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1.
Molecules ; 28(2)2023 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-36677710

RESUMO

Endometriosis is a common gynecological illness in women of reproductive age that significantly decreases life quality and fertility. Paeonol has been shown to play an important part in endometriosis treatments. Understanding the mechanism is critical for treating endometriosis. In this study, autologous transplantation combined with a 28 day ice water bath was used to create a rat model of endometriosis with cold clotting and blood stagnation. The levels of estradiol and progesterone in plasma were detected by ELISA, and the pathological changes of ectopic endometrial tissue were examined by H&E staining, which proved the efficacy of paeonol. For metabolomic analysis of plasma samples, UPLC-Q/TOF-MS was combined with multivariate statistical analysis to identify the influence of paeonol on small molecule metabolites relevant to endometriosis. Finally, the key targets were screened using a combination of network pharmacology and molecular docking approaches. The results showed that the pathological indexes of rats were improved and returned to normal levels after treatment with paeonol, which was the basis for confirming the efficacy of paeonol. Metabolomics results identified 13 potential biomarkers, and paeonol callbacks 7 of them, involving six metabolic pathways. Finally, four key genes were found for paeonol therapy of endometriosis, and the results of molecular docking revealed a significant interaction between paeonol and the four key genes. This study was successful in establishing a rat model of endometriosis with cold coagulation and blood stagnation. GCH1, RPL8, PKLR, and MAOA were the key targets of paeonol in the treatment of endometriosis. It is also demonstrated that metabolomic techniques give the potential and environment for comprehensively understanding drug onset processes.


Assuntos
Medicamentos de Ervas Chinesas , Endometriose , Humanos , Ratos , Feminino , Animais , Endometriose/tratamento farmacológico , Simulação de Acoplamento Molecular , Metabolômica/métodos , Acetofenonas/análise , Medicamentos de Ervas Chinesas/farmacologia , Cromatografia Líquida de Alta Pressão/métodos
2.
Molecules ; 28(1)2023 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-36615564

RESUMO

Each metabolite, regardless of its molecular simplicity or complexity, has a mission or function in the organism biosynthesizing it. In this review, the biological, allelochemical, and chemical properties of acetophenone, as a metabolite involved in multiple interactions with various (mi-cro)organisms, are discussed. Further, the details of its biogenesis and chemical synthesis are provided, and the possibility of its application in different areas of life sciences, i.e., the status quo of acetophenone and its simple substituted analogs, is examined. In particular, natural and synthetic simple acetophenone derivatives are analyzed as promising agrochemicals and useful scaffolds for drug research and development.


Assuntos
Disciplinas das Ciências Biológicas , Cetonas , Acetofenonas/química
3.
Int J Mol Sci ; 23(21)2022 Oct 29.
Artigo em Inglês | MEDLINE | ID: mdl-36361953

RESUMO

The acetophenone-based 3,4-dihydropyrimidine-2(1H)-thione was synthesized by the reaction of 4-methylpent-3-en-2-one (1), 4-acetyl aniline (2) and potassium thiocyanate. The spectroscopic analysis including: FTIR, 1H-NMR, and single crystal analysis proved the structure of synthesized compound (4), with the six-membered nonplanar ring in envelope conformation. In crystal structure, the intermolecular N-H ⋯ S and C-H ⋯ O hydrogen bonds link the molecule in a two-dimensional manner which is parallel to (010) the plane enclosing R22 (8) and R22 (10) ring motifs. After that, the Hirshfeld surfaces and their related two-dimensional fingerprint plots were used for thorough investigation of intermolecular interactions. According to Hirshfeld surface analysis, the most substantial contributions to the crystal packing are from H ⋯ H (59.5%), H ⋯ S/S ⋯ H (16.1%), and H ⋯ C/C ⋯ H (13.1%) interactions. The electronic properties and stability of the compound were investigated through density functional theory (DFT) studies using B3LYP functional and 6-31G* as a basis set. The compound 4 displayed the high chemical reactivity with chemical softness of 2.48. In comparison to the already reported known tyrosinase inhibitor, the newly synthesized derivatives exhibited almost seven-fold better inhibition of tyrosinase (IC50 = 1.97 µM), which was further supported by molecular docking studies. The compound 4 inside the active pocket of ribonucleotide reductase (RNR) exhibited a binding energy of -19.68 kJ/mol, and with mammalian deoxy ribonucleic acid (DNA) it acts as an effective DNA groove binder with a binding energy of -21.32 kJ/mol. The results suggested further exploration of this compound at molecular level to synthesize more potential leads for the treatment of cancer.


Assuntos
Monofenol Mono-Oxigenase , Ribonucleotídeo Redutases , Tionas/farmacologia , Simulação de Acoplamento Molecular , Acetofenonas/farmacologia , DNA
4.
Proc Natl Acad Sci U S A ; 119(43): e2213450119, 2022 10 25.
Artigo em Inglês | MEDLINE | ID: mdl-36256818

RESUMO

Bacterial catabolic pathways have considerable potential as industrial biocatalysts for the valorization of lignin, a major component of plant-derived biomass. Here, we describe a pathway responsible for the catabolism of acetovanillone, a major component of several industrial lignin streams. Rhodococcus rhodochrous GD02 was previously isolated for growth on acetovanillone. A high-quality genome sequence of GD02 was generated. Transcriptomic analyses revealed a cluster of eight genes up-regulated during growth on acetovanillone and 4-hydroxyacetophenone, as well as a two-gene cluster up-regulated during growth on acetophenone. Bioinformatic analyses predicted that the hydroxyphenylethanone (Hpe) pathway proceeds via phosphorylation and carboxylation, before ß-elimination yields vanillate from acetovanillone or 4-hydroxybenzoate from 4-hydroxyacetophenone. Consistent with this prediction, the kinase, HpeHI, phosphorylated acetovanillone and 4-hydroxyacetophenone. Furthermore, HpeCBA, a biotin-dependent enzyme, catalyzed the ATP-dependent carboxylation of 4-phospho-acetovanillone but not acetovanillone. The carboxylase's specificity for 4-phospho-acetophenone (kcat/KM = 34 ± 2 mM-1 s-1) was approximately an order of magnitude higher than for 4-phospho-acetovanillone. HpeD catalyzed the efficient dephosphorylation of the carboxylated products. GD02 grew on a preparation of pine lignin produced by oxidative catalytic fractionation, depleting all of the acetovanillone, vanillin, and vanillate. Genomic and metagenomic searches indicated that the Hpe pathway occurs in a relatively small number of bacteria. This study facilitates the design of bacterial strains for biocatalytic applications by identifying a pathway for the degradation of acetovanillone.


Assuntos
Biotina , Lignina , Lignina/metabolismo , Acetofenonas , Trifosfato de Adenosina
5.
Int J Mol Sci ; 23(19)2022 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-36232899

RESUMO

ATP-binding cassette subfamily G and tubulin pharmacological mechanisms decrease the effectiveness of anticancer drugs by modulating drug absorption and by creating tubulin assembly through polymerization. A series of natural and synthetic chalcones have been reported to have very good anticancer activity, with a half-maximal inhibitory concentration lower than 1 µM. By modulation, it is observed in case of the first mechanism that methoxy substituents on the aromatic cycle of acetophenone residue and substitution of phenyl nucleus by a heterocycle and by methoxy or hydroxyl groups have a positive impact. To inhibit tubulin, compounds bind to colchicine binding site. Presence of methoxy groups, amino groups or heterocyclic substituents increase activity.


Assuntos
Antineoplásicos , Chalcona , Chalconas , Acetofenonas/farmacologia , Trifosfato de Adenosina/farmacologia , Antineoplásicos/química , Proliferação de Células , Chalcona/farmacologia , Chalconas/química , Colchicina/metabolismo , Colchicina/farmacologia , Estrutura Molecular , Relação Estrutura-Atividade , Tubulina (Proteína)/metabolismo , Moduladores de Tubulina/química , Moduladores de Tubulina/farmacologia
6.
Oxid Med Cell Longev ; 2022: 2457687, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36211827

RESUMO

Background: Activation of endothelial cells by inflammatory mediators secreted by CD4+ T lymphocytes plays a key role in the inflammatory response. Exosomes represent a specific class of signaling cues transporting a mixture of proteins, nucleic acids, and other biomolecules. So far, the impact of exosomes shed by T lymphocytes on cardiac endothelial cells remained unknown. Methods and Results: Supernatants of CD4+ T cells activated with anti-CD3/CD28 beads were used to isolate exosomes by differential centrifugation. Activation of CD4+ T cells enhanced exosome production, and these exosomes (CD4-exosomes) induced oxidative stress in cardiac microvascular endothelial cells (cMVECs) without affecting their adhesive properties. Furthermore, CD4-exosome treatment aggravated the generation of mitochondrial reactive oxygen species (ROS), reduced nitric oxide (NO) levels, and enhanced the proliferation of cMVECs. These effects were reversed by adding the antioxidant apocynin. On the molecular level, CD4-exosomes increased NOX2, NOX4, ERK1/2, and MEK1/2 in cMVECs, and ERK1/2 and MEK1/2 proteins were found in CD4-exosomes. Inhibition of either MEK/ERK with U0126 or ERK with FR180204 successfully protected cMVECs from increased ROS levels and reduced NO bioavailability. Treatment with NOX1/4 inhibitor GKT136901 effectively blocked excessive ROS and superoxide production, reversed impaired NO levels, and reversed enhanced cMVEC proliferation triggered by CD4-exosomes. The siRNA-mediated silencing of Nox4 in cMVECs confirmed the key role of NOX4 in CD4-exosome-induced oxidative stress. To address the properties of exosomes under inflammatory conditions, we used the mouse model of CD4+ T cell-dependent experimental autoimmune myocarditis. In contrast to exosomes obtained from control hearts, exosomes obtained from inflamed hearts upregulated NOX2, NOX4, ERK1/2, MEK1/2, increased ROS and superoxide levels, and reduced NO bioavailability in treated cMVECs, and these changes were reversed by apocynin. Conclusion: Our results point to exosomes as a novel class of bioactive factors secreted by CD4+ T cells in immune response and represent potential important triggers of NOX4-dependent endothelial dysfunction. Neutralization of the prooxidative aspect of CD4-exosomes could open perspectives for the development of new therapeutic strategies in inflammatory cardiovascular diseases.


Assuntos
Células Endoteliais , Exossomos , Acetofenonas , Animais , Antioxidantes/farmacologia , Antígenos CD28/metabolismo , Células Endoteliais/metabolismo , Exossomos/metabolismo , Mediadores da Inflamação/metabolismo , Sistema de Sinalização das MAP Quinases , Camundongos , Quinases de Proteína Quinase Ativadas por Mitógeno/metabolismo , NADPH Oxidase 4/metabolismo , NADPH Oxidases/metabolismo , Óxido Nítrico/metabolismo , Estresse Oxidativo , RNA Interferente Pequeno/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Superóxidos/metabolismo , Linfócitos T/metabolismo
7.
Org Biomol Chem ; 20(41): 8042-8048, 2022 10 26.
Artigo em Inglês | MEDLINE | ID: mdl-36200914

RESUMO

A metal-free visible-light-driven cascade cyclization reaction to synthesize 3-methyl-3-acetophenone-2-oxindoles and 3-methyl-3-(methylsulfonyl)benzene-2-oxindoles in yields up to 96% and 99%, via benzoyl and phenylsulfinyl radicals with acrylamide derivatives is reported, respectively. Extensive studies, including gram-scale, radical capture and isotope experiments, were performed to indicate that the reaction may involve a radical process.


Assuntos
Acrilamida , Benzeno , Ciclização , Oxindóis , Indóis , Metais , Acetofenonas
8.
Neurotoxicology ; 93: 45-59, 2022 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-36100143

RESUMO

We aimed to identify the molecular mechanisms through which prolactin protects against 1,2-Diacetylbenzene (DAB)-induced memory and motor impairments. The gene expression omnibus database (no. GSE119435), transcriptomic data, GeneMANIA, ToppGeneSuite, Metascape, STRING database, Cytoscape, and Autodock were used as the core tools in in-silico analyses. We observed that prolactin may improve memory and motor deficits caused by DAB via 13 genes (Scn5a, Lmntd1, LOC100360619, Rgs9, Srpk3, Syndig1l, Gpr88, Egr2, Ctxn3, Drd2, Ttr, Gpr6, and Ecel1) in young rats and 9 genes (Scn5a, Chat, RGD1560608, Ucma, Lrrc31, Gpr88, Col1a2, Cnbd1, and Ttr) in old rats. Almost all of these genes were downregulated in both young and old rats given DAB, but they were increased in both young and old rats given prolactin. Co-expression interactions were identified as the most important interactions (83.2 % for young rats and 100 % for old rats). The most important mechanisms associated with prolactin's ability to counteract DAB were identified, including "learning and memory," and "positive regulation of ion transport" in young rats, as well as "acetylcholine related pathways," "inflammatory response pathway," and "neurotransmitter release cycle" in old rats. We also identified several key miRNAs associated with memory and motor deficits, as well as prolactin and DAB exposure (rno-miR-141-3p, rno-miR-200a-3p, rno-miR-124-3p, rno-miR-26, and rno-let-7 families). The most significant transcription factors associated with differentially expressed gene regulation were Six3, Rxrg, Nkx26, and Tbx20. These findings will contribute to our understanding of the processes through which prolactin's beneficial effects counteract DAB-induced memory and motor deficits.


Assuntos
MicroRNAs , Prolactina , Ratos , Animais , Ratos Sprague-Dawley , MicroRNAs/genética , MicroRNAs/metabolismo , Acetofenonas , Transtornos da Memória/induzido quimicamente , Transtornos da Memória/genética , Transtornos da Memória/prevenção & controle , Receptores Acoplados a Proteínas G
9.
Int J Pharm ; 626: 122165, 2022 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-36089210

RESUMO

Apocynin (APO), a specific nicotinamide adenine dinucleotide phosphate-oxidase (NADPH-oxidase, NOX) inhibitor, has recently emerged as a bioactive phytochemical with eminent anti-inflammatory and anti-oxidant activities. To our knowledge, no research has been conducted to fabricate a mucoadhesive nanostructured delivery system of APO that targets the liver. Accordingly, chitosan (CS) surface decorated polymeric nanoparticulate delivery system (PNDS) was victoriously fabricated by double emulsion-solvent evaporation method. Herein, a randomized full 33 factorial design was employed to assess the impact of the independently processing parameters (IPPs) namely; (poly(d,l-lactide-co-glycolide) (PLGA) amount (A)), (polyvinyl alcohol (PVA) concentration (B)), and (CS concentration (C)), on different dependently measured attributes (DMAs). The optimal APO-loaded chitosan-coated poly(d,l-lactide-co-glycolide) nanoparticles (APO-loaded CS-coated PLGA NPs) formula (F19) would be extensively appraised through meticulous in vitro-in vivo studies. Crucially, the results revealed that oral pre-treatment with the optimal formula evoked a prodigious in vivo hepatoprotective efficacy against lipopolysaccharide (LPS)/D-(+)-galactosamine (D-GalN) induced fulminant hepatitis (FH) in BALB/c mice when compared with pure APO, uncoated F19, and plain NPs (P NPs) pretreated groups. In conclusion, APO-loaded CS-coated PLGA NPs could be considered as a promising oral mucoadhesive phytopharmaceutical PNDS to open new prospects for therapeutic intervention in inflammatory based liver diseases.


Assuntos
Quitosana , Necrose Hepática Massiva , Nanopartículas , Acetofenonas , Animais , Antioxidantes , Emulsões , Galactosamina , Lipopolissacarídeos , Camundongos , Camundongos Endogâmicos BALB C , NADP , Oxirredutases , Tamanho da Partícula , Compostos Fitoquímicos , Copolímero de Ácido Poliláctico e Ácido Poliglicólico , Álcool de Polivinil , Solventes
10.
Biomed Res Int ; 2022: 5866824, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36147631

RESUMO

Objective: This study was designed to establish quality standards of Burnet gels and investigate the effects and mechanism of Burnet gels on steroid-dependent dermatitis (HDD) in guinea pigs. Methods: HPLC was used to determine the content of gallic acid, Gentiopicrin, and paeonol. A total of 48 male guinea pigs were recruited and randomly divided into control group, model group, tacrolimus ointment group, and Burnet gel group (Low, medium, and high concentration). The HDD guinea pig model was established by the 0.5% clobetasol propionate tincture. After HDD model establishment, control group and model group smeared normal saline and the rest of the group with corresponding drugs for three weeks. The contents of IFN-γ, IL-4, and IgE in the guinea pig serum were detected by the ELISA; the protein expression levels of FLG, LOR, and Caspase-14 in the epidermis of guinea pigs were detected by the immunohistochemical and Western blotting method. Results: The content of gallic acid, Gentiopicrin, and paeonol was 0.30 mg/g, 1.06 mg/g, and 0.56 mg/g. Compared with the normal group, the IFN-γ, IL-4, and IgE of guinea pig serum in the model group were significantly increased; the FLG, LOR, and Caspase-14 of guinea pig epidermis in the model group were significantly decreased; compared with the model group, the IFN-γ, IL-4, and IgE of guinea pig serum in the tacrolimus ointment group and Burnet gel group were significantly decreased; the FLG, LOR, and Caspase-14 of guinea pig epidermis in the tacrolimus ointment group and Burnet gel group were significantly increased. Conclusion: Burnet gels can improve guinea pig HDD model, and the mechanism may be related to inhibiting skin inflammation and promoting the formation of epidermal skin barrier.


Assuntos
Dermatite , Sanguisorba , Acetofenonas , Animais , Caspase 14 , Clobetasol , Ácido Gálico , Géis , Cobaias , Imunoglobulina E , Interleucina-4 , Glucosídeos Iridoides , Masculino , Pomadas , Solução Salina , Tacrolimo/farmacologia
11.
Fitoterapia ; 163: 105303, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-36152926

RESUMO

Two novel prenylated acetophenones with new carbon skeletons, acronyrones A and B (1 and 2), and a new analogue, acronyrone C (3), together with two known compounds (4 and 5) were isolated from the leaves of Acronychia pedunculata. Their structures with absolute configurations were identified by interpretation of spectroscopic data, single crystal X-ray diffraction, and electronic circular dichroism (ECD) calculations. Compounds 1 and 2 represent the first example of prenylated acetophenones possessed a C7 (1) and a C6 (2) side chain, forming a 4-isobutylchroman-2-one unit and a 3-(2-methylpropylidene)benzofuran-2(3H)-one moiety with the acetophenone core, respectively. In addition, compound 4 exhibited significant dose-dependent transcriptional activation effect against retinoid X receptor-α (RXRα), and could be regarded as a new type of non-classical RXR ligand.


Assuntos
Rutaceae , Thoracica , Animais , Estrutura Molecular , Rutaceae/química , Acetofenonas/química , Folhas de Planta/química
12.
Life Sci ; 308: 120962, 2022 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-36113732

RESUMO

l-Amino acid oxidase isolated from Calloselasma rhodostoma (Cr-LAAO) snake venom is a potent stimulus for neutrophil activation and production of inflammatory mediators, contributing to local inflammatory effects in victims of envenoming. Cr-LAAO triggered the activation of nicotinamide adenine dinucleotide phosphatase (NADPH) oxidase complex and protein kinase C (PKC)-α signaling protein for reactive oxygen species (ROS) production. This study aims to evaluate the ROS participation in the NLRP3 inflammasome complex activation in human neutrophil. Human neutrophils were isolated and stimulated for 1 or 2 h with RPMI (negative control), LPS (1 µg/mL, positive control) or Cr-LAAO (50 µg/mL). The neutrophil transcriptome was examined using the microarray technique, and RT-qPCR for confirmation of gene expression. Immunofluorescence assays for NLRP3, caspase-1, IL-1ß and GSDMD proteins was performed by Western blot in the presence and/or absence of Apocynin, an inhibitor of NADPH oxidase. IL-1ß release was also detected in the presence and/or absence of NLRP3, caspase-1 and NADPH oxidase inhibitors. Results showed that Cr-LAAO upregulated the expression of genes that participate in the NADPH oxidase complex formation and inflammasome assembly. NLRP3 was activated and accumulated in the cytosol forming punctas, indicating its activation. Gasdermin D was not cleaved but lactate dehydrogenase was released. Furthermore, ROS inhibition decreased the expression of NLRP3 inflammasome complex proteins, as observed by protein expression in the presence and/or absence of apocynin, an NADPH oxidase inhibitor. IL-1ß was also released, and pharmacological inhibition of NLRP3, caspase-1, and ROS reduced the amount of released cytokine. This is the first report demonstrating the activation of the NLRP3 inflammasome complex via ROS generation by Cr-LAAO, which may lead to the development of local inflammatory effects observed in snakebite victims.


Assuntos
Inflamassomos , L-Aminoácido Oxidase , Acetofenonas , Caspase 1/metabolismo , Citocinas/metabolismo , Humanos , Inflamassomos/metabolismo , Mediadores da Inflamação/metabolismo , Interleucina-1beta/metabolismo , L-Aminoácido Oxidase/metabolismo , L-Aminoácido Oxidase/farmacologia , Lactato Desidrogenases/metabolismo , Lipopolissacarídeos/farmacologia , NAD/metabolismo , NADP/metabolismo , NADPH Oxidases/metabolismo , Proteína 3 que Contém Domínio de Pirina da Família NLR/genética , Proteína 3 que Contém Domínio de Pirina da Família NLR/metabolismo , Neutrófilos/metabolismo , Monoéster Fosfórico Hidrolases/metabolismo , Proteína Quinase C/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Venenos de Serpentes/metabolismo , Venenos de Serpentes/farmacologia
13.
J Am Soc Mass Spectrom ; 33(10): 1982-1989, 2022 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-36126229

RESUMO

The Paternò-Büchi (PB) reaction is a cycloaddition reaction between a carbon-carbon double bond (C═C) and a photochemically excited carbonyl-containing compound. The constrained ring formed between the C═C bond and the PB reagent is more susceptible to fragmentation by collision-induced dissociation, which facilitates identification of the C═C position within the fatty acyl tails of lipids. Although the original PB reaction using acetone had a low yield of derivatized lipids and therefore a low yield of diagnostic ions, a new generation of PB reagents based on halogenated acetophenones has improved the reaction yield substantially. In this study, we investigated the use of halogenated PB reagents and ion mobility to improve the identification of PB-derivatized lipids by shifting them out of the densely populated lipid region of ion mobility-mass spectrometry (IM-MS) space. Several halogenated PB reagents containing fluorine, chlorine and bromine were investigated for their ability to decrease the collision cross-section (CCS) values of derivatized lipids and yield sufficient intensity for both the derivatized lipid and its diagnostic ions. We found that 4'-chloro-2',6'-difluoroacetophenone (CDFAP) displayed the best performance, with an average decrease in CCS of 4.4% and yield of derivatized lipids and diagnostic ions comparable to the trifluorinated acetophenone reagent proposed by the Xia group. The unique isotope pattern resulting from the chlorine substituent aided in identification of the derivatized lipids and their diagnostic ions, as well. We further demonstrate that derivatization with CDFAP preserves the separation of lipids classes in IM-MS space.


Assuntos
Acetona , Bromo , Acetona/química , Acetofenonas , Carbono/química , Cloro , Flúor , Indicadores e Reagentes , Íons , Isótopos , Lipídeos/química
14.
Water Res ; 225: 119120, 2022 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-36126426

RESUMO

The triplet states of dissolved organic matter (3DOM*) have been well known to oxidize various organic contaminants, but evidence of their reducing properties are largely scarce. In this work, chlorine dioxide (ClO2) as a single-electron oxidant was used as a probe to evaluate the reduction property of 3DOM*. The reduction of ClO2 to chlorite was observed in the solutions of model photosensitizers (i.e., 4-carboxybenzophenone, benzophenone, acetophenone, 3-methoxyacetophenone, naphthalene, and xanthone) during UV irradiation with the presence of ClO2, though they are resistant to ClO2 oxidation in the dark. The reducing property of the triplet states of photosensitizers was verified and their second-order reaction rate constants with ClO2 were determined to be in the range of 1.45(± 0.03)× 109 - 2.18(± 0.06) × 109 M-1 s-1 at pH 7.0. The quenching tests excluded the role of other reactive species (e.g., HO•, O(3P), Cl•, ClO• and HOCl/OCl-, O2•- and eaq-) in ClO2 reduction to chlorite when using model photosensitizers and DOM isolates. Chlorite formation was 48.1-90.4% and 4812.8-7721.8% higher during UV irradiation with the presence of ClO2 and DOM than those without UV irradiation or without DOM present, respectively. The enhancement was attributed to the enhanced electron donating capacity (chlorite precursors) of DOM upon UV irradiation and also to 3DOM* acting as an electron donor reducing ClO2 to chlorite. This study highlighted the important role of 3DOM* as a reductant.


Assuntos
Compostos Clorados , Purificação da Água , Xantonas , Fármacos Fotossensibilizantes , Substâncias Redutoras , Compostos Clorados/química , Óxidos/química , Oxirredução , Oxidantes , Benzofenonas , Naftalenos , Acetofenonas , Cloro/química
15.
J Org Chem ; 87(19): 13236-13258, 2022 10 07.
Artigo em Inglês | MEDLINE | ID: mdl-36128804

RESUMO

A Rh(III)-catalyzed weak enone carbonyl/ketone-assisted aerobic oxidative C-H olefination of aromatics with unactivated alkenes has been developed. This protocol involves cross-dehydrogenative Heck-type olefination reaction of various substituted biologically relevant chalcones and aromatic ketones such as acetophenones and chromones with various functionalized unactivated olefins in moderate to good yields. Further, ortho-alkylation of chalcones with norbornene is also demonstrated. A possible reaction mechanism involving weak chelation-assisted C-H activation/insertion/ß-hydride elimination was proposed and supported by the deuterium labeling studies.


Assuntos
Alcenos , Chalconas , Acetofenonas , Catálise , Deutério , Cetonas , Estrutura Molecular , Norbornanos
16.
Org Biomol Chem ; 20(36): 7226-7231, 2022 09 21.
Artigo em Inglês | MEDLINE | ID: mdl-36053547

RESUMO

3-Arylquinoxaline-2-thiones were conveniently synthesized via three-component oxidative condensation of acetophenones with o-phenylenediamines and sulfur in DMSO in the presence of piperidine as a catalyst. The products could be readily isolated from the reaction mixture by simple precipitation and washing with methanol. This set of reaction conditions applied to higher homologs of acetophenones as well as benzyl phenyl ketones led to 2,3-di-C-substituted quinoxalines. Further functionalization of 3-phenylquinoxaline-2-thione via reaction on the thione group could be readily performed to provide quinoxaline derivatives in good yields.


Assuntos
Quinoxalinas , Tionas , Acetofenonas , Catálise , Dimetil Sulfóxido , Cetonas , Metanol , Fenilenodiaminas , Piperidinas , Enxofre
18.
Chemosphere ; 307(Pt 3): 135859, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-35987270

RESUMO

The aim of this study was to isolate thermotolerant alkali lignin-degrading bacteria and to investigate their degradation characteristics and application in food waste composting. Two thermotolerant alkali lignin-degrading bacteria isolates were identified as Bacillus sp. LD2 (LD2) and a novel species Aneurinibacillus sp. LD3 (LD3). Compared with strain LD2, LD3 had a higher alkali lignin degradation rate (61.28%) and ligninolytic enzyme activities, and the maximum lignin peroxidase, laccase, and manganese peroxidase activities were 3117.25, 1484.5, and 1770.75 U L-1, respectively. GC-MS analysis revealed that low-molecular-weight compounds such as 4'-hydroxy-3'-methoxy acetophenone, vanillic acid, 1-(4-hydroxy-3,5-dimethoxyphenyl), benzoic acid, and octadecanoic acid were formed in the degradation of alkali lignin by LD3, indicating the cleavage of ß-aryl ether, Cα-Cß bonds, and aromatic rings in lignin. Composting results showed that inoculating LD3 improved the degradation of organic matter by 20.11% and reduced the carbon-to-nitrogen (C/N) ratio (15.66). Additionally, a higher decrease in the content of lignocellulose was observed in the LD treatment. FTIR and 3D-EEM spectra analysis indicated that inoculating LD3 promoted the decomposition of easily available organic substances and lignocellulose and the formation of aromatic structures and humic acid-like substances. In brief, the thermotolerant lignin-degrading bacterium Aneurinibacillus sp. LD3 is effective in degrading lignin and improving the quality of composting.


Assuntos
Compostagem , Eliminação de Resíduos , Acetofenonas , Álcalis , Bactérias/metabolismo , Ácido Benzoico , Carbono/metabolismo , Éteres , Alimentos , Substâncias Húmicas , Lacase/metabolismo , Lignina/metabolismo , Nitrogênio/metabolismo , Ácido Vanílico
19.
Bioorg Chem ; 128: 106058, 2022 11.
Artigo em Inglês | MEDLINE | ID: mdl-35917750

RESUMO

Bis-Schiff's base derivatives of 4-nitroacetophenone (1-18) were synthesized in good yields by reacting hydrazone of 4-nitroacetophenone with substituted aldehydes and ketones with catalytic amount of acetic acid. The structures of synthesized products (1-18) were deduced with the help of spectroscopic techniques like 1H NMR, 13C NMR and HR-ESIMS. The synthesized bis-Schiff's bases were assessed for their α-glucosidase inhibitory activity where compound 4 (IC50 = 2.79 ± 0.04 µM), 1 (IC50 = 9.76 ± 0.31 µM), 6 (IC50 = 11.37 ± 0.20 µM), 17 (IC50 = 14.10 ± 0.12 µM), 14 (IC50 = 17.21 ± 0.28 µM), and 8 (IC50 = 20.73 ± 0.53 µM), showed a very high potential for inhibition of α-glucosidase. Compounds 11, 15, 16, 2, 18, 7, and 5 showed significant inhibition against alpha-glucosidase with IC50 values 22.98 ± 0.34, 24.45 ± 0.53, 27.31 ± 0.29, 40.56 ± 0.60, 41.58 ± 0.47, 46.53 ± 0.76, and 47.46 ± 0.89 µM, respectively. Furthermore, compound 10 (IC50 = 52.63 ± 0.74 µM), 12 (IC50 = 70.80 ± 3.59 µM), 3 (IC50 = 82.68 ± 0.69 µM), 13 (IC50 = 88.89 ± 4.25 µM), and 9 (IC50 = 94.58 ± 0.86 µM) showed moderate activity towards the inhibition of α-glucosidase enzyme. All these compounds were compared with acarbose (IC50 = 875.75 ± 1.24 µM) as a standard α-glucosidase inhibitor. Molecular docking was used to know the molecular bases of such high activities against α-glucosidase. High docking scores were recorded implying significant interactions between the active compounds and amino acid residues of the active site of α-glucosidase.


Assuntos
Inibidores de Glicosídeo Hidrolases , alfa-Glucosidases , Acetofenonas , Inibidores de Glicosídeo Hidrolases/química , Simulação de Acoplamento Molecular , Estrutura Molecular , Relação Estrutura-Atividade , alfa-Glucosidases/metabolismo
20.
Appl Environ Microbiol ; 88(16): e0072422, 2022 08 23.
Artigo em Inglês | MEDLINE | ID: mdl-35938864

RESUMO

Acetovanillone is a major aromatic monomer produced in oxidative/base-catalyzed lignin depolymerization. However, the production of chemical products from acetovanillone has not been explored due to the lack of information on the microbial acetovanillone catabolic system. Here, the acvABCDEF genes were identified as specifically induced genes during the growth of Sphingobium sp. strain SYK-6 cells with acetovanillone and these genes were essential for SYK-6 growth on acetovanillone and acetosyringone (a syringyl-type acetophenone derivative). AcvAB and AcvF produced in Escherichia coli phosphorylated acetovanillone/acetosyringone and dephosphorylated the phosphorylated acetovanillone/acetosyringone, respectively. AcvCDE produced in Sphingobium japonicum UT26S carboxylated the reaction products generated from acetovanillone/acetosyringone by AcvAB and AcvF into vanilloyl acetic acid/3-(4-hydroxy-3,5-dimethoxyphenyl)-3-oxopropanoic acid. To demonstrate the feasibility of producing cis,cis-muconic acid from acetovanillone, a metabolic modification on a mutant of Pseudomonas sp. strain NGC7 that accumulates cis,cis-muconic acid from catechol was performed. The resulting strain expressing vceA and vceB required for converting vanilloyl acetic acid to vanillic acid and aroY encoding protocatechuic acid decarboxylase in addition to acvABCDEF successfully converted 1.2 mM acetovanillone to approximately equimolar cis,cis-muconic acid. Our results are expected to help improve the yield and purity of value-added chemical production from lignin through biological funneling. IMPORTANCE In the alkaline oxidation of lignin, aromatic aldehydes (vanillin, syringaldehyde, and p-hydroxybenzaldehyde), aromatic acids (vanillic acid, syringic acid, and p-hydroxybenzoic acid), and acetophenone-related compounds (acetovanillone, acetosyringone, and 4'-hydroxyacetophenone) are produced as major aromatic monomers. Also, base-catalyzed depolymerization of guaiacyl lignin resulted in vanillin, vanillic acid, guaiacol, and acetovanillone as primary aromatic monomers. To date, microbial catabolic systems of vanillin, vanillic acid, and guaiacol have been well characterized, and the production of value-added chemicals from them has also been explored. However, due to the lack of information on the microbial acetovanillone and acetosyringone catabolic system, chemical production from acetovanillone and acetosyringone has not been achieved. This study elucidated the acetovanillone/acetosyringone catabolic system and demonstrates the potential of using these genes for the production of value-added chemicals from these compounds.


Assuntos
Lignina , Ácido Vanílico , Acetofenonas , Escherichia coli/genética , Guaiacol , Lignina/metabolismo , Ácido Vanílico/metabolismo
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