Barrierless HONO and HOS(O)2-NO2 Formation via NH3-Promoted Oxidation of SO2 by NO2.

In the troposphere, the knowledge about nitrous acid (HONO) sources is incomplete. The missing source of sulfate and fine particles cannot be explained during haze events. Air quality models cannot predict high levels of secondary fine-particle pollution. Despite extensive studies, one challenging issue in atmospheric chemistry is identifying the source of HONO. Here, we present direct ab initio molecular dynamics simulation evidence and typical air pollution events of the formation of gaseous HONO, nitrogen dioxide/hydrogen sulfite (HOS(O)2-NO2 or NO2-HSO3) from nitrogen dioxide (NO2), sulfur dioxide (SO2), water (H2O), and ammonia (NH3) molecules in a proportion of 2:1:3:3. The reactions show a new mechanism for the formation of HONO and NO2-HSO3 in the troposphere, especially when the concentration of NO2, SO2, H2O, and NH3 is high (e.g., 2:1:3:3 or higher) in the air. Contrary to the proportion NO2, SO2, H2O, and NH3 equaling to 1:1:3:1 and 1:1:3:2, the proportion (2:1:3:3) enables barrierless reactions and weak interactions between molecules via the formation of HONO, NO2-HSO3, and NH3/H2O. In addition, field observations are carried out, and the measured data are summarized. Correlation analysis supported the conversion of NO2 to HONO during observational studies. The weak interactions promote proton transfer, resulting in the generation of HONO, NO2-HSO3, and NH3/H2O pairs.

Hydroxyl, hydroperoxyl free radicals determination methods in atmosphere and troposphere.

The hydroxyl radical (•OH) has a crucial function in the oxidation and removal of many atmospheric compounds that are harmful to health. Nevertheless, high reactivity, low atmospheric abundance, determination of hydroxyl, and hydroperoxyl radical's quantity is very difficult. In the atmosphere and troposphere, hydroperoxyl radicals (HO2) are closely demanded in the chemical oxidation of the troposphere. But advances in technology have allowed researchers to improve the determination methods on the research of free radicals through some spectroscopic techniques. So far, several methods such as laser-induced fluorescence (LIF), high-performance liquid chromatography (HPLC), and chemical ionization mass spectroscopy have been identified and mostly used in determining the quantity of hydroxyl and hydroperoxyl radicals. In this systematic review, we have advised the use of scavenger as an advance for further researchers to circumvent some of these problems caused by free radicals. The primary goal of this review is to deepen our understanding of the functions of the most critical free radical (•OH, HO2) and also understand the currently used methods to quantify them in the atmosphere and troposphere.

Seasonal variation characteristics of hydroxyl radical pollution and its potential formation mechanism during the daytime in Lanzhou.

Hydroxyl free radicals (OH radicals) play the main role in atmospheric chemistry and their involving reactions are the dominant rate determining step in the formation of secondary fine particulate matter and in the removal of air pollutants from the atmosphere. In this paper, we studied the seasonal variation characteristics of OH radicals during the daytime in Lanzhou and explored the potential formation mechanism of high concentration OH radicals. We found that the OH radicals in four seasons was 2.7 × 106, 2.6 × 106, 3.1 × 106, and 2.2 × 106 cm-3, respectively. Since the rainfall was concentrated in summer, the wet deposition had a significant effect on removing OH radicals. Among the four pollutants (including ozone (O3), volatile organic compounds (VOCs), nitrogen dioxide (NO2) and fine particulate matter (PM2.5)), the variation of OH radicals were closely related to ozone concentration especially in spring and summer. In autumn, the correlation between PM2.5 and OH radicals were the closest among the observing pollutants and its formation mechanism was different conventional regeneration pathway. In Event 1, high concentration of ozone was the main source of OH radicals; under the high humidity condition, except for ozone, the multiple factors including VOCs, NO2 and PM2.5 interplayed and leaded to the Event 2.

Preparation of Electrospun Active Molecular Membrane and Atmospheric Free Radicals Capture.

We load the natural active molecules onto the spin film in an array using electrospinning techniques. The electrospun active molecular membranes we obtain in optimal parameters exhibit excellent capacity for scavenging radical. The reaction capacity of three different membranes for free radicals are shown as follow, glycyrrhizin acid membrane > quercetin membrane > α-mangostin membrane. The prepared active molecular electrospun membranes with a large specific surface area and high porosity could increase the interaction area between active molecules and free radicals. Additionally, it also has improved anti-airflow impact strength, anti-contaminant air molecular interference ability, and the ability to capture free radicals.

Potential factors and mechanism of particulate matters explosive increase induced by free radicals oxidation.

Atmospheric particulate pollution in China has attracted much public attention. Occasionally, the particle number concentration increases sharply in a short time period, which is defined as a "particulate matter explosive increase". Heavy particulate matter pollution not only reduces visibility but also has an adverse effect on human health. Hence, there is an urgent need to discover the causes of particulate matter explosive increase. During this campaign, the particle number concentration and free radicals were measured at a tall building on the campus of Lanzhou University of Technology. Additionally, we examined a series of chemicals to reproduce the observed particulate matter explosive increase in a smog chamber to determine its potential factors. Then, we analyzed the mechanism of particulate matter explosive increase in the presence of free radicals. We found that, among the potential inorganic and organic sources analyzed, a mixture of organic and SO2 in the research region had a major effect on particulate matter explosive increase. Moreover, free radical oxidation has a large effect, especially in the formation of organic particulates.

Detection of peroxyl radicals from polluted air by free radical reaction combined with liquid chromatography signal amplification technique.

Free radicals play an important role in the oxidizing power of polluted air, the development of aging-related diseases, the formation of ozone, and the production of secondary particulate matter. The high variability of peroxyl radical concentration has prevented the detection of possible trends or distributions in the concentration of free radicals. We present a new method, free radical reaction combined with liquid chromatography photodiode array detection, for identifying and quantifying peroxyl radicals in polluted air. Functionalized graphene was used for loading peroxyl radicals and reactive molecules in air sampling system, which can facilitate reaction kinetics (charge transfers) between peroxyl radicals and reaction molecules. Separation was performed with and without a preliminary exposure of the polluted air sample to reactive molecule(s) system. The integral chromatographic peak areas before and after air sampling are used to quantify the atmospheric peroxyl radicals in polluted air. The utility of the new technique was tested with measurements carried out in the field.

Total free radical species and oxidation equivalent in polluted air.

Free radicals are the most important chemical intermediate or agent of the atmosphere and influenced by thousands of reactants. The free radicals determine the oxidizing power of the polluted air. Various gases present in smog or haze are oxidants and induce organ and cellular damage via generation of free radical species. At present, however, the high variability of total free radicals in polluted air has prevented the detection of possible trends or distributions in the concentration of those species. The total free radicals are a kind of contaminants with colorless, tasteless characteristics, and almost imperceptible by human body. Here we present total free radical detection and distribution characteristics, and analyze the effects of total free radicals in polluted air on human health. We find that the total free radical values can be described by not only a linear dependence on ozone at higher temperature period, but also a linear delay dependence on particulate matter at lower temperature period throughout the measurement period. The total free radical species distribution is decrease from west to east in Lanzhou, which closely related to the distribution of the air pollutants. The total free radical oxidation capacity in polluted air roughly matches the effects of tobacco smoke produced by the incomplete combustion of a controlled amount of tobacco in a smoke chamber. A relatively unsophisticated chromatographic fingerprint similarity is used for indicating preliminarily the effect of total free radicals in polluted air on human health.

Functionalized graphene quantum dots loaded with free radicals combined with liquid chromatography and tandem mass spectrometry to screen radical scavenging natural antioxidants from Licorice and Scutellariae.

A novel screening method was developed for the detection and identification of radical scavenging natural antioxidants based on a free radical reaction combined with liquid chromatography with tandem mass spectrometry. Functionalized graphene quantum dots were prepared for loading free radicals in the complex screening system. The detection was performed with and without a preliminary exposure of the samples to specific free radicals on the functionalized graphene quantum dots, which can facilitate charge transfer between free radicals and antioxidants. The difference in chromatographic peak areas was used to identify potential antioxidants. This is a novel approach to simultaneously evaluate the antioxidant power of a component versus a free radical, and to identify it in a vegetal matrix. The structures of the antioxidants in the samples were identified using tandem mass spectrometry and comparison with standards. Fourteen compounds were found to possess potential antioxidant activity, and their free radical scavenging capacities were investigated. The order of scavenging capacity of 14 compounds was compared according to their free radical scavenging rate. 4',5,6,7-Tetrahydroxyflavone (radical scavenging rate: 0.05253 mL mg(-1) s(-1) ) showed the strongest capability for scavenging free radicals.

Highly sensitive and selective dopamine biosensor based on 3,4,9,10-perylene tetracarboxylic acid functionalized graphene sheets/multi-wall carbon nanotubes/ionic liquid composite film modified electrode.

A sensitive and selective electrochemical sensor for determination of dopamine (DA) was fabricated based on 3,4,9,10-perylene tetracarboxylic acid functionalized graphene sheets, multi-wall carbon nanotubes and ionic liquid modified glass carbon electrode and the properties of modified electrode were characterized by scanning electron microscopy, transmission electron microscope and electrochemical impedance spectroscopy. The modified electrode showed excellent electrocatalytic activity toward the oxidation of DA. Meanwhile, a possible reaction mechanism related to the oxidation of DA was proposed. The differential pulse voltammetry was used for the determination of DA in the presence of 500 µM ascorbic acid and 330 µM uric acid under the optimum conditions and a good linear relationship between peak current and the concentration of DA was obtained in the concentration range from 0.03 µM to 3.82 mM with a detection limit of 1.2×10(-9) M (S/N=3). Moreover, the proposed method was successfully applied to determine DA in real sample and satisfactory results were obtained. The results showed that the modified electrode exhibits an excellent catalytic activity, good sensitivity, reproducibility and long-term stability.

A novel and simple strategy for simultaneous determination of dopamine, uric acid and ascorbic acid based on the stacked graphene platelet nanofibers/ionic liquids/chitosan modified electrode.

A promising electrochemical sensor for simultaneous determination of dopamine (DA), uric acid (UA) and ascorbic acid (AA) was fabricated based on the stacked graphene platelet nanofibers (SGNF)/ionic liquid (IL)/chitosan (CS) modified electrode. The SGNF/IL/CS modified electrode possessed excellent electrocatalytic activity towards the oxidation of DA, UA and AA with obvious reduction of over-potential and increased peak current, and the separations of oxidation peak potentials of DA-UA, DA-AA, and UA-AA were of 151, 213 and 364 mV, respectively. Under the optimum conditions, the linear range for the detection of DA, UA and AA were 0.05-240, 0.12-260, and 30-350 µM with the lowest detection limits of 0.05, 0.10 and 14.8 µM for DA, UA and AA, respectively. In addition, the electrochemical sensor showed high sensitivity, excellent selectivity, reproducibility and long-term stability.