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1.
Anal Chem ; 96(16): 6106-6111, 2024 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-38594830

RESUMO

This study explores the innovative field of pulsed direct current arc-induced nanoelectrospray ionization mass spectrometry (DCAI-nano-ESI-MS), which utilizes a low-temperature direct current (DC) arc to induce ESI during MS analyses. By employing a 15 kV output voltage, the DCAI-nano-ESI source effectively identifies various biological molecules, including angiotensin II, bradykinin, cytochrome C, and soybean lecithin, showcasing impressive analyte signals and facilitating multicharge MS in positive- and negative-ion modes. Notably, results show that the oxidation of fatty acids using a DC arc produces [M + O - H]- ions, which aid in identifying the location of C═C bonds in unsaturated fatty acids and distinguishing between isomers based on diagnostic ions observed during collision-induced dissociation tandem MS. This study presents an approach for identifying the sn-1 and sn-2 positions in phosphatidylcholine using phosphatidylcholine and nitrate adduct ions, accurately determining phosphatidylcholine molecular configurations via the Paternò-Büchi reaction. With all the advantages above, DCAI-nano-ESI holds significant promise for future analytical and bioanalytical applications.


Assuntos
Nanotecnologia , Espectrometria de Massas por Ionização por Electrospray , Espectrometria de Massas por Ionização por Electrospray/métodos , Citocromos c/química , Citocromos c/análise , Bradicinina/química , Bradicinina/análise , Angiotensina II/química , Angiotensina II/análise , Fosfatidilcolinas/química , Fosfatidilcolinas/análise , Glycine max/química
2.
Anal Chem ; 96(22): 8886-8892, 2024 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-38771107

RESUMO

Illegal addition of drugs is common but seriously threatens public health safety. Conventional mass spectrometry methods are difficult to realize direct analysis of drugs existing in some complex matrices such as seawater or soil due to the ion suppression effect and contamination to MS parts caused by nonvolatile salts. In this work, a novel crystallization and solvent evaporation ionization mass spectrometry (CSEI-MS) method was constructed and developed to achieve rapid desalting detection. CSEI only consists of a heated plate and a nebulizer and exhibits excellent desalting performance, enabling direct analysis of six drugs dissolved in eight kinds of salt solutions (up to 200 mmol/L) and three complex salty matrices. Under optimized conditions, CSEI-MS presents high sensitivity, accuracy, linearity, and intraday and interday precision. Finally, this method is applied to the quantitative analysis of drugs in seawater, hand cream, and soil. Furthermore, the highly sensitive detection of CSEI-MS is demonstrated to remain even if the detection processes are conducted within 5 s via common commercial tools.


Assuntos
Cristalização , Solventes , Solventes/química , Preparações Farmacêuticas/química , Preparações Farmacêuticas/análise , Água do Mar/química , Água do Mar/análise , Espectrometria de Massas/métodos , Volatilização , Solo/química
3.
Anal Chem ; 96(14): 5664-5668, 2024 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-38530953

RESUMO

Per- and polyfluoroalkyl substances (PFAS) have caused widespread environmental concern in recent years. Among them, the levels of perfluoroalkane sulfonyl fluorides (PFASFs) in the environment have rarely been reported due to the lack of sensitive analytical methods. Herein, a novel liquid chromatography-microwave plasma torch ionization-mass spectrometry (LC-MPTI-MS) technique was designed for the direct analysis of PFASFs in the environment. The collaborative action of reactive oxygen species (such as hydroxyl radicals) and the elevated temperature within the ambient MPTI environment results in the replacement of the fluorine atom in sulfonyl fluoride by oxygen, leading to the detection of perfluoroalkanesulfonic acid (PFSA) ions by MS. Concurrently, LC was employed to separate other PFSAs that are present in the environment. Three PFASFs exhibited good linearity within the range of 1-500 µg/L with R2 > 0.994. The limit of detections (LODs) and the limit of quantifications (LOQs) were measured at 39.32-87.87 and 131.07-292.90 ng/L, respectively. The method was utilized for the direct detection of spiked perfluorooctane sulfonyl fluoride (PFOSF) in wastewater with recoveries of 77.16 to 124.81%. Our approach circumvents the laborious process of chemical derivatization and is anticipated to serve as a robust tool for determining the levels and behaviors of PFASFs in the environment.

4.
Chemistry ; : e202401809, 2024 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-38802327

RESUMO

The abiotic synthesis of peptides, widely regarded as one of the key chemical reactions on the prebiotic Earth, is thermodynamically constrained in solution. Herein, a simulation of the lightning phenomenon on the sea surface using bubble bursting and arc plasma under ambient conditions enables dipeptide formation of six amino acids with conversion ratios ranging from 2.6 % to 25.5 %. Additionally, we observed the formation of biologically active tripeptides and investigated the stereoselectivity of the dipeptide formation reaction. By utilizing a mixture of 20 amino acids in the reaction, 102 possible dipeptides were generated. These results establish experimental constructions to mimic achievable prebiotic conditions and provide a credible pathway for endogenous biopolymer synthesis on prebiotic Earth.

5.
Anal Chem ; 95(36): 13683-13689, 2023 Sep 12.
Artigo em Inglês | MEDLINE | ID: mdl-37624983

RESUMO

Ultratrace organic pollutants in the environment pose severe threats to human health; hence, their accurate detection is essential. In this study, we develop a secondary solvent-free enrichment strategy based on bubbling extraction (BE). Especially, we used BE solid-phase microextraction and BE carbon nanotube paper absorption to capture aerosols from a liquid water surface, desorb analytes, and analyze the analytes using mass spectrometry. The application of a solvent-free enrichment strategy helps overcome technical challenges in implementing BE technology, including reproducibility, quantification, and sensitivity. This approach objectively demonstrates the enrichment efficiency of BE, resulting in improved mass spectrometry response and quantification. It effectively tackles the difficulties in detecting and quantifying ultratrace environmental pollutants in mass spectrometric analysis. The present study successfully conducted a quantitative analysis of 16 polycyclic aromatic hydrocarbons and 7 antibiotics in 48 environmental water samples. This strategy proved effective in detecting the presence and distribution of polar and nonpolar environmental pollutants in rivers and lakes. Moreover, this strategy has several advantages, such as ultrahigh sensitivity at the femtograms per liter level, good greenness, multiplexed quantitation, low sample consumption, and ease of operation. Overall, the utilization of the ultrasensitive and environmentally friendly BE approach presents a reliable and adaptable method for the identification of ultratrace environmental pollutants in water specimens, thereby enabling early monitoring of pollutant levels.

6.
Anal Chem ; 95(45): 16505-16513, 2023 11 14.
Artigo em Inglês | MEDLINE | ID: mdl-37902600

RESUMO

De novo sequencing of oligonucleotides remains challenging, especially for oligonucleotides with post-transcriptional or synthetic modifications. Mass spectrometry (MS) sequencing can reliably detect and locate all of the modification sites in oligonucleotides via m/z variance. However, current MS-based sequencing methods exhibit complex spectra and low ion abundance and usually require coupled instrumentation. Herein, we demonstrate a method of oligonucleotide sequencing using TiO2/ZnAl-layered double oxide (LDO)-assisted laser desorption/ionization (LDI)-MS based on radical-induced dissociation (RID). ·CH2OH radicals can be produced on the surface of a TiO2/ZnAl-LDO matrix via ultraviolet light, inducing an attack on the active site of the oligonucleotide phosphate skeleton to create typical "a-, a-B-, c·-, d-, w-, and y"-type fragments. Compared with the spectra obtained via collision-based methods, such as collision-induced dissociation and higher-energy collisional dissociation, the LDI-MS spectra based on RID exhibit single-charged signals, fewer types of fragments, and a lower proportion of unknown noise peaks. We demonstrate full sequence coverage for a 6-mer 2'-O-methyl-modified oligonucleotide and a 21-mer small interfering RNA and show that RID can sequence oligonucleotides with modifications. Importantly, the mechanism responsible for the RID of the oligonucleotide phosphate skeleton was investigated through offline experiments, demonstrating consistent results with density functional theory calculations.


Assuntos
Oligonucleotídeos , Óxidos , Oligonucleotídeos/química , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/métodos , Fosfatos
7.
Environ Sci Technol ; 57(10): 4180-4186, 2023 03 14.
Artigo em Inglês | MEDLINE | ID: mdl-36848521

RESUMO

Perfluorooctane sulfonyl fluoride (PFOSF) and perfluorohexane sulfonyl fluoride (PFHxSF) were listed as persistent organic pollutants by the Stockholm Convention in 2009 and 2022, respectively. To date, their concentrations in environmental samples have not been reported due to the lack of sensitive methods. Herein, a novel chemical derivatization was developed for quantitative analysis of trace PFOSF and PFHxSF in soil by derivatizing them to the corresponding perfluoroalkane sulfinic acids. The method showed good linearity in the range from 25 to 500 ng L-1 with correlation coefficients (R2) better than 0.99. The detection limit of PFOSF in soil was 0.066 ng g-1 with recoveries in the range of 96-111%. Meanwhile, the detection limit of PFHxSF was 0.072 ng g-1 with recoveries in the range of 72-89%. Simultaneously, perfluorooctane sulfonic acid (PFOS) and perfluorohexane sulfonic acid (PFHxS) were also detected accurately without being affected by the derivative reaction. By applying this method in an abandoned fluorochemical manufacturing facility, PFOSF and PFHxSF were successfully detected at concentrations ranging from 2.7 to 357 ng g-1 and 0.23 to 26 ng g-1 dry weight, respectively. It is very interesting that 2 years after factory relocation, there still exists high concentrations of PFOSF and PFHxSF, which is of concern.


Assuntos
Fluorocarbonos , Ácidos Sulfínicos , Espectrometria de Massas em Tandem/métodos , Solo , Cromatografia Líquida , Fluorocarbonos/análise
8.
J Sep Sci ; 46(23): e2300415, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37802974

RESUMO

Sucrose esters (SEs) are crucial tobacco smoke flavor precursors and play a significant role in tobacco's functionality. Due to their structural complexity, the separation and analysis of SEs in tobacco remain a major challenge, and massive structures of SEs have not yet been fully identified. In this study, the fractions enriched in SEs were obtained from oriental and flue-cured tobacco through a series of pretreatments, and two types of SEs (Types I and II) were distinguished by liquid chromatography-tandem mass spectrometry (LC-MSn ) analysis, with Type II SEs newly characterized in tobacco. Five groups of main SEs were further purified using preparative high-performance LC (HPLC) coupled to an evaporative light scattering detector, and their structures were characterized by nuclear magnetic resonance spectrometry techniques including 1 H, 13 C, correlation spectroscopy, heteronuclear single quantum correlation, and heteronuclear multiple bond correlation. By combining LC-MSn and nuclear magnetic resonance spectrometry, the structures of eight SE isomers were finally proposed, of which four were newly identified. These findings further enhance the understanding of the structural diversity of SEs in tobacco, serving as a valuable reference for future research on the elucidation, synthesis, and metabolism of SEs.


Assuntos
Ésteres , Sacarose , Espectrometria de Massas , Cromatografia Líquida , Isomerismo , Cromatografia Líquida de Alta Pressão/métodos
9.
Altern Ther Health Med ; 29(4): 210-217, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36947655

RESUMO

Context: In recent years, the number of women with unexplained infertility has increased, and clinicians consider poor endometrial receptivity (ER) to be one of the main reasons. ER can have great predictive value for in-vitro fertilization embryo transfer (IVF-ET)-induced pregnancy. Objective: The study intended to investigate the predictive value of ER-endometrial thickness (EMT) and type and hemodynamic parameters-using color-doppler ultrasound on the pregnancy outcome of IVF-ET for women of different ages. Design: The research team performed a prospective controlled study. Setting: The study took place at the Department of Reproductive Medicine at Hebei Reproductive Hospital in Shijiazhuang, China. Participants: Participants were 841 infertile patients undergoing IVF-ET treatment at the hospital between March 01, 2018 and December 30, 2018. The research team divided participants into two groups: (1) participants diagnosed as having a clinical pregnancy after IVF-ET became the pregnancy group, with 439 participants, and (2) participants who didn't become pregnant became the nonpregnancy group, with 402 participants. Outcome Measures: The research team: (1) measured EMT, (2) determined endometrium types, (3) classified the intimal and subintimal blood flow, and (4) determined the hemodynamic parameters of the endometrium and subendometrium. The team also measured: (1) the systolic blood flow velocity (VS), (2) diastolic blood flow velocity (VD), and (3) average blood flow velocity (VM) three times and recorded the average value. Results: Statistically significant differences existed in the pregnancy and implantation rates among the different age groups for the groups with EMTs of <8 mm and 8-13 mm (P < .05). The results were similar in the endometrial Type A and endometrial Type B groups as well as between the endometrial blood flow Type 1 and Type 2 groups (P < .05). The distribution of endometrial blood flow types was significantly different between the groups (P = .002). In addition, statistically significant differences existed in the implantation rates between the <30 years and 30-34 groups in different blood-flow-type groups (P < .05). Based on the results of the ROC curve, high-quality embryos (0.566, 95%CI: 0.527-0.605) and endometrial blood flow types (0.554, 95%CI: 0.515-0.593) could not predict clinical pregnancy. Conclusions: The pregnancy and implantation rates increased between the <30 and 30-34 age groups and them decreased between the age groups as age increased. EMT, endometrial type, and blood flow type can be valuable parameters in predicting the implantation and pregnancy rates of patients of different ages.


Assuntos
Infertilidade Feminina , Resultado da Gravidez , Gravidez , Humanos , Feminino , Fertilização in vitro/métodos , Estudos Prospectivos , Transferência Embrionária , Endométrio/diagnóstico por imagem , Endométrio/irrigação sanguínea , Endométrio/fisiologia , Taxa de Gravidez , Infertilidade Feminina/terapia , Fertilização
10.
Anal Chem ; 94(43): 15002-15009, 2022 11 01.
Artigo em Inglês | MEDLINE | ID: mdl-36255385

RESUMO

In mass spectrometry (MS), nonvolatile salts contaminate the transmission system and cause ion suppression, hampering MS analysis. When MS is combined with liquid chromatography (LC) that uses a salty mobile phase, the problems become more intractable due to long analysis time. Here, a novel heat-assisted dual neutral spray ionization (HADSI) method was developed, which projected sample solution spray and solvent spray onto a heated plate to achieve online desalting and high ionization. The experimental parameters of HADSI were optimized, which indicated that the plate temperature was crucial for ionization and desalination. Eight drug compounds dissolved in various commonly used buffers were directly analyzed using HADSI-MS, even though the concentration of PBS buffer reached 500 mmol/L. The established method showed considerable sensitivity in the positive ion mode with the limits of detection at the level of nmol/L, and good linearity (R2 > 0.99) was achieved for all the analyzed compounds. The repeatability and intra- and interday precisions of the method were evaluated, demonstrating the feasibility and reliability of the analysis of salty samples by HADSI-MS. Further, the method was demonstrated to tolerate the long-time analysis of high-salt LC eluates and the device was easy to maintain. Finally, a crude roxithromycin product was separated by LC and then analyzed by HADSI-MS, and seven unknown impurities and nine known impurities were successfully detected. Our results indicated that HADSI-MS may have potential applications in academic and industrial fields.


Assuntos
Temperatura Alta , Espectrometria de Massas por Ionização por Electrospray , Espectrometria de Massas por Ionização por Electrospray/métodos , Reprodutibilidade dos Testes , Cromatografia Líquida/métodos , Cromatografia Líquida de Alta Pressão
11.
Anal Chem ; 2022 Dec 23.
Artigo em Inglês | MEDLINE | ID: mdl-36562720

RESUMO

The atmospheric oxidation of chemicals has produced many new unpredicted pollutants. A microwave plasma torch-based ion/molecular reactor (MPTIR) interfacing an online mass spectrometer has been developed for creating and monitoring rapid oxidation reactions. Oxygen in the air is activated by the plasma into highly reactive oxygen radicals, thereby achieving oxidation of thioethers, alcohols, and various environmental pollutants on a millisecond scale without the addition of external oxidants or catalysts (6 orders of magnitude faster than bulk). The direct and real-time oxidation products of polycyclic aromatic hydrocarbons and p-phenylenediamines from the MPTIR match those of the long-term multistep environmental oxidative process. Meanwhile, two unreported environmental compounds were identified with an MPTIR and measured in the actual water samples, which demonstrates the considerable significance of the proposed device for both predicting the environmental pollutants (non-target screening) and studying the mechanism of atmospheric oxidative processes.

12.
Analyst ; 146(18): 5682-5690, 2021 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-34397059

RESUMO

A novel, convenient ambient electric arc ionization (AEAI) device was developed as a mass spectrometry ion source for versatile sample analysis. AEAI could be considered as a soft ionization technique in which the protonated ion ([M + H]+) is the main ion species with little or no in-source fragmentation for most analytes. Coupled with a high-resolution Orbitrap mass spectrometer, AEAI could be applied to the analysis of a variety of organic compounds having a wide range of polarities, ranging from non-polar species such as polybenzenoid aromatic hydrocarbons (PAHs) to highly polar species such as amino acids. With its versatile capabilities in the mass spectrometric analysis of small molecules, AEAI has the potential to be an alternative to traditional ionization methods such as electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and electron impact (EI) ionization. The limitations of AEAI are also discussed.


Assuntos
Pressão Atmosférica , Compostos Orgânicos , Aminoácidos , Espectrometria de Massas , Espectrometria de Massas por Ionização por Electrospray
13.
Environ Sci Technol ; 54(22): 14514-14524, 2020 11 17.
Artigo em Inglês | MEDLINE | ID: mdl-33111528

RESUMO

The potential estrogenic activities of perfluoroalkyl substances (PFASs) are controversial. Here, we investigated the estrogenic/antiestrogenic activities of PFASs and explored the corresponding interaction mode of PFASs with the estrogen receptor (ER) by combining in vitro assays and in silico modeling. We found that three PFASs (perfluorobutanoic acid, perfluorobutane sulfonate, and perfluoropentanoic acid) exerted antiestrogenic effects by inhibiting luciferase activity, whereas perfluorohexane sulfonate (PFHxS) and perfluorooctane sulfonate (PFOS) exerted estrogenic effects by inducing luciferase activity. When coexposed to 17ß-estradiol (E2), all tested PFASs attenuated the E2-stimulated luciferase activity; unexpectedly, each PFAS could further attenuate the luciferase activity generated by the cotreatment with ICI 182,780 and E2, with a minimal effective concentration comparable to that found in human serum. PFHxS and PFOS significantly induced the gene expression of TFF1; additionally, all PFASs inhibited the E2-induced gene expression of TFF1 and EGR3. Furthermore, the results of the blind docking analyses suggested that the interaction with the coactivator-binding region on the ER surface should be included as a pathway through which PFASs exert estrogenic and antiestrogenic activities. Finally, we revealed the critical molecular property of the zero-order molecular connectivity index (MCI) (0χ) that affects the antiestrogenic activity of PFASs.


Assuntos
Ácidos Alcanossulfônicos , Fluorocarbonos , Alcanossulfonatos , Ácidos Alcanossulfônicos/toxicidade , Simulação por Computador , Antagonistas de Estrogênios , Fluorocarbonos/toxicidade , Humanos , Receptores de Estrogênio/genética
14.
J Pharmacol Sci ; 143(2): 74-82, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32192854

RESUMO

BACKGROUND: Circular RNAs (circRNAs) play an important role in the tumorigenesis of glioma. Our study indicated that low hsa_circ_0008225 expression was associated with poor overall survival in patients with glioma. However, the relevant mechanism of hsa_circ_0008225 in glioma tumorigenesis remains unclear. METHODS: Two datasets (GSE86202 and GSE92322) were downloaded from the Gene Expression Omnibus (GEO) database. The differentially expressed circRNAs (DEcircRNAs) between glioma tissues and matched normal tissues were screened using R language. RESULTS: A total of 79 overlapping DEcircRNAs were identified by comparison of glioma and matched normal tissues. In addition, low hsa_circ_0008225 expression was associated with poor overall survival in patients with glioma. Overexpression of hsa_circ_0008225 markedly inhibited the proliferation, migration and invasion of SHG44 cells via inducing apoptosis. Mechanically, overexpression of hsa_circ_0008225 increased the expression of miR-890 targeted gene ZMYND11 via acting as a competitive 'sponge' of miR-890. CONCLUSION: Our results suggested that hsa_circ_0008225 functions as a tumor inhibitor in glioma by sponging miR-890 and then promoting the function of ZMYND11. Therefore, hsa_circ_0008225 could be a potential prognostic biomarker for the treatment of glioma.


Assuntos
Carcinogênese/genética , Proteínas de Ciclo Celular/genética , Proteínas de Ciclo Celular/metabolismo , Transformação Celular Neoplásica/genética , Proteínas Correpressoras/genética , Proteínas Correpressoras/metabolismo , Proteínas de Ligação a DNA/genética , Proteínas de Ligação a DNA/metabolismo , Glioma/genética , Glioma/patologia , MicroRNAs , RNA Circular/fisiologia , Apoptose/genética , Movimento Celular/genética , Expressão Gênica , Glioma/mortalidade , Humanos , Invasividade Neoplásica/genética , RNA Circular/genética , Taxa de Sobrevida , Células Tumorais Cultivadas
15.
Ecotoxicol Environ Saf ; 181: 404-411, 2019 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-31220780

RESUMO

Disinfection byproducts (DBPs) are generated by disinfectants reacting with organic matters. Previous studies have focused on DBPs in drinking water, but they have not paid sufficient attention to DBPs in sewage treatment plants (STPs), where the sources and compositions of DBPs are much more complicated, and there is a likelihood of more toxic DBPs being formed. In this study, the occurrence of DBPs in six STPs in Hong Kong and the potential impact of the effluents from the STPs on the marine environment were investigated. In STPs, the mean concentrations of the total DBPs ranged from 1160 to 17,019 ng/L, 1562 to 20,795 ng/L, and 289 to 1037 ng/L in the influent, effluent, and seawater, respectively. Trihalomethanes, haloacetonitriles, and trihalophenols were the most commonly detected DBPs, whereas hexachloro-1,3-butadiene and halocarbazoles were not detected in the STPs and in the marine environment in Hong Kong. Secondary treatment efficiently removed DBPs and DBP precursors. Regarding disinfection techniques, UV irradiation showed little effect on the concentrations of DBPs, whereas sodium hypochlorite significantly elevated the levels of both traditional and emerging DBPs. The effluents from two selected STPs that use chlorination have an obvious impact on the marine environment. This work presents the potential sources of DBPs in sewage, the influence of the treatment processes and disinfection techniques employed in STPs on the removal/formation of DBPs, and the impact of the effluents from the STPs on the marine environment. This work also highlights the need for investigating the emerging DBPs generated in STPs and their related environmental concerns.


Assuntos
Desinfetantes/análise , Água do Mar/química , Esgotos/química , Poluentes Químicos da Água/análise , Desinfecção , Halogenação , Hong Kong , Hipoclorito de Sódio , Raios Ultravioleta , Purificação da Água
16.
Ecotoxicol Environ Saf ; 171: 647-656, 2019 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-30658300

RESUMO

Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have been reported to cause adverse health effects on wildlife as well as humans. Numerous studies demonstrated that PFOA and PFOS could interfere with the transcriptional activation of estrogen receptor α (ERα) by mimicking the function of endogenous ligand, whereas some reports suggested that the two compounds present non-estrogenic activities. These conflicting results bring a confusion to understand their molecular mechanism on the ERα-mediated signaling pathway. To address this issue, we performed the molecular docking and molecular dynamics simulations to elaborate the structural characteristics for the binding of PFOA and PFOS to ERα. Our results indicated that the two opposite binding orientations were modulated by the protonation states of key residue His524. In sub-acidic condition, PFOA and PFOS prefer to form the H-bonding interactions with the protonated His524, whereas Arg394 provided the H-bonding interactions for stable binding in sub-alkaline condition. Conformational analyses implied that the diverse binding modes were closely related to the conformational propensity of ERα for subsequent coactivator recruitment and transcription activation. Generally, our findings provide a flexible strategy to assess the pH impacts of microenvironment on the toxicities of perfluoroalkyl acids by their interactions with proteins.


Assuntos
Ácidos Alcanossulfônicos/metabolismo , Caprilatos/metabolismo , Simulação por Computador , Receptor alfa de Estrogênio/metabolismo , Fluorocarbonos/metabolismo , Humanos , Simulação de Acoplamento Molecular , Conformação Proteica , Transdução de Sinais
17.
Environ Sci Technol ; 52(24): 14228-14234, 2018 12 18.
Artigo em Inglês | MEDLINE | ID: mdl-30444355

RESUMO

Soil organic matter (SOM) is ubiquitous in the environment. Intensive efforts have been made to find effective ways to assess the interaction of SOM with contaminants since such interactions are one of the important criteria used to evaluate the migration, persistency and bioavailability of chemicals in the environment. This study aims to extend the application of coarse-grained (CG) dissipative particle dynamics (DPD) to the water/SOM system and predict contaminant mobility in the system. The CG model was based on the Vienna Soil-Organic-Matter Modeler, which can generate flexible condensed-phase models of SOM. A series of DPD simulations was performed to investigate the mobility of perfluorinated sulfonic acids (PFSAs) and hexachlorobutadiene (HCBD). The results indicated that the mobility of PFSAs decreased with increasing length in the carbon chain. In addition, HCBD and hexachlorobenzene (HCB) have similar diffusion coefficients, indicating analogous behavior in SOM. Moreover, water-containing SOM layers may reflect a more realistic situation. This work, coupling the CG method with DPD simulation, provides a new high-efficiency tool to assess the behavior of contaminants in the environment.


Assuntos
Poluentes do Solo , Solo , Carbono , Hexaclorobenzeno , Água
18.
J Am Soc Mass Spectrom ; 35(2): 178-184, 2024 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-38165091

RESUMO

The present study investigates the gas-phase alcoholysis reaction of benzylic halides under atmospheric pressure chemical ionization (APCI) conditions. The APCI corona discharge is used to initiate the novel reaction, which is monitored by ion trap mass spectrometry (IT-MS). The model compound α,α,α-trifluorotoluene is applied to observe the cascade methoxylation reaction during the +APCI-MS analysis, resulting in the formation of [PhC(OCH3)2]+. Based on the results of isotopic labeling and substrate expansion experiments, an addition-elimination mechanism is proposed: initially, the reaction was initiated by the dissociation of fluorine from PhCF3 under APCI condition, leading to the formation of [PhCF2]+; subsequently, two methanol molecules nucleophilicly attack [PhCF2]+ stepwisely, accompanied by the elimination of HF, yielding the product ion [PhC(OCH3)2]+. The proposed mechanism was further corroborated by theoretical calculations. The results of substrate scope expansion experiments suggest that this in-source reaction has the potential to differentiate the positional isomers of alcohols and phenols.

19.
ChemistryOpen ; : e202400013, 2024 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-38873881

RESUMO

Cigarette smoke contains a large number of chemicals, including both flavor components and harmful substances. The mainstream smoke (MSS) generated by smoking is directly inhaled by individuals, making it crucial to establish an effective method for smoke detection and analysis. One promising technique for analyzing smoke is MPT-MS (Microwave plasma torch mass spectrometry). This approach offers several advantages in accurately detecting the composition of cigarette smoke. By combining MPT-MS with a smoke pumping device, we can achieve real-time online detection of smoke components. We successfully detected 22 flavor compounds present in the smoke. These compounds contribute to the distinct taste of cigarettes. Moreover, we identified 2 polycyclic aromatic hydrocarbons (PAHs) in the smoke. PAHs are known carcinogens and are of great concern in terms of their potential health risks. The successful detection and identification of flavor compounds and PAHs using our method confirm the online detection capability of MPT-MS. This approach provides an efficient and reliable means for analyzing the complex composition of cigarette smoke. By utilizing MPT-MS, we can gain valuable insights into the chemical composition of cigarette smoke and can inform the development of strategies and policies aimed at reducing the harmful effects of smoking and protecting public health.

20.
J Am Soc Mass Spectrom ; 35(5): 951-959, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38597607

RESUMO

C-H bond ortho-substitution reaction has always been a significant and challenging topic in organic chemistry. We proposed a synthesis method based on microwave plasma torches. High-resolution mass spectrometry was used to monitor rapid reaction products. 2-Alkylbenzimidazole can be formed through the reaction of phenylnitrenium ion and nitriles on a millisecond scale. This reaction can achieve the one-step formation of benzimidazoles from benzene ring single-substituted compounds without the addition of external oxidants or catalysts. A similar C-H bond activation reaction can be accomplished with ketones. Meanwhile, the microwave plasma reactor was modified, and the resulting 2-methylbenzimidazole was successfully collected, indicating the device has good application potential in organic reactions such as C-H bond activation reaction.

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