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Environmental Health Perspectives Nov 2022
Topics: Alkanesulfonic Acids; Fluorocarbons; Alkanesulfonates
PubMed: 36331817
DOI: 10.1289/EHP12012 -
Environmental Health Perspectives Jul 2023Nontargeted analysis (NTA) methods identify novel exposures; however, few chemicals have been quantified and interrogated with pregnancy complications.
BACKGROUND
Nontargeted analysis (NTA) methods identify novel exposures; however, few chemicals have been quantified and interrogated with pregnancy complications.
OBJECTIVES
We characterized levels of nine exogenous and endogenous chemicals in maternal and cord blood identified, selected, and confirmed in prior NTA steps, including linear and branched isomers perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), monoethylhexyl phthalate, 4-nitrophenol, tetraethylene glycol, tridecanedioic acid, octadecanedioic acid, and deoxycholic acid. We evaluated relationships between maternal and cord levels and between gestational diabetes mellitus (GDM) and hypertensive disorders of pregnancy in a diverse pregnancy cohort in San Francisco.
METHODS
We collected matched maternal and cord serum samples at delivery from 302 pregnant study participants from the Chemicals in Our Bodies cohort in San Francisco. Chemicals were identified via NTA and quantified using targeted approaches. We calculated distributions and Spearman correlation coefficients testing the relationship of chemicals within and between the maternal and cord blood matrices. We used adjusted logistic regression to calculate the odds of GDM and hypertensive disorders of pregnancy associated with an interquartile range increase in maternal chemical exposures.
RESULTS
We detected linear PFOS, PFHxS, octadecanedioic acid, and deoxycholic acid in at least 97% of maternal samples. Correlations ranged between and 0.9. We observed strong correlations between cord and maternal levels of PFHxS, linear PFOS, and branched PFOS (, 0.8, and 0.8, respectively). An interquartile range increase in linear and branched PFOS, tridecanedioic acid, octadecanedioic acid, and deoxycholic acid was associated with increased odds ratio (OR) of GDM [ (95% CI: 0.89, 2.01), 1.24 (95% CI: 0.86, 1.80), 1.26 (95% CI: 0.93, 1.73), 1.24 (95% CI: 0.86, 1.80), and 1.23 (95% CI: 0.87, 1.75), respectively]. Tridecanedioic acid was positively associated with hypertensive disorders of pregnancy [ (95% CI: 0.90, 1.86)].
DISCUSSION
We identified both exogenous and endogenous chemicals seldom quantified in pregnant study participants that were also related to pregnancy complications and demonstrated the utility of NTA to identify chemical exposures of concern. https://doi.org/10.1289/EHP11546.
Topics: Pregnancy; Female; Humans; Cross-Sectional Studies; Cohort Studies; Hypertension, Pregnancy-Induced; Pregnancy Complications; Diabetes, Gestational; Alkanesulfonic Acids; Alkanesulfonates; Fluorocarbons; Deoxycholic Acid; Environmental Pollutants
PubMed: 37466315
DOI: 10.1289/EHP11546 -
Molecules (Basel, Switzerland) May 2023Sulfonamides are one of the oldest groups of veterinary chemotherapeutic agents. Physico-chemical properties, the concentration and the nature of the environment are the...
Sulfonamides are one of the oldest groups of veterinary chemotherapeutic agents. Physico-chemical properties, the concentration and the nature of the environment are the factors responsible for the distribution of sulfonamides in the living organism. Although these drug compounds have been in use for more than half a century, knowledge about their behavior is still limited. Physiological activity is currently attributed to the sulfanyl radical. Our study is devoted to the spectral properties of aqueous solutions of sulfaguanidine, in which the formation of complexes with an H-bond and a protonated form takes place. The nature of the fluorescent state of sulfaguanidine was interpreted using computational chemistry, the electronic absorption method and the luminescence method. The structure of sulfaguanidine includes several active fragments: aniline, sulfonic and guanidine. To reveal the role of fragments in the physiological activity of the studied antibiotic, we calculated and compared the effective charges of the fragments of aniline and sulfaguanidine molecules. Chromophore groups were identified in molecules, which determine the intermolecular interaction between a molecule and a proton-donor solvent. The study also revealed the impact of sulfone and guanidine groups, as well as complexation, on the effective charge of the antibiotic fragment responsible for physiological activity and luminescent ability.
Topics: Sulfaguanidine; Luminescence; Anti-Bacterial Agents; Sulfonamides; Sulfanilamide; Aniline Compounds; Guanidines
PubMed: 37241901
DOI: 10.3390/molecules28104159 -
Nature Communications Sep 2020Natural biomolecules such as peptides and DNA can dynamically self-organize into diverse hierarchical structures. Mimicry of this homopolymer self-assembly using...
Natural biomolecules such as peptides and DNA can dynamically self-organize into diverse hierarchical structures. Mimicry of this homopolymer self-assembly using synthetic systems has remained limited but would be advantageous for the design of adaptive bio/nanomaterials. Here, we report both experiments and simulations on the dynamic network self-assembly and subsequent collapse of the synthetic homopolymer poly(propylene sulfone). The assembly is directed by dynamic noncovalent sulfone-sulfone bonds that are susceptible to solvent polarity. The hydration history, specified by the stepwise increase in water ratio within lower polarity water-miscible solvents like dimethylsulfoxide, controls the homopolymer assembly into crystalline frameworks or uniform nanostructured hydrogels of spherical, vesicular, or cylindrical morphologies. These electrostatic hydrogels have a high affinity for a wide range of organic solutes, achieving >95% encapsulation efficiency for hydrophilic small molecules and biologics. This system validates sulfone-sulfone bonding for dynamic self-assembly, presenting a robust platform for controllable gelation, nanofabrication, and molecular encapsulation.
Topics: Alkenes; Hydrogels; Hydrophobic and Hydrophilic Interactions; Polypropylenes; Static Electricity; Sulfones
PubMed: 32994414
DOI: 10.1038/s41467-020-18657-5 -
The Journal of Organic Chemistry Dec 2021A serendipitous one-step transformation of 5'-deoxy-5'-heteroarylsulfonylnucleosides into cyclopentene derivatives is reported. This unique transformation likely...
A serendipitous one-step transformation of 5'-deoxy-5'-heteroarylsulfonylnucleosides into cyclopentene derivatives is reported. This unique transformation likely proceeds via a domino reaction initiated by α-deprotonation of the heteroaryl sulfone and subsequent elimination reaction to generate a nucleobase and an α,β-unsaturated sulfone that contains a formyl group. The Michael addition of the nucleobase to the α,β-unsaturated sulfone and the subsequent intramolecular Julia-Kocienski reaction eventually generate the cyclopentene ring. Heteroarylthio and acylthio groups can be incorporated into the cyclopentene core in place of the nucleobase by conducting this reaction in the presence of a heteroarylthiol and a thiocarboxylic acid, respectively. ,-Trisubstituted cyclopentene derivatives are obtained as a single stereoisomer from ribonucleoside-derived Julia-Kocienski sulfones.
Topics: Cyclopentanes; Indicators and Reagents; Nucleosides; Stereoisomerism; Sulfones
PubMed: 34762430
DOI: 10.1021/acs.joc.1c01940 -
The Science of the Total Environment Mar 2022Gestation and lactation are critical and vulnerable stages for fetuses and newborns. During these periods, per-/polyfluoroalkyl substances (PFASs) accumulated in mothers...
Gestation and lactation are critical and vulnerable stages for fetuses and newborns. During these periods, per-/polyfluoroalkyl substances (PFASs) accumulated in mothers can be transferred to newborns through placenta and/or breastfeeding, causing potential health risks. To investigate the pre- and postnatal PFAS exposure of newborns, we analyzed 21 emerging and legacy PFASs in 60 sets of matched maternal serum, cord serum, and breast milk samples. In serum, perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), and 6:2 chlorinated polyfluorinated ether sulfonates (6:2 Cl-PFESA) were the most predominant PFASs, while PFOA, PFOS and 6:2 fluorotelomer phosphate diester (6:2 diPAP) contributed most to breast milk. For most PFASs, the levels followed the order of maternal serum > cord serum > breast milk. The 6:2 Cl-PFESA was positively associated with birth weight and ponderal index (p < 0.05). The breastfeeding transfer efficiencies (R, median: 0.02-0.10) of most PFASs were 1-2 orders of magnitude lower than transplacental transfer efficiencies (R, median: 0.40-1.45), except for perfluorobutanesulfonic acid (PFBS) showing high transfer efficiency both through placenta (median at 0.89) and breastfeeding (median at 0.86). The one-month postnatal exposure to PFASs via breastfeeding was much higher than prenatal exposure in utero. This study enhances the understanding of transplacental and breastfeeding transfer of PFASs and provides assessments of prenatal and postnatal exposure of newborns to emerging and legacy PFASs.
Topics: Alkanesulfonates; Alkanesulfonic Acids; China; Ether; Ethers; Female; Fluorocarbons; Humans; Infant, Newborn; Milk, Human; Placenta; Pregnancy
PubMed: 34952085
DOI: 10.1016/j.scitotenv.2021.152446 -
The Science of the Total Environment Mar 2023Skeleton develops extremely fast during fetal and neonatal stages; thus, fetuses and newborns exhibit unique vulnerabilities to vitamin D metabolism dysregulation,...
Skeleton develops extremely fast during fetal and neonatal stages; thus, fetuses and newborns exhibit unique vulnerabilities to vitamin D metabolism dysregulation, giving vitamin D's principal role in calcium homeostasis. Previous studies linked legacy per and polyfluoroalkyl ether sulfonic acids (PFAS) with vitamin D biomarker status in adults and children; however, how PFAS, especially emerging CI-PFESAs, influence vitamin D among newborns is unknown. This study focused on the epidemiological linkages between PFAS and vitamin D biomarkers. Eleven PFAS, including legacy PFAS and emerging CI-PFESAs, as well as two vitamin D metabolites [25-hydroxyvitamin D2 (25(OH)D2) and 25-hydroxyvitamin D3 (25(OH)D3)], were determined in cord sera of 992 newborns from a birth cohort in Wuhan, China. The cord serum levels of 25(OH)D2 and 25(OH)D3 were summed as total 25(OH)D, which is a reliable biomarker of vitamin D status. The associations of separated PFAS with vitamin D biomarker levels were analyzed via multiple linear models, whereas the mixture effect was estimated by utilizing the weighted quantile sum (WQS) regression. We observed that per doubling changes in perfluorotridecanoate (PFTrDA), perfluorohexane sulfonate (PFHxS), and perfluorooctane sulfonate (PFOS) were associated with a 6.04 to 9.05 % change in total 25(OH)D levels. PFHxS contributed over half of the PFAS mixture effect on total 25(OH)D. Stratified analysis indicated that the associations of certain PFAS with vitamin D biomarkers were more pronounced among boys. The emerging CI-PFESAs were not robustly related to vitamin D biomarker levels. The results suggested that exposure to legacy PFAS might disturb vitamin D status in newborns. Future epidemiological studies are required to confirm the association and to determine healthy implications at a later age.
Topics: Humans; Infant, Newborn; Male; Alkanesulfonates; Alkanesulfonic Acids; Biomarkers; East Asian People; Environmental Pollutants; Ether; Ethers; Fluorocarbons; Sulfonic Acids; Vitamin D
PubMed: 36621489
DOI: 10.1016/j.scitotenv.2023.161410 -
Environmental Research Aug 2023Per- and polyfluoroalkyl substances (PFAS) are ubiquitous, environmentally persistent chemicals, and prenatal exposures have been associated with adverse child health...
BACKGROUND
Per- and polyfluoroalkyl substances (PFAS) are ubiquitous, environmentally persistent chemicals, and prenatal exposures have been associated with adverse child health outcomes. Prenatal PFAS exposure may lead to epigenetic age acceleration (EAA), defined as the discrepancy between an individual's chronologic and epigenetic or biological age.
OBJECTIVES
We estimated associations of maternal serum PFAS concentrations with EAA in umbilical cord blood DNA methylation using linear regression, and a multivariable exposure-response function of the PFAS mixture using Bayesian kernel machine regression.
METHODS
Five PFAS were quantified in maternal serum (median: 27 weeks of gestation) among 577 mother-infant dyads from a prospective cohort. Cord blood DNA methylation data were assessed with the Illumina HumanMethylation450 array. EAA was calculated as the residuals from regressing gestational age on epigenetic age, calculated using a cord-blood specific epigenetic clock. Linear regression tested for associations between each maternal PFAS concentration with EAA. Bayesian kernel machine regression with hierarchical selection estimated an exposure-response function for the PFAS mixture.
RESULTS
In single pollutant models we observed an inverse relationship between perfluorodecanoate (PFDA) and EAA (-0.148 weeks per log-unit increase, 95% CI: -0.283, -0.013). Mixture analysis with hierarchical selection between perfluoroalkyl carboxylates and sulfonates indicated the carboxylates had the highest group posterior inclusion probability (PIP), or relative importance. Within this group, PFDA had the highest conditional PIP. Univariate predictor-response functions indicated PFDA and perfluorononanoate were inversely associated with EAA, while perfluorohexane sulfonate had a positive association with EAA.
CONCLUSIONS
Maternal mid-pregnancy serum concentrations of PFDA were negatively associated with EAA in cord blood, suggesting a pathway by which prenatal PFAS exposures may affect infant development. No significant associations were observed with other PFAS. Mixture models suggested opposite directions of association between perfluoroalkyl sulfonates and carboxylates. Future studies are needed to determine the importance of neonatal EAA for later child health outcomes.
Topics: Infant; Infant, Newborn; Pregnancy; Child; Female; Humans; Fetal Blood; Prenatal Exposure Delayed Effects; Prospective Studies; Bayes Theorem; Environmental Pollutants; Fluorocarbons; Alkanesulfonates; Mothers; Carboxylic Acids; Epigenesis, Genetic; Alkanesulfonic Acids
PubMed: 37224946
DOI: 10.1016/j.envres.2023.116215 -
The Journal of Organic Chemistry May 2022We report a cascaded oxidative sulfonylation of -propargylamine via a three-component coupling reaction using DABCO·(SO) (DABSO). 3-Arylsulfonylquinolines were obtained...
We report a cascaded oxidative sulfonylation of -propargylamine via a three-component coupling reaction using DABCO·(SO) (DABSO). 3-Arylsulfonylquinolines were obtained by mixing diazonium tetrafluoroborate, -propargylamine, and DABSO under argon atmosphere in dichloroethane (DCE) for 1 h. In a radical pathway, DABSO was utilized as the sulfone source and an oxidant in this radical-mediated cascaded reaction.
Topics: Oxidative Stress; Pargyline; Propylamines; Sulfones
PubMed: 35509227
DOI: 10.1021/acs.joc.2c00499 -
The Journal of Organic Chemistry Jan 2022Chabrolobenzoquinone H (), a meroditerpene metabolite with cytotoxic activity, is synthesized via a stereoselective Julia-Kocienski olefination between a chiral pool...
Chabrolobenzoquinone H (), a meroditerpene metabolite with cytotoxic activity, is synthesized via a stereoselective Julia-Kocienski olefination between a chiral pool derived aliphatic PT-sulfone and a benzoquinone aldehyde partner. The latter was obtained via consecutive chain extension steps involving a Stille coupling and a stereospecific olefin cross-metathesis reaction followed by malonic ester synthesis and a Krapcho decarboxylation. Furthermore, this total synthesis securely determined the absolute configuration of the targeted natural product.
Topics: Aldehydes; Alkenes; Biological Products; Stereoisomerism; Sulfones
PubMed: 34936369
DOI: 10.1021/acs.joc.1c02634