 3-hydroxy-1H-pyrrol-2 (5H)-one based drugs in water solution.

Enhancement of chlorine on Pd catalyst for H2O2 in-situ synthesis in electro-Fenton system: Kinetics and Mechanism

Palladium-based catalyst has been widely employed in electro-Fenton process for in-situ generation of H2O2. However, the selectivity to H2O2 achieved so far is still far below application level. In this work, a series of Cl-FePd/γ-Al2O3/Al catalysts were prepared by a three-step-impregnation method, exhibiting excellent activity in H2O2 in-situ synthesis and high efficiency in phenol degradation. The characterization results showed that the Cl could assist in increasing the content of Pd0 and reducing the isoelectric point of catalyst, leading to the dramatic promotion in synthesis of H2O2. Moreover, theoretical calculation and kinetics further demonstrated that the Cl doping could facilitate the main reaction in H2O2 synthesis, as well as inhibit side reactions, including the dissociation of O-O bond, hydrogenation and decomposition. Furthermore, plausible mechanism and degradation pathways were elaborated based on ESR and GC-MS results. These findings illustrate the value of palladium-based Cl-FePd/γ-Al2O3/Al catalyst in its application in electro-Fenton process.

One-Pot Synthesis of Ni0.05Ce0.95O2−δ Catalysts with Nanocubes and Nanorods Morphology for CO2 Methanation Reaction and in Operando DRIFT Analysis of Intermediate Species

The valorization of CO2 via renewable energy sources allows one to obtain carbon-neutral fuels through its hydrogenation, like methane. In this study, Ni0.05Ce0.95O2−δ catalysts were prepared using a simple one-pot hydrothermal method yielding nanorod and nanocube particles to be used for the methanation reaction. Samples were characterized by XRD, BET, TEM, H2-TPR, and H2-TPD experiments. The catalytic activity tests revealed that the best performing catalyst was Ni0.05Ce0.95O2−δ, with nanorod morphology, which gave a CO2 conversion of 40% with a selectivity of CH4 as high as 93%, operating at 325 °C and a GHSV of 240,000 cm3 h−1 g−1. However, the lower activation energy was found for Ni0.05Ce0.95O2−δ catalysts with nanocube morphology. Furthermore, an in operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis was performed flowing CO2:H2 or CO:H2 mixture, showing that the main reaction pathway, for the CO2 methanation, is the direct hydrogenation of formate intermediate.

Polyimides from 2,5-bis[4-(4-aminophenoxy)benzoyl]furan and their thermal crosslinking reaction

Several polyimides were prepared via two-step polycondensation from novel 2,5-furandicarboxylic acid–based diamine, 2,5-bis[4-(4-aminophenoxy)benzoyl]furan, with commercial dianhydrides. The chemical structures of the monomers and polymers were characterized by FT-IR and NMR in detail, respectively. The polyimides exhibited high performances with 5 wt% weight loss temperatures of over 410 oC, glass transition temperatures of over 214 oC, and tensile strengths and Young’s moduli of up to 130 MPa and 3.2 GPa, respectively. The thermal crosslinking mechanism was studied by FT-IR, Raman spectroscopy, and model reaction analysis, which showed the Diels–Alder reaction between the furan group and diphenylethylene group was the main reaction. The crosslinked polyimide films showed improved solvent resistance, and thermal and mechanical properties.

Responses to corporate governance code: evidence from a longitudinal study

Drawing upon neo-institutional theory as the perspective for research on corporate governance, we present the results of empirical studies on compliance with best practice codes. We view the declarations of conformity as the organizational response to institutional pressure and address questions on (1) how companies respond to recommendations on board best practice and (2) how these reactions evolve over time. The study employs the mixed method approach and is based on a time-series sample of conformity declarations published by 126 companies listed on the Warsaw Stock Exchange during the period 2006–2019. Descriptive statistics indicate an increase in the number of complying companies, an improvement in compliance quality and the growing length of conformity declarations. In the content analysis we identify two main reaction strategies (acceptance and rejection) with seven selected responses. We discuss the contribution to the existing literature on reactions to new practices in corporate governance.

Degradation of 17 Benzodiazepines by the UV/H2O2 Treatment

Benzodiazepines are one group of psychoactive drugs widely detected in water environments, and their persistence during conventional wastewater treatment has raised great concerns. Here we investigated the degradation of 17 benzodiazepines in water by UV/H2O2 treatment. The results showed that the UV/H2O2 treatment significantly increased the degradation of 17 benzodiazepines in phosphate buffer solutions at pH 7.0. This can be attributed to the high reactivity of hydroxyl radicals (·OH) towards benzodiazepines with second-order rate constants of 3.48 × 109 M−1 s−1–2.44 × 1010 M−1 s−1. The degradation of alprazolam, a typical benzodiazepine, during the UV/H2O2 treatment was increased with the increasing H2O2 dosage. The solution pH influenced the alprazolam degradation significantly, with the highest degradation at pH 7.0. Water matrix, such as anions (Cl−, HCO3−, NO3−) and humic acid, decreased the degradation of alprazolam by UV/H2O2 treatment. Based on the degradation products identified using quadrupole time-of-flight mass spectrometer, the degradation mechanisms of alprazolam by UV/H2O2 treatment were proposed, and hydroxylation induced by ·OH was the main reaction pathway. The degradation of 17 benzodiazepines by UV/H2O2 treatment in wastewater treatment plant effluent and river water was lower than that in phosphate buffer solutions. The results showed that the benzodiazepine psychoactive drugs in natural water can be effectively removed by the UV/H2O2 treatment.

The oxidation of 4-bromacetophenone by ozone in acetic acid

The kinetics and mechanism of oxidation of 4-bromoacetophenone by ozone in acetic acid solution have been studied. It was shown that 77% of the starting material is oxidized by the benzene ring; 8% of 4-bromobenzoic acid and small amounts of carbon (IV) oxide were identified among the side chain ozonation products. The main reaction products are aliphatic peroxide compounds, which have in their structure one hydroperoxide group. Manganese (II) acetate was shown to be the most effective catalyst for the side chain reaction of 4-bromoacetophenone in acetic acid. High selectivity for the side chain is achieved only at sufficiently high concentrations of catalyst ([Mn(OAc)2]0:[ArH]0=1:4). The main product of the catalytic oxidation of 4-bromoacetophenone is 4-bromobenzoic acid with a yield of 82.5%. The found dependences of the rate of oxidation of 4-bromoacetophenone by ozone on the concentration of reactants are described by the kinetic equation of the third order, the reaction rate has the first order with respect to each reagent. It was found that the decisive role in the selective oxidation of 4-bromoacetophenone is played by two-stage oxidation, in which ozone predominantly reacts with the reduced form of manganese, and the introduction of the substrate into side chain oxidation is carried out by the reaction with the oxidized form of metal. According to the research results, the mechanism of catalytic ozonation of 4-bromoacetophenone in acetic acid has been proposed, which involves ion-radical non-chain oxidation of the substrate.