Peroxyl Radicals Research Articles

Damage of amino acids by aliphatic peroxyl radicals: a kinetic and computational study.

Absolute second-order rate coefficients for the reaction of the N- and C-protected amino acids tyrosine (Tyr), tryptophan (Trp), methionine (Met) and proline (Pro) with triethylamine-derived aliphatic peroxyl radical TEAOO˙, which was used as a model for lipid peroxyl radicals, were determined using laser flash photolysis. For Ac-Tyr-OMe a rate coefficient of 1.4 × 104 M-1 s-1 was obtained, whereas the reactions with Ac-Trp-OMe and Ac-Met-OMe were slower by a factor of 4 and 6, respectively. For the reaction with Ac-Pro-OMe only an upper value of 103 M-1 s-1 could be determined, suggesting that Pro residues are not effective traps for lipid peroxyl radicals. Density functional theory (DFT) calculations revealed that the reactions proceed via radical hydrogen atom transfer (HAT) from the Cα position, indicating that the rate is determined by the exothermicity of the reaction. In the case of Ac-Tyr-OMe, HAT from the phenolic OH group is the kinetically preferred pathway, which shuts down when hydrogen bonding with an amine occurs. In an alkaline environment, where the phenolic OH group is deprotonated, the reaction is predicted to occur preferably at Cβ, likely through a proton-coupled electron transfer (PCET) mechanism.

Synergistic or antagonistic antioxidant combinations - a case study exploring flavonoid-nitroxide hybrids.

Neurodegenerative diseases impose a considerable medical and public health burden on populations throughout the world. Oxidative stress, an imbalance in pro-oxidant/antioxidant homeostasis that leads to the generation of reactive oxygen species (ROS), has been implicated in the progression of a number of neurodegenerative diseases. The manipulation of ROS levels may represent a promising treatment option to slow down neurodegeneration, although adequate potency of treatments has not yet been achieved. Using a hybrid pharmacology approach, free radical nitroxide antioxidants were hybridised with a class of natural antioxidants, flavonoids, to form a potential multitargeted antioxidant. Modification of the Baker-Venkataraman reaction achieved the flavonoid-nitroxide hybrids (6-9) in modest yields. Antioxidant evaluation of the hybrids by cyclic voltammetry showed both redox functionalities were still active, with little influence on oxidation potential. Assessment of the peroxyl radical scavenging ability through an ORAC assay showed reduced antioxidant activity of the hybrids compared to their individual components. It was hypothesized that the presence of the phenol in the hybrids creates a more acidic medium which does not favour regeneration of the nitroxide from the corresponding oxammonium cation, disturbing the typical catalytic cycle of peroxyl radical scavenging by nitroxides. This work highlights the potential intricacies involved with drug hybridization as a strategy for new therapeutic development.

The antioxidant glutathione.

Reduced glutathione (GSH) is an essential non-enzymatic antioxidant in mammalian cells. GSH can act directly as an antioxidant to protect cells against free radicals and pro-oxidants, and as a cofactor for antioxidant and detoxification enzymes such as glutathione peroxidases, glutathione S-transferases, and glyoxalases. Glutathione peroxidases detoxify peroxides by a reaction that is coupled to GSH oxidation to glutathione disulfide (GSSG). GSSG is converted back to GSH by glutathione reductase and cofactor NADPH. GSH can regenerate vitamin E following detoxification reactions of vitamin E with lipid peroxyl radicals (LOO). GSH is a cofactor for GST during detoxification of electrophilic substances and xenobiotics. Dicarbonyl stress induced by methylglyoxal and glyoxal is alleviated by glyoxalase enzymes and GSH. GSH regulates redox signaling through reversible oxidation of critical protein cysteine residues by S-glutathionylation. GSH is involved in other cellular processes such as protein folding, protecting protein thiols from oxidation and crosslinking, degradation of proteins with disulfide bonds, cell cycle regulation and proliferation, ascorbate metabolism, apoptosis and ferroptosis.

Disinfection of the air and surfaces in the dental clinic using hydroxyl radical (OH-) based technology: A systematic review.

A systematic review was carried out to compare the disinfectant capacity of hydroxyl radicals (OH-) versus other products commonly used for disinfecting the air and surfaces. A literature search was made of the Cochrane Library, PubMed (MEDLINE) and Scopus databases. "In vitro" studies evaluating disinfection methods applicable to several surfaces and room air were included in the search. The search was carried out in April 2022, with no restrictions in terms of language or publication date. Of the 308 articles identified from the initial search, 8 were included for the quantitative analysis. All publications corresponded to experimental "in vitro" studies. Seven of them evaluated biocidal action against bacteria, and only two assessed activity against viral loads. The generation of contaminants secondary to application of the disinfectants was only analyzed in one of the studies, with the conclusion that the production of peroxyl radicals (RO2) derived from the oxidation of volatile organic compounds (VOCs) is greater when chemical surface disinfectants are used versus air disinfection systems. The disinfection capacities of the currently available methods are similar, and none of them are able to replace the use of additional physical protection measures. Key words:Disinfection methods, hydroxyl radical, environment, surfaces, dentistry.

The dose-response relationships of the direct scavenging activity of amide-based local anesthetics against multiple free radicals.

This study aimed to illustrate the dose-response relationships of the direct scavenging activity of amide-based local anesthetics against multiple free radicals in vitro. We have demonstrated that amide-type local anesthetics selectively and directly scavenge some free radicals. Three kinds of free radicals were eliminated by all the four local anesthetics examined. Mepivacaine, lidocaine, bupivacaine, and dibucaine scavenged hydroxyl radicals in dose-dependent manners. Ascorbyl free radicals were also scavenged in dose-dependent manners, and lastly singlet oxygen was scavenged in dose-dependent manners. Three other free radicals were not scavenged by all of the four local anesthetics; tert-butoxyl radical was scavenged by all the anesthetics examined but dibucaine, nitric oxide by mepivacaine but not by the other three, and tyrosyl radical by mepivacaine and lidocaine but not by the other two. Some free radicals (superoxide anion, tert-butyl peroxyl radical, DPPH) were not scavenged by any of the four local anesthetics. The local anesthetics were also shown to inhibit lipid peroxidation by TBARS assay. These results suggest that local anesthetics have antioxidant properties through their free radical scavenging activities.

Spin Trapping Analysis of Radical Intermediates on the Thermo-Oxidative Degradation of Polypropylene.

The purpose of this study is to investigate the thermo-oxidative degradation behavior of polypropylene (PP) by comparing three types of pristine PP granules (consisting of homopolymer, random copolymer, and block copolymer) with their corresponding oxidized analogues. These analogues were intensely oxidized under oxygen at 90 °C for 1000 h by using the electron spin resonance (ESR) spin trapping method that can detect short-lived radical intermediates during the degradation. The degrees of oxidation could be evaluated by chemiluminescence (CL) intensity, which was related to the concentration of hydroperoxide groups generated in the PP chain. In the pristine PP samples, a small amount of hydroperoxides were found to be formed unintentionally, and their homolysis produces alkoxy radicals, RO•, which then undergo β-scission to yield chain-end aldehydes or chain-end ketones. These oxidation products continue to take part in homolysis to produce their respective carbonyl and carbon radicals. On the other hand, in the oxidized PP granules, because of their much higher hydroperoxide concentration, the two-stage cage reaction and the bimolecular decomposition of hydroperoxides are energetically favorable. Carbonyl compounds are formed in both reactions, which are then homolyzed to form the carbonyl radical species, •C(O)-. PP homopolymer produced the largest amount of carbonyl radical spin adduct; thus, it was found that the homopolymer is most sensitive to oxygen attack, and the presence of ethylene units in copolymers enhances the oxidation resistance of PP copolymers.

Modulation Effect on Tubulin Polymerization, Cytotoxicity and Antioxidant Activity of 1H-Benzimidazole-2-Yl Hydrazones

1H-benzimidazol-2-yl hydrazones with varying hydroxy and methoxy phenyl moieties were designed. Their effect on tubulin polymerization was evaluated in vitro on porcine tubulin. The compounds elongated the nucleation phase and slowed down the tubulin polymerization comparably to nocodazole. The possible binding modes of the hydrazones with tubulin were explored by molecular docking at the colchicine binding site. The anticancer activity was evaluated against human malignant cell lines MCF-7 and AR-230, as well as against normal fibroblast cells 3T3 and CCL-1. The compounds demonstrated a marked antineoplastic activity in low micromolar concentrations in both screened in vitro tumor models. The most active were the trimethoxy substituted derivative 1i and the positional isomers 1j and 1k, containing hydroxy and methoxy substituents: they showed IC50 similar to the reference podophyllotoxin in both tumor cell lines, accompanied with high selectivity towards the malignantly transformed cells. The compounds exerted moderate to high ability to scavenge peroxyl radicals and certain derivatives-1l containing metha-hydroxy and para-methoxy group, and 1b-e with di/trihydroxy phenyl moiety, revealed HORAC values high or comparable to those of well-known phenolic antioxidants. Thus the 1H-benisimidazol-2-yl hydrazones with hydroxy/methoxy phenyl fragments were recognized as new agents exhibiting promising combined antioxidant and antineoplastic action.

Oxidation of Cyclohexane/Cyclohexanone Mixture with Oxygen as Alternative Method of Adipic Acid Synthesis

Herein, an alternative method for adipic acid (AA) synthesis of industrial importance has been reported. The proposed novel method involves the one-step, solvent-free oxidation of a cyclohexane/cyclohexanone (CH/CH=O) mixture, with a cheap oxidizing agent such as O2 or air under mild conditions in the presence of N-hydroxyphtalimide (NHPI) and transition metals as catalysts. It has been showed that CH/CH=O mixture under applied mild conditions oxidized faster than CH and CH=O separately. This was due to the greater oxidizability of CH=O compared to CH. The peroxyl radicals formed by CH=O oxidation initiated the oxidation of the less reactive CH. Additionally, CH=O increased the polarity of the reaction mixture, promoting the solubility of NHPI. The influence of type and amount of catalyst, cyclohexane to cyclohexanone ratio, temperature, time, type of oxidizing agent on the composition of CH/CH=O oxidation products have been reported.

Phenolic Profile and the Antioxidant, Anti-Inflammatory, and Antimicrobial Properties of Açaí (Euterpe oleracea) Meal: A Prospective Study

The mechanical extraction of oils from Brazilian açaí (Euterpe oleracea Mart) produces significant amounts of a byproduct known as "meal", which is frequently discarded in the environment as waste material. Nevertheless, plant byproducts, especially those from oil extraction, may contain residual polyphenols in their composition and be a rich source of natural bioactive compounds. In this study, the phenolic composition and in vitro biological properties of a hydroethanolic açaí meal extract were elucidated. The major compounds tentatively identified in the extract by high-resolution mass spectrometry were anthocyanins, flavones, and flavonoids. Furthermore, rhamnocitrin is reported in an açaí byproduct for the first time. The extract showed reducing power and was effective in scavenging the ABTS radical cation (820.0 µmol Trolox equivalent∙g-1) and peroxyl radical (975.7 µmol Trolox equivalent∙g-1). NF-κB activation was inhibited at 10 or 100 µg∙mL-1 and TNF-α levels were reduced at 100 µg∙mL-1. However, the antibacterial effects against ESKAPE pathogens was not promising due to the high concentration needed (1250 or 2500 µg∙mL-1). These findings can be related to the diverse polyphenol-rich extract composition. To conclude, the polyphenol-rich extract obtained from açaí meal showed relevant biological activities that may have great applicability in the food and nutraceutical industries.

Pristine, carboxylated, and hybrid multi-walled carbon nanotubes exert potent antioxidant activities in in vitro-cell free systems

Multi-walled carbon nanotubes (MWCNTs) are tubular-shaped carbon allotropes, composed of multiple concentric graphene cylinders. The extended systems of conjugated double bonds, that MWCNTs are constituted by, provide them with high electron affinities, enabling them to act as electron donors or acceptors. Consequently, their potential biomedical applications, as synthetic antioxidant agents, are of particular interest. Based on the above, the purpose of the present study was to evaluate the intrinsic antioxidant properties of pristine and carboxylated MWCNTs, as well as of novel hybrid nanocomposites of MWCNTs and inorganic nanoparticles. To this end, after the synthesis and characterization of MWCNTs, their antiradical, reducing, and antigenotoxic properties were assessed in cell-free assays, using a methodological approach that has been recently proposed by our research group. According to our results, most of the tested MWCNTs exhibited strong antioxidant activities. More elaborately, the hybrid material of MWCNTs and ferrous oxide nanoparticles, i.e., CNTs@Fe3O4, showed robust scavenging capacities in all free-radical scavenging assays examined. As regards reducing properties, the pristine MWCNTs, i.e., CNTs-Ref, exhibited the greater electron donating capacity. Finally, in terms of antigenotoxic properties, the hybrid material of MWCNTs and silicon carbide nanoparticles, i.e., CNTs@SiC, exhibited potent ability to inhibit the formation of peroxyl radicals, thus preventing from the oxidative DNA damage. Conclusively, our findings suggest that the MWCNTs of the study could be considered as promising broad-spectrum antioxidants, however, further investigations are required to evaluate their toxicological profile in cell-based and in vivo systems.

Investigation of hydrogen superoxide adsorption during ORR on Pt/C catalyst in acidic solution for PEFC by in-situ high energy resolution XAFS

Oxygen Reduction Reaction (ORR) is one of the key electrochemical reactions, especially in Polymer Electrolyte Fuel Cells (PEFCs). In this work, the reaction pathway and intermediate species such as molecular-type oxygen during ORR were discussed. High energy resolution X-ray absorption fine structure spectra at the Pt L3-edge were obtained to observe the electronic structure of Pt catalyst. Carbon-supported Pt nanoparticles as powder catalysts were used for measurement as more realistic conditions, and the species adsorbed on the Pt nanoparticles were analyzed while controlling under the potentials in acidic electrolyte solution with N2 or O2 gas bubbling. Molecular-type oxygen adsorption species is observed only in the O2-bubbled electrolyte solution. This intermediate adsorption species is assigned to a hydrogen superoxide.

Visible Light Induces Site-Specific Oxidative Heavy Chain Fragmentation of a Monoclonal Antibody (IgG1) Mediated by an Iron(III)-Containing Histidine Buffer

Fragmentation of therapeutic monoclonal antibodies represents a critical quality attribute. Here, we report a novel visible light-induced heavy chain fragmentation of IgG1 mediated by an Fe(III)-containing histidine (His) buffer. Based on non-reducing sodium dodecylsulfate-polyacrylamide gel electrophoresis and mass spectrometry analysis, IgG1 fragments with apparent molecular weights of ∼130, ∼110, and ∼22 kDa were detected in photo-irradiated samples and were mechanistically rationalized with an oxidative cleavage at Thr259. Specifically, the reactions are proposed to involve the generation of an intermediary alkoxyl radical, which undergoes β-cleavage to yield a glycyl radical. The latter either converts into Gly or adds oxygen and follows a peroxyl radical chemistry. The cleavage process requires the presence of His, while only negligible yields of cleavage products are formed when His is replaced by acetate, succinate, or phosphate buffer. Importantly, the fragmentation can be prevented by ethylenediaminetetraacetic acid (EDTA) only when the EDTA concentrations are in significant excess over the concentrations of Fe(III) and proteins, suggesting a strong binding between Fe(III) and IgG1.

Effect of Oxidative Modification by Peroxyl Radical on the Characterization and Identification of Oxidative Aggregates and In Vitro Digestion Products of Walnut (Juglans regia L.) Protein Isolates.

Walnut protein is a key plant protein resource due to its high nutritional value, but walnuts are prone to oxidation during storage and processing. This article explored the oxidative modification and digestion mechanism of walnut protein isolates by peroxyl radical and obtained new findings. SDS-PAGE and spectral analysis were used to identify structural changes in the protein after oxidative modification, and LC-MS/MS was used to identify the digestion products. The findings demonstrated that as the AAPH concentration increased, protein carbonyl content increased from 2.36 to 5.12 nmol/mg, while free sulfhydryl content, free amino content, and surface hydrophobicity decreased from 4.30 nmol/mg, 1.47 μmol/mg, and 167.92 to 1.72 nmol/mg, 1.13 μmol/mg, and 40.93 nmol/mg, respectively. Furthermore, the result of Tricine-SDS-PAGE in vitro digestion revealed that protein oxidation could cause gastric digestion resistance and a tendency for intestinal digestion promotion. Carbonyl content increased dramatically during the early stages of gastric digestion and again after 90 min of intestine digestion, and LC-MS/MS identified the last digestive products of the stomach and intestine as essential seed storage proteins. Oxidation causes walnut proteins to form aggregates, which are then re-oxidized during digestion, and proper oxidative modification may benefit intestinal digestion.

The formation mechanism of highly oxygenated organic molecules produced by toluene in the urban atmosphere

Highly oxygenated organic molecules (HOMs) with low volatility from atmospheric toluene oxidation play an important role in new particle formation and contribute significantly to secondary organic aerosols in cities. In this work, quantum chemical calculations were performed to study the formation mechanism of HOM monomers and dimers from toluene oxidation initiated by OH radicals. Under 0.4 ppbv NO and 40 pptv HO2 radical conditions, the formed initial mono- and multi–OH–substituted organic peroxyl radicals (RO2) first undergo intramolecular H-shift and cyclization reactions to promote autoxidation, which is followed by bimolecular reactions of highly oxidized RO2 with NO and HO2 radical, resulting in the formation of HOM monomers. It implies that high NO concentration hardly inhibits the formation of RO2 with a low O:C ratio in the aforementioned processes, but mainly intercepts the formation of RO2 with a high O:C ratio. Except for the self- and cross-reaction of RO2, the addition reactions of RO2 and acyl peroxy radicals (RC(O)O2) with toluene-derived alkenes (RO2 + alkene and RC(O)O2 + alkene reactions) have sufficiently low potential barriers, which are non-ignorable pathways for the HOM dimers formation. The present work expands our knowledge of the mechanism of HOMs formation from the oxidation of atmospheric aromatic hydrocarbons.

Implications of differential peroxyl radical-induced inactivation of glucose 6-phosphate dehydrogenase and 6-phosphogluconate dehydrogenase for the pentose phosphate pathway

Escherichia coli glucose-6-phosphate dehydrogenase (G6PDH) and 6-phosphogluconate dehydrogenase (6PGDH) are key enzymes of the pentose phosphate pathway, responsible for the NADPH production in cells. We investigated modification of both enzymes mediated by peroxyl radicals (ROO·) to determine their respective susceptibilities to and mechanisms of oxidation. G6PDH and 6PGDH were incubated with AAPH (2,2′-azobis(2-methylpropionamidine)dihydrochloride), which was employed as ROO· source. The enzymatic activities of both enzymes were determined by NADPH release, with oxidative modifications examined by electrophoresis and liquid chromatography (LC) with fluorescence and mass (MS) detection. The activity of G6PDH decreased up to 62.0 ± 15.0% after 180 min incubation with 100 mM AAPH, whilst almost total inactivation of 6PGDH was determined under the same conditions. Although both proteins contain abundant Tyr (particularly 6PGDH), these residues were minimally affected by ROO·, with Trp and Met being major targets. LC–MS and in silico analysis showed that the modification sites of G6PDH are distant to the active site, consistent with a dispersed distribution of modifications, and inactivation resulting from oxidation of multiple Trp and Met residues. In contrast, the sites of oxidation detected on 6PGDH are located close to its catalytic site indicating a more localized oxidation, and a consequent high susceptibility to ROO·-mediated inactivation.

Glyphosate-based herbicide (GBH) causes damage in embryo-larval stages of zebrafish (Danio rerio)

Glyphosate-Based Herbicides (GBH) show risks to the environment and also to aquatic organisms, such as fish. The present work aimed to evaluate the effects of GBH and Pure Glyphosate (PG) exposure on Danio rerio embryos at drinking water concentrations. Zebrafish embryos were exposed to 250, 500, and 1000 μg L−1 of Roundup Original DI® and pure glyphosate for 96 h. Glyphosate concentration in water, parameters physicochemical water, survival, hatching rate, heart rate, malformations, behavior, and biomarkers were evaluated. We verified that at 6 h post-fertilization (hpf), animals exposed to GBH 500 showed decreased survival as compared to the control. The hatching rate increased in all groups exposed to GBH at 48 hpf as compared to the control group. The embryos exposed did not present changes in the spontaneous movement and touch response. Exposed groups to GBH demonstrated a higher number of malformations in fish embryos as compared to the control. Most malformations were: pericardial edema, yolk sac edema, body malformations, and curvature of the spine. In heart rate, bradycardia occurred in groups exposed, as predicted due to cardiac abnormalities. As biochemical endpoints, we observed a decrease in Glutathione S-transferase (GBH 250, GBH 500 and PG 250) and Acetylcholinesterase (GBH 250 and PG 250) activity. No differences were found between the groups in the concentration of protein, Total Antioxidant Capacity Against Peroxyl Radicals, Lipid peroxidation, Reactive Oxygen Species, Non-protein thiols, and Catalase. In conclusion, the damage in all evaluated stages of development was aggravated by survival and malformations. Therefore, the large-scale use of GBHs, coupled with the permissiveness of its presence could be the cause damage to the aquatic environment affecting the embryonic development of non-target organisms.

Anti-Oxidant and Anti-Inflammatory Effects of Astaxanthin on Gastrointestinal Diseases.

A moderate amount of reactive oxygen species (ROS) is produced under normal conditions, where they play an important role in cell signaling and are involved in many aspects of the immune response to pathogens. On the other hand, the excessive production of ROS destructs macromolecules, cell membranes, and DNA, and activates pro-inflammatory signaling pathways, which may lead to various pathologic conditions. Gastrointestinal (GI) mucosa is constantly exposed to ROS due to the presence of bacteria and other infectious pathogens in food, as well as alcohol consumption, smoking, and the use of non-steroidal anti-inflammatory drugs (NSAID). Prolonged excessive oxidative stress and inflammation are two major risk factors for GI disorders such as ulcers and cancers. Bioactive food compounds with potent anti-oxidant and anti-inflammatory activity have been tested in experimental GI disease models to evaluate their therapeutic potential. Astaxanthin (AST) is a fat-soluble xanthophyll carotenoid that is naturally present in algae, yeast, salmon, shrimp, and krill. It has been shown that AST exhibits protective effects against GI diseases via multiple mechanisms. Residing at the surface and inside of cell membranes, AST directly neutralizes ROS and lipid peroxyl radicals, enhances the activity of anti-oxidant enzymes, and suppresses pro-inflammatory transcription factors and cytokines. In addition, AST has been shown to inhibit cancer cell growth and metastasis via modulating cell proliferation-related pathways, apoptosis, and autophagy. Considering the potential benefits of AST in GI diseases, this review paper aims to summarize recent advances in AST research, focusing on its anti-oxidant and anti-inflammatory effects against gastric and intestinal ulcers and cancers.

Physiological and Biochemical Changes in Vegetable and Field Crops under Drought, Salinity and Weeds Stresses: Control Strategies and Management

Weeds are one of the most damaging biotic stresses in crop production, and drought and salinity are considered the most serious abiotic stresses. These factors harmfully affect growth and development in several vegetable and field crops by causing harmful effects on physiological and biochemical characteristics such as water uptake, photosynthesis, relative water content, electrolyte leakage, and antioxidant compounds linked with oxidative stress and the accumulation of reactive oxygen species (ROS). These oxidative stress-related components affect most physiological and biochemical characteristics in plants under natural conditions and environmental stresses, especially weed infestation, salinity, and drought stress. ROS such as superoxide (O2•−), hydrogen peroxide (H2O2), peroxyl radical (ROO•), and singlet oxygen (1O2) are very important molecules produced naturally as by-products of metabolic processes in chloroplasts, mitochondria, peroxisomes, and the apoplast. Under stress conditions such as weed infestation, drought and salinity, the morphological and yield characteristics of stressed plants are negatively affected; however, superoxide (O2•−) and hydrogen peroxide (H2O2) are significantly increased. The negative impact of weeds can be mitigated with integrated controls which include herbicides, allelopathy, and crop rotation as well as the different methods for weed control. The defense system in various crops mainly depends on both enzymatic and nonenzymatic antioxidants. The enzymatic antioxidants include superoxide dismutase, glutathione reductase, and catalase; nonenzymatic antioxidants include ascorbic acid, carotenoids, α-Tocopherols, proline, glutathione, phenolics, and flavonoids. These antioxidant components can scavenge various ROS under several stresses, particularly weeds, drought and salinity. In this review, our objective is to shed light on integrated weeds management and plant tolerance to salinity and drought stresses associated with the ROS and the induction of antioxidant components to increase plant growth and yield in the vegetable and field crops.

Meadow sage (Salvia pratensis L.): A neglected sage species with valuable phenolic compounds and biological potential

The genus Salvia is well-known for its use in food as aromatic and spicy herbs, as well as in the pharmaceutical and fragrance industries. Regardless of their importance, some Salvia species have not been thoroughly examined and chemically characterized, including Salvia pratensis L. In the present study, the detailed phenolic composition using LC/MS analysis, some bioactivities, and in vitro digestion stability of S. pratensis aerial part (SPA) and root (SPR) methanol extracts were determined. The results showed that both extracts possess high phenolic content, while SPR was richer in rosmarinic (11065.56 µg/g) and caffeic (509.00 µg/g) acids, as well as salvianolic acid A (519.22 µg/g) and B (291.60 µg/g) amounts quantified by UHPLC-DAD/(-)HESI-MS/MS analysis than SPA. The extracts demonstrated considerable antioxidant activity, particularly radical scavenger activity with IC50 values ranging between 24 and 90 µg/mL. The high inhibitory effect of extracts against DNA oxidative damage induced by peroxyl and hydroxyl radicals was noticed. The root extract was the most effective in inhibiting bacterial growth with MIC < 0.156 mg/mL for some G+ bacterial species. SPR extract was substantially more cytotoxic than SPA against all examined cell lines, particularly on cancer cells. The IC50 values of SPR for two cancerogenic cell lines A431 and SVT2 were 24.3 and 49.6 µg/mL, respectively. S. pratensis, especially its root, possess valuable phenolic compounds and biological properties for potential application as a substitute for some commonly used Salvia species.

Preparation of Mo-based catalyst appreciated from agricultural waste for efficient high-value conversion of 1-hexene

A Mo-based catalyst (Mo/CBC) was successfully prepared by a hydrothermal method in which the carbon support was derived from agricultural waste. Physio-chemical properties showed that Mo/CBC had uniformly dispersed particles, large pores, excellent thermal stability and high molybdenum loading. The catalytic performance was systematically investigated, including types of loading metal, oxidants, catalyst usage, substrate concentration, oxidant ratio, reaction temperature, reaction time, reusability, and scalability. Mo/CBC exhibited excellent catalytic performance in the epoxidation of 1-hexene with 98.5% of 1-hexene oxide selectivity, 94.4% of 1-hexene conversion and 99.1% of TBHP consumption efficiency under optimal reaction conditions. The catalytic performance of Mo/CBC did not decrease significantly after five cycles, showing excellent cycle stability. In addition, the scalability showed that Mo/CBC had a good universality for linear olefins, cyclic olefins, aromatic olefins and so on. Thermodynamics showed that the epoxidation system presented as an endothermic and disordered process. Kinetics study showed the rate of the reaction obeyed the pseudo-second-order model with an apparent activation energy of 75.2 kJ/mol. The mechanism study revealed that Mo4+ species played a key role in the reaction system, promoting the generation of peroxyl radical intermediates from TBHP to directly epoxidize 1-hexene into 1-hexene oxide.