scholarly journals Atmospheric protein chemistry influenced by anthropogenic air pollutants: nitration and oligomerization upon exposure to ozone and nitrogen dioxide

2017 ◽  
Vol 200 ◽  
pp. 413-427 ◽  
Author(s):  
Fobang Liu ◽  
Pascale S. J. Lakey ◽  
Thomas Berkemeier ◽  
Haijie Tong ◽  
Anna Theresa Kunert ◽  
...  

The allergenic potential of airborne proteins may be enhanced via post-translational modification induced by air pollutants like ozone (O3) and nitrogen dioxide (NO2). The molecular mechanisms and kinetics of the chemical modifications that enhance the allergenicity of proteins, however, are still not fully understood. Here, protein tyrosine nitration and oligomerization upon simultaneous exposure of O3 and NO2 were studied in coated-wall flow-tube and bulk solution experiments under varying atmospherically relevant conditions (5–200 ppb O3, 5–200 ppb NO2, 45–96% RH), using bovine serum albumin as a model protein. Generally, more tyrosine residues were found to react via the nitration pathway than via the oligomerization pathway. Depending on reaction conditions, oligomer mass fractions and nitration degrees were in the ranges of 2.5–25% and 0.5–7%, respectively. The experimental results were well reproduced by the kinetic multilayer model of aerosol surface and bulk chemistry (KM-SUB). The extent of nitration and oligomerization strongly depends on relative humidity (RH) due to moisture-induced phase transition of proteins, highlighting the importance of cloud processing conditions for accelerated protein chemistry. Dimeric and nitrated species were major products in the liquid phase, while protein oligomerization was observed to a greater extent for the solid and semi-solid phase states of proteins. Our results show that the rate of both processes was sensitive towards ambient ozone concentration, but rather insensitive towards different NO2 levels. An increase of tropospheric ozone concentrations in the Anthropocene may thus promote pro-allergic protein modifications and contribute to the observed increase of allergies over the past decades.

2021 ◽  
Vol 22 (14) ◽  
pp. 7616
Author(s):  
Anna T. Backes ◽  
Kathrin Reinmuth-Selzle ◽  
Anna Lena Leifke ◽  
Kira Ziegler ◽  
Carola S. Krevert ◽  
...  

The allergenic and inflammatory potential of proteins can be enhanced by chemical modification upon exposure to atmospheric or physiological oxidants. The molecular mechanisms and kinetics of such modifications, however, have not yet been fully resolved. We investigated the oligomerization and nitration of the grass pollen allergen Phl p 5 by ozone (O3), nitrogen dioxide (NO2), and peroxynitrite (ONOO–). Within several hours of exposure to atmospherically relevant concentration levels of O3 and NO2, up to 50% of Phl p 5 were converted into protein oligomers, likely by formation of dityrosine cross-links. Assuming that tyrosine residues are the preferential site of nitration, up to 10% of the 12 tyrosine residues per protein monomer were nitrated. For the reaction with peroxynitrite, the largest oligomer mass fractions (up to 50%) were found for equimolar concentrations of peroxynitrite over tyrosine residues. With excess peroxynitrite, the nitration degrees increased up to 40% whereas the oligomer mass fractions decreased to 20%. Our results suggest that protein oligomerization and nitration are competing processes, which is consistent with a two-step mechanism involving a reactive oxygen intermediate (ROI), as observed for other proteins. The modified proteins can promote pro-inflammatory cellular signaling that may contribute to chronic inflammation and allergies in response to air pollution.


2021 ◽  
Vol 22 (7) ◽  
pp. 3463
Author(s):  
Chia-Hung Lin ◽  
Chen-Chung Liao ◽  
Mei-Yu Chen ◽  
Teh-Ying Chou

Protein O-GlcNAcylation is a dynamic post-translational modification involving the attachment of N-acetylglucosamine (GlcNAc) to the hydroxyl groups of Ser/Thr residues on numerous nucleocytoplasmic proteins. Two enzymes are responsible for O-GlcNAc cycling on substrate proteins: O-GlcNAc transferase (OGT) catalyzes the addition while O-GlcNAcase (OGA) helps the removal of GlcNAc. O-GlcNAcylation modifies protein functions; therefore, dysregulation of O-GlcNAcylation affects cell physiology and contributes to pathogenesis. To maintain homeostasis of cellular O-GlcNAcylation, there exists feedback regulation of OGT and OGA expression responding to fluctuations of O-GlcNAc levels; yet, little is known about the molecular mechanisms involved. In this study, we investigated the O-GlcNAc-feedback regulation of OGT and OGA expression in lung cancer cells. Results suggest that, upon alterations in O-GlcNAcylation, the regulation of OGA expression occurs at the mRNA level and likely involves epigenetic mechanisms, while modulation of OGT expression is through translation control. Further analyses revealed that the eukaryotic translation initiation factor 4E-binding protein 1 (4E-BP1) contributes to the downregulation of OGT induced by hyper-O-GlcNAcylation; the S5A/S6A O-GlcNAcylation-site mutant of 4E-BP1 cannot support this regulation, suggesting an important role of O-GlcNAcylation. The results provide additional insight into the molecular mechanisms through which cells may fine-tune intracellular O-GlcNAc levels to maintain homeostasis.


2006 ◽  
Vol 510-511 ◽  
pp. 782-785 ◽  
Author(s):  
Suk Won Kang ◽  
Ki Bae Kim ◽  
Dock Young Lee ◽  
Jung-Hwa Mun ◽  
Eui Pak Yoon

Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2350
Author(s):  
Jianing Zhang ◽  
Fengjie Yu ◽  
Yunmin Tao ◽  
Chunping Du ◽  
Wenchao Yang ◽  
...  

In the present work, a novel sample preparation method, micro salting-out assisted matrix solid-phase dispersion (μ-SOA-MSPD), was developed for the determination of bisphenol A (BPA) and bisphenol B (BPB) contaminants in bee pollen. The proposed method was designed to combine two classical sample preparation methodologies, matrix solid-phase dispersion (MSPD) and homogenous liquid-liquid extraction (HLLE), to simplify and speed-up the preparation process. Parameters of μ-SOA-MSPD were systematically investigated, and results indicated the significant effect of salt and ACN-H2O extractant on the signal response of analytes. In addition, excellent clean-up ability in removing matrix components was observed when primary secondary amine (PSA) sorbent was introduced into the blending operation. The developed method was fully validated, and the limits of detection for BPA and BPB were 20 μg/kg and 30 μg/kg, respectively. Average recoveries and precisions were ranged from 83.03% to 94.64% and 1.76% to 5.45%, respectively. This is the first report on the analysis of bisphenol contaminants in bee pollen sample, and also on the combination of MSPD and HLLE. The present method might provide a new strategy for simple and fast sample preparation of solid and semi-solid samples.


2013 ◽  
Vol 80 (2) ◽  
Author(s):  
Ranena V. Ponce F. ◽  
Márcio A. Murad ◽  
Sidarta A. Lima

We propose a new two-scale model to compute the swelling pressure in colloidal systems with microstructure sensitive to pH changes from an outer bulk fluid in thermodynamic equilibrium with the electrolyte solution in the nanopores. The model is based on establishing the microscopic pore scale governing equations for a biphasic porous medium composed of surface charged macromolecules saturated by the aqueous electrolyte solution containing four monovalent ions (Na+,Cl-,H+,OH-). Ion exchange reactions occur at the surface of the particles leading to a pH-dependent surface charge density, giving rise to a nonlinear Neumann condition for the Poisson–Boltzmann problem for the electric double layer potential. The homogenization procedure, based on formal matched asymptotic expansions, is applied to up-scale the pore-scale model to the macroscale. Modified forms of Terzaghi's effective stress principle and mass balance of the solid phase, including a disjoining stress tensor and electrochemical compressibility, are rigorously derived from the upscaling procedure. New constitutive laws are constructed for these quantities incorporating the pH-dependency. The two-scale model is discretized by the finite element method and applied to numerically simulate a free swelling experiment induced by chemical stimulation of the external bulk solution.


2018 ◽  
Vol 18 (9) ◽  
pp. 6331-6351 ◽  
Author(s):  
Wing-Sy Wong DeRieux ◽  
Ying Li ◽  
Peng Lin ◽  
Julia Laskin ◽  
Alexander Laskin ◽  
...  

Abstract. Secondary organic aerosol (SOA) accounts for a large fraction of submicron particles in the atmosphere. SOA can occur in amorphous solid or semi-solid phase states depending on chemical composition, relative humidity (RH), and temperature. The phase transition between amorphous solid and semi-solid states occurs at the glass transition temperature (Tg). We have recently developed a method to estimate Tg of pure compounds containing carbon, hydrogen, and oxygen atoms (CHO compounds) with molar mass less than 450 g mol−1 based on their molar mass and atomic O : C ratio. In this study, we refine and extend this method for CH and CHO compounds with molar mass up to ∼ 1100 g mol−1 using the number of carbon, hydrogen, and oxygen atoms. We predict viscosity from the Tg-scaled Arrhenius plot of fragility (viscosity vs. Tg∕T) as a function of the fragility parameter D. We compiled D values of organic compounds from the literature and found that D approaches a lower limit of ∼ 10 (±1.7) as the molar mass increases. We estimated the viscosity of α-pinene and isoprene SOA as a function of RH by accounting for the hygroscopic growth of SOA and applying the Gordon–Taylor mixing rule, reproducing previously published experimental measurements very well. Sensitivity studies were conducted to evaluate impacts of Tg, D, the hygroscopicity parameter (κ), and the Gordon–Taylor constant on viscosity predictions. The viscosity of toluene SOA was predicted using the elemental composition obtained by high-resolution mass spectrometry (HRMS), resulting in a good agreement with the measured viscosity. We also estimated the viscosity of biomass burning particles using the chemical composition measured by HRMS with two different ionization techniques: electrospray ionization (ESI) and atmospheric pressure photoionization (APPI). Due to differences in detected organic compounds and signal intensity, predicted viscosities at low RH based on ESI and APPI measurements differ by 2–5 orders of magnitude. Complementary measurements of viscosity and chemical composition are desired to further constrain RH-dependent viscosity in future studies.


PeerJ ◽  
2020 ◽  
Vol 8 ◽  
pp. e9859
Author(s):  
Tingting Song ◽  
Yingyue Shen ◽  
Qunli Jin ◽  
Weilin Feng ◽  
Lijun Fan ◽  
...  

Light plays an important role in the growth and differentiation of Lentinula edodes mycelia, and mycelial morphology is influenced by light wavelengths. The blue light-induced formation of brown film on the vegetative mycelial tissues of L. edodes is an important process. However, the mechanisms of L. edodes’ brown film formation, as induced by blue light, are still unclear. Using a high-resolution liquid chromatography-tandem mass spectrometry integrated with a highly sensitive immune-affinity antibody method, phosphoproteomes of L. edodes mycelia under red- and blue-light conditions were analyzed. A total of 11,224 phosphorylation sites were identified on 2,786 proteins, of which 9,243 sites on 2,579 proteins contained quantitative information. In total, 475 sites were up-regulated and 349 sites were down-regulated in the blue vs red group. To characterize the differentially phosphorylated proteins, systematic bioinformatics analyses, including gene ontology annotations, domain annotations, subcellular localizations, and Kyoto Encyclopedia of Genes and Genomes pathway annotations, were performed. These differentially phosphorylated proteins were correlated with light signal transduction, cell wall degradation, and melanogenesis, suggesting that these processes are involved in the formation of the brown film. Our study provides new insights into the molecular mechanisms of the blue light-induced brown film formation at the post-translational modification level.


Atmosphere ◽  
2021 ◽  
Vol 12 (12) ◽  
pp. 1604
Author(s):  
Tao Zhu ◽  
Furong Li ◽  
Wenfeng Niu ◽  
Zijun Gao ◽  
Yiwei Han ◽  
...  

Monitoring of toxic and hazardous air pollutants (HAPs) in a petrochemical company in the Beijing-Tianjin-Hebei region of China to assess the impact of HAPs on the health risks of workers in the petrochemical company. The samples were tested by solid-phase adsorption thermal desorption/gas chromatography-mass spectrometry (HJ734-2014), and the pollutant emission list was obtained. According to the pollutant emission inventory, it can be seen that benzene, toluene and xylene are the main components of toxic and harmful air pollutants emitted by the petrochemical enterprise. The method of combining actual monitoring and CALPUFF model prediction was used to evaluate the impact of the toxic and harmful air pollutants emitted by the enterprise on the health of workers. The risk characterization results show that when benzene is the maximum concentration value predicted by the model, it will pose a carcinogenic risk to the factory workers. Therefore, based on the results of this study, it is recommended not to allow residents to live within the predicted concentration range of the model. The results of this study can enable China’s oil refining industry to better understand the characteristics of pollutant emissions from petrochemical companies in the Beijing-Tianjin-Hebei region. Moreover, the results of this study can be used as a policy basis for improving the health of workers in petrochemical enterprises, and are of great significance to the protection of public health.


2016 ◽  
Vol 16 (10) ◽  
pp. 6495-6509 ◽  
Author(s):  
Karoliina Ignatius ◽  
Thomas B. Kristensen ◽  
Emma Järvinen ◽  
Leonid Nichman ◽  
Claudia Fuchs ◽  
...  

Abstract. There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate heterogeneous ice nucleation and thus influence cloud properties. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles. The SOA particles were produced from the ozone initiated oxidation of α-pinene in an aerosol chamber at temperatures in the range from −38 to −10 °C at 5–15 % relative humidity with respect to water to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. The ice nucleation ability of SOA particles with different sizes was investigated with a new continuous flow diffusion chamber. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA for ice saturation ratios between 1.3 and 1.4 significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between −39.0 and −37.2 °C ranged from 6 to 20 % and did not depend on the particle surface area. Global modelling of monoterpene SOA particles suggests that viscous biogenic SOA particles are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle budget.


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