Unconventional mechanism and selectivity of the Pd-catalyzed C–H bond lactonization in aromatic carboxylic acid

The search for more effective and highly selective C–H bond oxidation of accessible hydrocarbons and biomolecules is a greatly attractive research mission. The elucidating of mechanism and controlling factors will, undoubtedly, help to broaden scope of these synthetic protocols, and enable discovery of more efficient, environmentally benign, and highly practical new C–H oxidation reactions. Here, we reveal the stepwise intramolecular SN2 nucleophilic substitution mechanism with the rate-limiting C–O bond formation step for the Pd(II)-catalyzed C(sp3)–H lactonization in aromatic 2,6-dimethylbenzoic acid. We show that for this reaction, the direct C–O reductive elimination from both Pd(II) and Pd(IV) (oxidized by O2 oxidant) intermediates is unfavorable. Critical factors controlling the outcome of this reaction are the presence of the η3-(π-benzylic)–Pd and K+–O(carboxylic) interactions. The controlling factors of the benzylic vs ortho site-selectivity of this reaction are the: (a) difference in the strains of the generated lactone rings; (b) difference in the strengths of the η3-(π-benzylic)–Pd and η2-(π-phenyl)–Pd interactions, and (c) more pronounced electrostatic interaction between the nucleophilic oxygen and K+ cation in the ortho-C–H activation transition state. The presented data indicate the utmost importance of base, substrate, and ligand in the selective C(sp3)–H bond lactonization in the presence of C(sp2)–H.

VOCs Photothermo-Catalytic Removal on MnOx-ZrO2 Catalysts

Solar photothermo-catalysis is a fascinating multi-catalytic approach for volatile organic compounds (VOCs) removal. In this work, we have explored the performance and the chemico-physical features of non-critical, noble, metal-free MnOx-ZrO2 mixed oxides. The structural, morphological, and optical characterizations of these materials pointed to as a low amount of ZrO2 favoured a good interaction and the ionic exchange between the Mn and the Zr ions. This favoured the redox properties of MnOx increasing the mobility of its oxygens that can participate in the VOCs oxidation through a Mars-van Krevelen mechanism. The further application of solar irradiation sped up the oxidation reactions promoting the VOCs total oxidation to CO2. The MnOx-5 wt.%ZrO2 sample showed, in the photothermo-catalytic tests, a toluene T90 (temperature of 90% of conversion) of 180 °C and an ethanol T90 conversion to CO2 of 156 °C, 36 °C, and 205 °C lower compared to the thermocatalytic tests, respectively. Finally, the same sample exhibited 84% toluene conversion and the best selectivity to CO2 in the ethanol removal after 5 h of solar irradiation at room temperature, a photoactivity similar to the most employed TiO2-based materials. The as-synthetized mixed oxide is promising for an improved sustainability in both catalyst design and environmental applications.

Visible Light-Induced Aerobic Oxidative Dehydrogenation of C–N/C–O to C=N/C=O Bonds Using Metal-Free Photocatalysts: Recent Developments

Performing synthetic transformation using visible light as energy source, in the presence of a photocatalyst as a promoter, is currently of high interest, and oxidation reactions carried out under these conditions using oxygen as the final oxidant are particularly convenient from an environmental point of view. This review summarizes the recent developments achieved in the oxidative dehydrogenation of C–N and C–O bonds, leading to C=N and C=O bonds, respectively, using air or pure oxygen as oxidant and metal-free homogeneous or recyclable heterogeneous photocatalysts under visible light irradiation.

Large-eddy simulation of diesel pilot spray ignition in lean methane-air and methanol-air mixtures at different ambient temperatures

In dual-fuel compression-ignition engines, replacing common fuels such as methane with renewable and widely available fuels such as methanol is desirable. However, a fine-grained understanding of diesel/methanol ignition compared to diesel/methane is lacking. Here, large-eddy simulation (LES) coupled with finite rate chemistry is utilized to study diesel spray-assisted ignition of methane and methanol. A diesel surrogate fuel ( n-dodecane) spray is injected into ambient methane-air or methanol-air mixtures at a fixed lean equivalence ratio [Formula: see text] = 0.5 at various ambient temperatures ([Formula: see text] = 900, 950, 1000 K). The main objectives are to (1) compare the ignition characteristics of diesel/methanol with diesel/methane at different [Formula: see text], (2) explore the relative importance of low-temperature chemistry (LTC) to high-temperature chemistry (HTC), and (3) identify the key differences between oxidation reactions of n-dodecane with methane or methanol. Results from homogeneous reactor calculations as well as 3 + 3 LES are reported. For both DF configurations, increasing [Formula: see text] leads to earlier first- and second-stage ignition. Methanol/ n-dodecane mixture is observed to have a longer ignition delay time (IDT) compared to methane/ n-dodecane, for example ≈ three times longer IDT at [Formula: see text] = 950 K. While the ignition response of methane to [Formula: see text] is systematic and robust, the [Formula: see text] window for n-dodecane/methanol ignition is very narrow and for the investigated conditions, only at 950 K robust ignition is observed. For methanol at [Formula: see text] = 1000 K, the lean ambient mixture autoignites before spray ignition while at [Formula: see text] = 900 K full ignition is not observed after 3 ms, although the first-stage ignition is reported. For methanol, LTC is considerably weaker than for methane and in fully igniting cases, heat release map analysis demonstrates the dominant contribution of HTC to total heat release rate for methanol. Reaction sensitivity analysis shows that stronger consumption of OH radicals by methanol compared to methane leads to the further delay in the spray ignition of n-dodecane/methanol. Finally, a simple and novel approach is developed to estimate IDT in reacting LES using zero-dimensional IDT calculations weighted by residence time from non-reacting LES data.

Mechanochemical Applications of Reactive Extrusion from Organic Synthesis to Catalytic and Active Materials

In the past, the use of mechanochemical methods in organic synthesis was reported as somewhat of a curiosity. However, perceptions have changed over the last two decades, and this technology is now being appreciated as a greener and more efficient synthetic method. The qualified “offer” of ball mills that make use of different set-ups, materials, and dimensions has allowed this technology to mature. Nevertheless, the intrinsic batch nature of mechanochemical methods hinders industrial scale-ups. New studies have found, in reactive extrusion, a powerful technique with which to activate chemical reactions with mechanical forces in a continuous flow. This new environmentally friendly mechanochemical synthetic method may be able to miniaturize production plants with outstanding process intensifications by removing organic solvents and working in a flow mode. Compared to conventional processes, reactive extrusions display high simplicity, safety, and cleanliness, which can be exploited in a variety of applications. This paper presents perspective examples in the better-known areas of reactive extrusions, including oxidation reactions, polymer processing, and biomass conversion. This work should stimulate further developments, as it highlights the versatility of reactive extrusion and the huge potential of solid-phase flow chemistry.

Molecular insights into the unusually promiscuous and catalytically versatile Fe(II)/α-ketoglutarate-dependent oxygenase SptF

Non-heme iron and α-ketoglutarate-dependent (Fe/αKG) oxygenases catalyze various oxidative biotransformations. Due to their catalytic flexibility and high efficiency, Fe/αKG oxygenases have attracted keen attention for their application as biocatalysts. Here, we report the biochemical and structural characterizations of the unusually promiscuous and catalytically versatile Fe/αKG oxygenase SptF, involved in the biosynthesis of fungal meroterpenoid emervaridones. The in vitro analysis revealed that SptF catalyzes several continuous oxidation reactions, including hydroxylation, desaturation, epoxidation, and skeletal rearrangement. SptF exhibits extremely broad substrate specificity toward various meroterpenoids, and efficiently produced unique cyclopropane-ring-fused 5/3/5/5/6/6 and 5/3/6/6/6 scaffolds from terretonins. Moreover, SptF also hydroxylates steroids, including androsterone, testosterone, and progesterone, with different regiospecificities. Crystallographic and structure-based mutagenesis studies of SptF revealed the molecular basis of the enzyme reactions, and suggested that the malleability of the loop region contributes to the remarkable substrate promiscuity. SptF exhibits great potential as a promising biocatalyst for oxidation reactions.

EFFECTS OF LEAD AND CADMIUM INTOXICATION ON ANTIOXIDANT STATUS OF BROILER CHICKENS AND ITS CORRECTION WITH SYNTHETIC PREPARATIONS

The authors present the results of a study of the effects of long-term (1.5 MPa) and short-term (5, 10 and 15 MPa) intoxication with heavy metals on the antioxidant status of broiler chickens. The authors found that the addition of increased concentrations of toxicants to the diet leads to their accumulation in poultry’s muscle, fat tissues, and skin. According to the study, lead content increases by 2.25 times, cadmium content increases by 6.5 times. Lipophilic compounds Tiofan and Tiofan M have the most pronounced detoxifying effect in chronic intoxication. Fantox 11-1 is the most pronounced detoxifying effect among hydrophilic compounds, which are inferior to lipophilic ones. Accumulation of heavy metals in the body led to a decrease in the antioxidant status of poultry. There was an acceleration of oxidative processes in long-term experimental toxicosis up to 3.10, up to 21.00 times in the short-term. The addition of 100 mg of lipophilic antioxidants per 1 kg of live weight to the diet with 7.5 mg of lead and 0.75 mg of cadmium per 1 kg of feed resulted in a decrease in the rate of oxidation reactions. The presence of lead and cadmium ions in the tissues of poultry caused a reduction of induction periods in the temperature-stabilized samples to 90 %. Enrichment of the diet with Thiophan and Fantox 11-1 increased this indicator up to 12.40 times. The hydrophilic antioxidant Fantox 11-1 dosage of 15 mg per 1 kg of live weight had a pronounced effect. Its introduction into the diet will correct the lack of endogenous antioxidants and increase the body’s antioxidant status under the influence of heavy metals.

Electrocatalytic Properties of a BaTiO3/MWCNT Composite for Citric Acid Detection

Although barium titanate (BaTiO3) shows prominent dielectric properties for fabricating electronic devices, its utilization in electrochemical applications is limited. Thus, this study examined the potential of a BaTiO3-based composite in the detection of a food additive, i.e., citric acid. First, a submicron-scale BaTiO3 powder was synthesized using the solution combustion method. Then, a BaTiO3/multiwalled carbon nanotube (MWCNT) composite was hydrothermally synthesized at BaTiO3:MWCNT mass ratios of 1:1 and 2:1. This composite was used as a working electrode in a nonenzymatic sensor to evaluate its electrocatalytic activity. Cyclic voltammetric measurements revealed that the BaTiO3/MWCNT composite (2:1) exhibited the highest electrocatalytic activity. Reduction reactions were observed at applied voltages of approximately 0.02 and −0.67 V, whereas oxidation reactions were detected at −0.65 and 0.47 V. With acceptable sensitivity, decent selectivity, and fair stability, the BaTiO3/MWCNT composite (2:1) showed good potential for citric acid detection.