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Physical Chemistry Chemical Physics :... Nov 2022Halogenated groups are relevant in pharmaceutical applications and potentially useful spectroscopic probes for infrared spectroscopy. In this work, the structural...
Halogenated groups are relevant in pharmaceutical applications and potentially useful spectroscopic probes for infrared spectroscopy. In this work, the structural dynamics and infrared spectroscopy of -fluorophenol (F-PhOH) and phenol (PhOH) is investigated in the gas phase and in water using a combination of experiment and molecular dynamics (MD) simulations. The gas phase and solvent dynamics around F-PhOH and PhOH is characterized from atomistic simulations using empirical energy functions with point charges or multipoles for the electrostatics, Machine Learning (ML) based parametrizations and with full (QM) and mixed Quantum Mechanical/Molecular Mechanics (QM/MM) simulations with a particular focus on the CF- and OH-stretch region. The CF-stretch band is heavily mixed with other modes whereas the OH-stretch in solution displays a characteristic high-frequency peak around 3600 cm most likely associated with the -OH group of PhOH and F-PhOH together with a characteristic progression below 3000 cm due to coupling with water modes which is also reproduced by several of the simulations. Solvent and radial distribution functions indicate that the CF-site is largely hydrophobic except for simulations using point charges which renders them unsuited for correctly describing hydration and dynamics around fluorinated sites. The hydrophobic character of the CF-group is particularly relevant for applications in pharmaceutical chemistry with a focus on local hydration and interaction with the surrounding protein.
Topics: Quantum Theory; Phenols; Spectrophotometry, Infrared; Water; Solvents; Phenol
PubMed: 36268728
DOI: 10.1039/d2cp02857c -
Scientific Reports Nov 2022Boron tribromide-mediated demethylation of rhenium-oxo and gold meso-tris(4-methoxyphenyl)corrole and meso-tris(3,5-dimethoxyphenylcorrole), M[TpOMePC] and...
Boron tribromide-mediated demethylation of rhenium-oxo and gold meso-tris(4-methoxyphenyl)corrole and meso-tris(3,5-dimethoxyphenylcorrole), M[TpOMePC] and M[T(3,5-OMe)PC] (M = ReO, Au), have yielded the corresponding phenol- and resorcinol-appended metallocorroles, M[TpOHPC] and M[T(3,5-OH)PC], in good yields. The latter compounds proved insoluble in dichloromethane and chloroform but soluble in THF. The M[T(3,5-OH)PC] derivatives also proved moderately soluble in 0.05 M aqueous KOH. Unlike oxidation-prone aminophenyl-substituted corroles, the phenol- and resorcinol-appended metallocorroles could be readily handled in air without special precautions. The phenolic metallocorroles could be readily alkylated with 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecyl iodide ("FtI") to afford the fluorous-tagged metallocorroles M[TpOFtPC] and M[T(3,5-OFt)PC] in > 90% yields. The simplicity of the synthetic protocols promise a wide range of phenolic and fluorous-tagged porphyrin analogues with potential applications to diverse fields such as sensors, catalysis, and photodynamic therapy, among others.
Topics: Phenol; Phenols; Resorcinols; Catalysis
PubMed: 36357501
DOI: 10.1038/s41598-022-23889-0 -
Environmental Science & Technology Apr 2022Permanganate oxidation is an attractive environmental remediation strategy due to its low cost, ease of use, and wide range in reactivity. Here, permanganate reactivity... (Review)
Review
Permanganate oxidation is an attractive environmental remediation strategy due to its low cost, ease of use, and wide range in reactivity. Here, permanganate reactivity trends are investigated for model organic compounds and organic contaminants. Second-order permanganate reaction rate constants were compiled for 215 compounds from 82 references (journal articles, conference proceedings, master's theses, and dissertations). Additionally, we validated some phenol rate constants and contribute a few additional phenol rate constants. Commonalities between contaminant oxidation products are also discussed, and we tentatively identify several model compound oxidation products. Aromatic rings, alcohols, and ether groups had low reaction rate constants with permanganate. Alkene reaction sites had the highest reaction rate constants, followed by phenols, anilines, and benzylic carbon-hydrogen bonds. Generally, permanganate reactivity follows electrophilic substitution trends at the reaction site where electron donating groups increase the rate of reaction, while electron withdrawing groups decrease the rate of reaction. Solution conditions, specifically, buffer type and concentration, may impact the rate of reaction, which could be due to either an ionic strength effect or the buffer ions acting as ligands. The impact of these solution conditions, unfortunately, precludes the development of a quantitative structure-activity relationship for permanganate reaction rate constants with the currently available data. We note that critical experimental details are often missing in the literature, which posed a challenge when comparing rate constants between studies. Future research directions on permanganate oxidation should seek to improve our understanding of buffer effects and to identify oxidation products for model compounds so that extrapolations can be made to more complex contaminant structures.
Topics: Kinetics; Manganese Compounds; Oxidation-Reduction; Oxides; Phenol; Phenols
PubMed: 35356836
DOI: 10.1021/acs.est.1c03621 -
Journal of Hazardous Materials May 2022In this study, the long-term fate of toluene and phenol in the soil was investigated, and the transformation products (TPs) and pathways of these compounds were studied...
In this study, the long-term fate of toluene and phenol in the soil was investigated, and the transformation products (TPs) and pathways of these compounds were studied by a high resolution mass spectrometry (HRMS)-based suspect and non-target screening approach for the first time, and 9 and 12 transformation products were identified for toluene and phenol, respectively in the lab-exposed soil samples. Salicylaldehyde, 4-hydroxybenzaldehyde, and benzaldehyde were identified in toluene-contaminated field soil samples for the first time, and the main mechanisms involved in the biodegradation and detoxification of toluene and phenol in soil were oxidation, carboxylation, dehydroxylation, and ring fission amongst others. 2-oxoglutarate, TP165-A, TP165-B, TP172, and TP195 were identified as novel phenol transformation products, while salicylaldehyde, 2-oxoglutarate, TP165-A, and TP165-B were identified as novel toluene transformation products, providing new possible evidence for additional degradation pathways, which could give new insights into the fate of toluene and phenol during the natural attenuation process in the environment. Finally, salicylaldehyde, 4-OH-benzaldehyde, and 4-OH-benzoic acid which were detected at Level 1 identification confidence were suggested as indicator chemicals of toluene and phenol exposure in the contaminated field.
Topics: Benzaldehydes; Ketoglutaric Acids; Mass Spectrometry; Phenol; Phenols; Soil; Toluene
PubMed: 35739654
DOI: 10.1016/j.jhazmat.2022.128429 -
Environment International Dec 2022Non-persistent endocrine-disrupting chemicals (EDCs), including phthalates and phenols, are ubiquitous in both the environment and human body. A growing body of... (Review)
Review
Non-persistent endocrine-disrupting chemicals (EDCs), including phthalates and phenols, are ubiquitous in both the environment and human body. A growing body of epidemiologic studies have identified concerning links between EDCs and adverse reproductive and developmental health effects. Despite consistent evidence, risk assessments and policy interventions often arrive late. This presents an urgent need to identify evidence-based interventions for implementation at both clinical and community levels to reduce EDC exposure, especially in susceptible populations. The reproductive life cycle (menarche to menopause for females and after pubertal onset for males) includes some of the most vulnerable periods to environmental exposures, such as the preconception and perinatal stages, representing a key window of opportunity to intervene and prevent unfavorable health outcomes. This review aims to synthesize and assess behavioral, dietary, and residential EDC-driven interventions to develop recommendations for subsequent, larger-scale studies that address knowledge-gaps in current interventions during the reproductive life cycle. We selected 21 primary interventions for evaluation, in addition to four supplemental interventions. Among these, accessible (web-based) educational resources, targeted replacement of (known) toxic products, and personalization of the intervention through meetings and support groups, were the most promising strategies for reducing EDC concentrations. However, we document a paucity of interventions to prevent phthalate and phenol exposures during the reproductive years, especially among men. Accordingly, we recommend additional, larger clinical and community-based intervention studies to reduce EDC exposure. Specifically, future intervention studies should focus on short-term, mid-, and long-term exposure reduction to phthalates and phenols. The latter, especially, is required for the development of clinical and public health guidelines to promote reproductive and developmental health globally.
Topics: Humans; Phenol
PubMed: 36283156
DOI: 10.1016/j.envint.2022.107576 -
Molecules (Basel, Switzerland) Dec 2022Prenylated diresorcinols exhibit various bioactivities, including cytotoxic, antibacterial, and antifungal activities. Therefore, establishing facile and efficient...
Prenylated diresorcinols exhibit various bioactivities, including cytotoxic, antibacterial, and antifungal activities. Therefore, establishing facile and efficient synthetic routes for prenylated diresorcinols facilitates their development as chemical probes or drugs with a novel mode of action. In this study, microwave-assisted copper catalysis was explored as a cost-effective and environmentally friendly method for the cross-coupling of sterically hindered -prenylated phenols and aryl halides to produce bioactive prenylated diresorcinols, diorcinol I and leotiomycene B. Notable advantages of microwave-assisted catalysis include not only operational simplicity and rapid heating but also shorter reaction times and higher chemical yields. In addition, highly regioselective prenylation of phenol was achieved for the preparation of -prenyl phenol via directed lithiation and subsequent alkylation. This study provides valuable insights for the preparation of other bioactive prenylated diresorcinols. Furthermore, considering that prenylated benzenoids are biosynthetic precursors of various polycyclic natural products, this synthetic route could be expanded to more complex bioactive compounds possessing diaryl ethers.
Topics: Phenol; Microwaves; Phenols; Ethers; Catalysis
PubMed: 36615257
DOI: 10.3390/molecules28010062 -
International Immunopharmacology Dec 2023Sepsis is a life-threatening disease with limited treatment options, and the inflammatory process represents an important factor affecting its progression. Many studies...
Sepsis is a life-threatening disease with limited treatment options, and the inflammatory process represents an important factor affecting its progression. Many studies have demonstrated the critical roles of signal transducer and activator of transcription 3 (STAT3) in sepsis pathophysiology and pro-inflammatory responses. Inhibition of STAT3 activity may therefore represent a promising treatment option for sepsis. We here used a mouse model to demonstrate that (E)-2-methoxy-4-(3-(4-methoxyphenyl)prop-1-en-1-yl)phenol (MMPP) treatment prevented the liver sepsis-related mortality induced by 30 mg/kg lipopolysaccharide (LPS) treatment and reduced LPS-induced increase in alanine transaminase, aspartate transaminase, and lactate dehydrogenase levels, all of which are markers of liver sepsis progression. These recovery effects were associated with decreased LPS-induced STAT3, p65, and JAK1 phosphorylation and proinflammatory cytokine (interleukin 1 beta, interleukin 6, and tumor necrosis factor alpha) level; expression of cyclooxygenase-2 and induced nitric oxide synthase were also reduced by MMPP. In an in vitro study using the normal liver cell line THLE-2, MMPP treatment prevented the LPS-induced increase of STAT3, p65, and JAK1 phosphorylation and inflammatory protein expression in a dose-dependent manner, and this effect was enhanced by combination treatment with MMPP and STAT3 inhibitor. The results clearly indicate that MMPP treatment prevents LPS-induced mortality by inhibiting the inflammatory response via STAT3 activity inhibition. Thus, MMPP represents a novel agent for alleviating LPS-induced liver sepsis.
Topics: Mice; Animals; Signal Transduction; Lipopolysaccharides; Phenol; Phosphorylation; STAT3 Transcription Factor; Phenols; Liver; Sepsis
PubMed: 37977740
DOI: 10.1016/j.intimp.2023.111124 -
Journal of Nutritional Science and... 2023Protein is an essential nutrient that plays several roles in the maintenance of the human body. A high-protein diet is also known to play an important role in weight...
Protein is an essential nutrient that plays several roles in the maintenance of the human body. A high-protein diet is also known to play an important role in weight management in obese individuals and in maintaining muscle strength in the elderly. However, over-consumption of protein can have negative effects on health, including deterioration of the intestinal environment by the production of amino acid metabolites such as phenols. Interest in the regulation of the intestinal environment to maintain health has gained attention recently. Resistant maltodextrin (RMD) is a prebiotic dietary fiber. Therefore, we investigated whether RMD suppressed the production of amino acid metabolites through intestinal regulation in rats. Wistar rats were fed either an AIN-93G diet or a modified AIN-93G diet containing 5% tyrosine. RMD (2.5% or 5.0%) was provided with drinking water. The rats were fed these diets and water ad libitum for 3 wk. Urine was collected overnight, after which serum, liver, kidneys, and the whole cecum were collected from rats under anesthesia with isoflurane for analysis of phenols and microbiota. RMD decreased the cecal, serum, and urinary levels of phenols, especially phenol. Moreover, the relative abundance of intestinal Romboutsia ilealis showed a significant correlation with the cecal phenols levels, and RMD decreased the abundance of this species. Thus, RMD may suppress phenols production and decrease serum phenols levels by altering the intestinal environment in rats.
Topics: Humans; Aged; Rats; Animals; Phenols; Rats, Wistar; Phenol; Amino Acids
PubMed: 37648513
DOI: 10.3177/jnsv.69.268 -
Food Research International (Ottawa,... Oct 2023Cranberry (poly)phenols may have potential health benefits. Circulating (poly)phenol metabolites can act as mediators of these effects, but they are subjected to an... (Randomized Controlled Trial)
Randomized Controlled Trial
Cranberry (poly)phenols may have potential health benefits. Circulating (poly)phenol metabolites can act as mediators of these effects, but they are subjected to an extensive inter-individual variability. This study aimed to quantify both plasma and urine (poly)phenol metabolites following a 12-week intake of a cranberry powder in healthy older adults, and to investigate inter-individual differences by considering the existence of urinary metabotypes related to dietary (poly)phenols. Up to 13 and 67 metabolites were quantified in plasma and urine respectively. Cranberry consumption led to changes in plasma metabolites, mainly hydroxycinnamates and hippuric acid. Individual variability in urinary metabolites was assessed using different data sets and a combination of statistical models. Three phenolic metabotypes were identified, colonic metabolism being the main driver for subject clustering. Metabotypes were characterized by quali-quantitative differences in the excretion of some metabolites such as phenyl-γ-valerolactones, hydroxycinnamic acids, and phenylpropanoic acids. Metabotypes were further confirmed when applying a model only focused on flavan-3-ol colonic metabolites. 5-(3',4'-dihydroxyphenyl)-γ-valerolactone derivatives were the most relevant metabolites for metabotyping. Metabotype allocation was well preserved after 12-week intervention. This metabotyping approach for cranberry metabolites represents an innovative step to handle the complexity of (poly)phenol metabolism in free-living conditions, deciphering the existence of metabotypes derived from the simultaneous consumption of different classes of (poly)phenols. These results will help contribute to studying the health effects of cranberries and other (poly)phenol-rich foods, mainly considering gut microbiota-driven individual differences.
Topics: Phenol; Vaccinium macrocarpon; Phenols; Cluster Analysis; Dietary Supplements
PubMed: 37689939
DOI: 10.1016/j.foodres.2023.113187 -
Applied Microbiology and Biotechnology Apr 2022Rhodococcus pyridinivorans B403 is a promising bacterium for degrading phenolic pollutants. In the application, the high-concentration substrate has a significant...
Rhodococcus pyridinivorans B403 is a promising bacterium for degrading phenolic pollutants. In the application, the high-concentration substrate has a significant inhibitory effect on cell growth and phenol degradation, which makes adaptive evolution study of bacteria an important guarantee for further application. The present work found evolved R. pyridinivorans (X1 and X2) had enhanced tolerance to phenolic pollutants as compared to the ancestor strain: the minimum inhibitory concentrations (MIC) of phenol, m-cresol, and catechol increased from 1.2, 0.7, 0.8 g/L to 1.8, 1.0, 1.2 g/L of strain X1, and to 2.4, 1.2, 1.4 g/L of strain X2, respectively. Furthermore, compared to B403, X1, and X2 accumulated more biomass in 500-mg/L cresol medium and degraded phenols more efficiently. Correspondingly, genome sequencing revealed that the mutation sites in genes were annotated as encoding phosphotransferase, MFS transporter, AcrR regulator, and GlpD regulator in the adapted strains, which were closely associated with improved phenol tolerance and degradation. The conclusions provided theoretical basis for the phenol tolerance and degradation, which could promote construction of engineering bacteria for practical application. KEY POINTS: • Evolved strains were more resistant to phenols • Evolved strains degraded phenols more quickly • Genome sequencing elucidated mechanisms of enhanced phenol tolerance and degradation.
Topics: Biodegradation, Environmental; Environmental Pollutants; Genomics; Phenol; Phenols; Rhodococcus
PubMed: 35278114
DOI: 10.1007/s00253-022-11858-6