Precursor Species Research Articles

Mechanistic Insight into the Precursor Chemistry of ZrO2 and HfO2 Nanocrystals; towards Size-Tunable Syntheses.

One can nowadays readily generate monodisperse colloidal nanocrystals, but a retrosynthetic analysis is still not possible since the underlying chemistry is often poorly understood. Here, we provide insight into the reaction mechanism of colloidal zirconia and hafnia nanocrystals synthesized from metal chloride and metal isopropoxide. We identify the active precursor species in the reaction mixture through a combination of nuclear magnetic resonance spectroscopy (NMR), density functional theory (DFT) calculations, and pair distribution function (PDF) analysis. We gain insight into the interaction of the surfactant, tri-n-octylphosphine oxide (TOPO), and the different precursors. Interestingly, we identify a peculiar X-type ligand redistribution mechanism that can be steered by the relative amount of Lewis base (L-type). We further monitor how the reaction mixture decomposes using solution NMR and gas chromatography, and we find that ZrCl4 is formed as a by-product of the reaction, limiting the reaction yield. The reaction proceeds via two competing mechanisms: E1 elimination (dominating) and SN1 substitution (minor). Using this new mechanistic insight, we adapted the synthesis to optimize the yield and gain control over nanocrystal size. These insights will allow the rational design and synthesis of complex oxide nanocrystals.

Frequent new particle formation at remote sites in the subboreal forest of North America

Abstract. The frequency and intensity of new particle formation (NPF) over remote forest regions in the temperate and boreal zones, and thus the importance of NPF for the aerosol budget and life cycle in the pristine atmosphere, remains controversial. Whereas NPF has been shown to occur relatively frequently at several sites in Scandinavia, it was found to be nearly absent at a mid-continental site in Siberia. To explore this issue further, we made measurements of aerosol size distributions between 10 and 420 nm diameter at two remote sites in the transition region between temperate and boreal forest in British Columbia, Canada. The measurements covered 23 d during the month of June 2019, at the time when NPF typically reaches its seasonal maximum in remote midlatitude regions. These are the first such measurements in a near-pristine region on the North American continent. Although the sites were only 150 km apart, there were clear differences in NPF frequency and intensity between them. At the Eagle Lake site, NPF occurred daily, and nucleation-mode particle concentrations reached above 5000 cm−3. In contrast, at the Nazko River site, there were only six NPF events in 11 d, and the nucleation-mode particle concentrations only reached about 800 cm−3. The reasons for this difference could not be conclusively resolved with the available data; they may include air mass origins, preexisting aerosols, and the density and type of forest cover in the surrounding regions. In contrast to observations in other temperate and boreal environments, we found that NPF at our sites occurred at nighttime just as frequently as during daytime. Together with the lack of identifiable sources of sulfuric acid precursor species in the fetch region of our sites, this suggests that nucleation of extremely low volatility organics was the predominant NPF mechanism. Our results indicate that extended measurement campaigns with a more comprehensive set of instrumentation to investigate the role of NPF in the remote forest regions of North America are essential for a deeper scientific understanding of this important process and its role in the global aerosol budget.

Modelling of laminar diffusion flames with biodiesel blends and soot formation

Modelling of soot formation and oxidation of biodiesel fuels is a challenge, due to the complexity of the chemical reactions and soot formation pathways. In this paper, the discretised population balance approach and a PAH-HACA based detailed soot model have been coupled with an in-house CFD code to simulate a laminar diffusion flame with blends of different components of oxygenated biodiesel fuel, and employed to predict combustion performance and soot formation. The simulation aims to reproduce a target experiment which investigated the effects of dibutyl ether (DBE) addition to the biodiesel surrogate (methyl decanoate, MD) by increasing the mole fraction of DBE from 0 to 40%. A combined and reduced MD–DBE–PAH mechanism developed from three sub-mechanism branches has been employed in the simulation. The simulation results show that temperature rises as the DBE percentage increases to 40%. The swallow-tail shape of the soot occurrence zone and the quantity of soot production are correctly predicted. Regarding the effect of soot suppression, the model has basically captured the reducing tendency of soot formation in the measurements as the DBE addition increases from 0% to 40%. Concentrations of PAHs and C3 species contributing to the formation of aromatic rings are slightly reduced due to the addition of DBE, which is a leading cause of soot suppression. However, on the whole, the numerical solution featured much smaller differences than those observed in the experiment among laminar flames with different MD/DBE ratios, because the combined MD–DBE–PAH mechanism only present a slight difference of concentrations of soot precursor species.

Quantifying the Chemical Desorption of H2S and PH3 from Amorphous Water-ice Surfaces

Abstract Nonthermal desorption of molecules from icy grain surfaces is required to explain molecular line observations in the cold gas of star-forming regions. Chemical desorption is one of the nonthermal desorption processes and is driven by the energy released by chemical reactions. After an exothermic surface reaction, the excess energy is transferred to products’ translational energy in the direction perpendicular to the surface, leading to desorption. The desorption probability of product species, especially that of product species from water-ice surfaces, is not well understood. This uncertainty limits our understanding of the interplay between gas-phase and ice-surface chemistry. In the present work, we constrain the desorption probability of H2S and PH3 per reaction event on porous amorphous solid water (ASW) by numerically simulating previous laboratory experiments. Adopting the microscopic kinetic Monte Carlo method, we find that the desorption probabilities of H2S and PH3 from porous ASW per hydrogen-addition event of the precursor species are 3% ± 1.5% and 4% ± 2%, respectively. These probabilities are consistent with a theoretical model of chemical desorption proposed in the literature if ∼7% of energy released by the reactions is transferred to the translational excitation of the products. As a byproduct, we find that approximately 70% (40%) of adsorption sites for atomic H on porous ASW should have a binding energy lower than ∼300 K (∼200 K). The astrochemical implications of our findings are briefly discussed.

Electron-Stimulated Formation and Release of Molecular Hydrogen and Oxygen from Boehmite Nanoplatelet Films

The production and release of H2 and O2 during and after electron (100–1000 eV) irradiation of boehmite nanoplatelet films was studied. H2 and O2 produced during irradiation likely correspond to electron-induced dissociation of the hydroxyls primarily in the terminal surface layers of the boehmite followed by the H· + H· → H2(g) and O + O → O2(g) combinative desorption reactions as well as the abstraction reactions H· + >OH– → H2(g) + >O·̅. Postirradiation temperature-programmed desorption shows a temperature-dependent release of H2 but no additional release of O2. This process likely involves diffusion and recombination of H· atoms initially trapped between the γ-AlOOH planes followed by recombination at edge and surface sites. H2 production upon thermal-annealing-irradiated material shows no dependence on incident electron flux, suggesting the precursor species (H·) trapped within the bulk are long-lived.

Raman Diagnostics of Cathode Materials for Li-Ion Batteries Using Multi-Wavelength Excitation

Lithium-ion batteries have been commonly employed as power sources in portable devices and are of great interest for large-scale energy storage. To further enhance the fundamental understanding of the electrode structure, we report on the use of multi-wavelength Raman spectroscopy for the detailed characterization of layered cathode materials for Li-ion batteries (LiCoO2, LiNixCo1−xO2, LiNi1/3Mn1/3Co1/3O2). Varying the laser excitation from the UV to the visible (257, 385, 515, 633 nm) reveals wavelength-dependent changes in the vibrational profile and overtone/combination bands, originating from resonance effects in LiCoO2. In mixed oxides, the influence of resonance effects on the vibrational profile is preserved but mitigated by the presence of Ni and/or Mn, highlighting the influence of resonance Raman spectroscopy on electronic structure changes. The use of UV laser excitation (257, 385 nm) is shown to lead to a higher scattering efficiency towards Ni in LiNi1/3Mn1/3Co1/3O2 compared to visible wavelengths, while deep UV excitation at 257 nm allows for the sensitive detection of surface species and/or precursor species reminiscent of the synthesis. Our results demonstrate the potential of multi-wavelength Raman spectroscopy for the detailed characterization of cathode materials for lithium-ion batteries, including phase/impurity identification and quantification, as well as electronic structure analysis.

Effects of Defect on Work Function and Energy Alignment of PbI2: Implications for Solar Cell Applications

Two-dimensional (2D) layered lead iodide (PbI2) is an important precursor and common residual species during the synthesis of lead-halide perovskites. There currently exist some debates and uncertainties about the effect of excess PbI2 on the efficiency and stability of the solar cell with respect to its energy alignment and energetics of defects. Herein, by applying the first-principles calculations, we investigate the energetics, changes of work function and the defective levels associated with the iodine vacancy (VI) and interstitial iodine (II) defects of monolayer PbI2 (ML-PbI2). We find that the PbI2 has a very low formation energy of VI of 0.77 and 0.19 eV for dilute and high concentration, respectively, reflecting coalescence tendency of isolated VI, much lower than that of vacancies in other 2D materials like phosphorene. Similar to VI, a low formation energy of II of 0.65 eV is found, implying a high population of such defects. Both defects generate in-gap defective levels which are mainly due to the unsaturated chemical bonds of p-orbitals of exposed Pb or inserted I. Such rich defective levels allow the VI and II as the reservoir or sinks of electron/hole carriers in PbI2. Our results suggest that the remnant PbI2 in perovskite MAPbI3 (or FAPbI3) would play dual opposite roles in affecting the efficiency of the perovskite: (1) Forming Schottky-type interface with MAPbI3 (or FAPbI3) in which the built-in potential would facilitate the electron-hole separation and prolong the carrier lifetime; (2) Acting as the recombination centers due to the deep defective levels. To promote the efficiency by the Schottky effect, our work reveals that the II defect is favored, and to reduce the recombination centers the VI defect should be suppressed. Our results shall be beneficial in improving strategies for the related optoelectronics applications.

Challenging Conditions for Gasoline Particulate Filters (GPFs)

The emission limit of non-volatile particles (i.e., particles that do not evaporate at 350 °C) with size >23 nm, in combination with the real driving emissions (RDE) regulation in 2017, resulted in the introduction of gasoline particulate filters (GPFs) in all light-duty vehicles with gasoline direct injection engines in Europe. Even though there are studies that have examined the particulate emissions at or beyond the current RDE boundary conditions, there is a lack of studies combining most or all worst cases (i.e., conditions that increase the emissions). In this study, we challenged a fresh (i.e., no accumulation of soot or ash) “advanced” prototype GPF at different temperatures (down to −9 °C), aggressive drive cycles and hard accelerations (beyond the RDE limits), high payload (up to 90%), use of all auxiliaries (air conditioning, heating of the seats and the rear window), and cold starts independently or simultaneously. Under hot engine conditions, the increase of the particulate emissions due to higher payload and lower ambient temperature was 30–90%. The cold start at low ambient temperature, however, had an effect on the emissions of up to a factor of 20 for particles >23 nm or 300 when considering particles <23 nm. We proposed that the reason for these high emissions was the incomplete combustion and the low efficiency of the three-way oxidation catalyst. This resulted in a high concentration of species that were in the gaseous phase at the high temperature of the close-coupled GPF and thus could not be filtered by the GPF. As the exhaust gas cooled down, these precursor species formed particles that could not be evaporated at 350 °C (the temperature of the particle number system). These results highlight the importance of the proper calibration of the engine out emissions at all conditions, even when a GPF is installed.

Evidence of a Tetrahedrally Coordinated RuO4 Surface Complex on RuO2(100): Density Functional Theory and Beyond

RuO2(100), an efficient low-temperature oxidation model catalyst, is able to undergo a c(2 × 2) reconstruction with a so far unknown surface structure that is accompanied by the loss of its catalytic activity. Here, the surface structure of the c(2 × 2) reconstruction of RuO2(100) is predicted by ab initio molecular dynamics simulations and shown to be consistent with available surface science experiments from the literature, including scanning tunneling microscopy (STM) images, low-energy electron diffraction (LEED) intensity versus voltage experiments, and thermal desorption experiments of O2. Mechanistically, the c(2 × 2) reconstruction starts from a simple c(2 × 2) overlayer structure of on-top O on RuO2(100), where the remaining undercoordinated surface Ru centers shift laterally toward the on-top O position, thereby breaking two Ru–O back bonds to lattice oxygen and forming a new Ru–O bond with on-top O. This leads to the formation of a tetrahedrally coordinated surface species Ru4f, a process that is activated by 0.95 eV and that results in an energy stabilization of 0.66 eV. The c(2 × 2) surface structure can readily explain the lack of activity in catalytic CO oxidation. The CO molecule is much more weakly bound on RuO2(100)-c(2 × 2) reconstruction than on the RuO2(110) or the RuO2(100)-(1 × 1) surface, and in addition, the Ru4f centers are too far apart to allow for O2 activation. The identified Ru4f surface species is expected to play a prevailing role as precursor species in the missing thermal and electrochemical stability of RuO2 under oxidizing reaction conditions by forming volatile RuO4.

An Investigation towards Coupling Molecular Dynamics with Computational Fluid Dynamics for Modelling Polymer Pyrolysis

Building polymers implemented into building panels and exterior façades have been determined as the major contributor to severe fire incidents, including the 2017 Grenfell Tower fire incident. To gain a deeper understanding of the pyrolysis process of these polymer composites, this work proposes a multi-scale modelling framework comprising of applying the kinetics parameters and detailed pyrolysis gas volatiles (parent combustion fuel and key precursor species) extracted from Molecular Dynamics models to a macro-scale Computational Fluid Dynamics fire model. The modelling framework was tested for pure and flame-retardant polyethylene systems. Based on the modelling results, the chemical distribution of the fully decomposed chemical compounds was realised for the selected polymers. Subsequently, the identified gas volatiles from solid to gas phases were applied as the parent fuel in the detailed chemical kinetics combustion model for enhanced predictions of toxic gas, charring, and smoke particulate predictions. The results demonstrate the potential application of the developed model in the simulation of different polymer materials without substantial prior knowledge of the thermal degradation properties from costly experiments.

Characteristic of TiO2&Ag0 nanocomposites formed via transformation of metatitanic acid and titanium (IV) isopropoxide

Composite nanoparticles TiO2&Ag0 were synthesized by coprecipitationin a weakly alkaline medium in the presence of various precursors - metatitanic acid and titanium (IV) isopropoxide. Comparative study of TiO2&Ag0 included analysis of morphology (SEM), phase (XRD) and chemical compositions (EDS). The formation of anatase structures was confirmed at a relatively low concentration of silver (0–8 wt% for metatitanic acid and 0–4 wt% for Ti (IV) isopropoxide). An increase in the Ag fraction to 8 wt% led to the appearance of the Ti2O3 and β-TiO2 phases in the Ti(IV) isopropoxide system. The size distribution of primary particles is 8.3–10.6 nm (Ti(IV) isopropoxide system) and 12.3–14.0 nm (metatitanic acid system). The anatase lattice parameters decrease with Ag wt% increasing in Ti(IV) isopropoxide system and do not change for the metatitanic acid system. TG-DTA study showed the effects corresponding to the removal of structural water (210 °C), destruction of isopropoxide and combustion of organic matter (300–410 °C), crystallization of anatase (510 °C) and the anatase transformation into the rutile phase (720–760 °C), but in the presence silver, the anatase structure did not change to 1000 °C. Morphological study shows high crystallinity of both kinds of structures but less aggregative stability composites formed in the metatitanic acid solution. All type nanocomposites include four chemical elements – Ti, Ag, O, and Na as well as a small number of various admixtures - S or Cl and K depending on precursor species. At the same time, a relatively high concentration of argentum in the initial solution led to obtaining chemically pure composite nanoparticlesandcore&shell type structures.

Observations and Explicit Modeling of Summer and Autumn Ozone Formation in Urban Beijing: Identification of Key Precursor Species and Sources

Observations and Explicit Modeling of Summer and Autumn Ozone Formation in Urban Beijing: Identification of Key Precursor Species and Sources

Numerical modelling of non-premixed biogas and LPG combustion to study carbon nanostructures formation in flame

This work presents the numerical simulation of biogas and LPG fuelled diffusion flames in an axisymmetric chamber to study in-depth, the formation mechanism of soot and carbon nanostructures in these flames. The simulation is formulated on the set of transport equations that involve the equations for conservation of mass (the continuity equation), momentum (Navier-Stokes equation), energy, and chemical species. The governing equations are solved using ANSYS FLUENT, which is centered on the finite volume method. To predict the soot formation, one step soot model has been incorporated. The solution of these equations permits the estimation of temperature field and species concentrations inside the flame. Simulation is conducted at fixed fuel flow rate and varied oxygen flow rates. The results reveal that the formation of soot and carbon nanostructures is strongly dependent on peak flame temperature and concentration of precursor species formed in the flame. Since two fuels produce an exclusive chemical environment in the flame, the flame temperature and CO concentration that is conducive to the growth of carbon nanostructures is higher for LPG fuel as compared to that for biogas. Hence, the nucleation process of carbon nanostructures is faster for LPG than biogas. Moreover, the reactions taking place inside the flame at different locations can also be predicted from flame temperature and species concentration at that location. Pyrolysis of fuel occur near the burner exit, followed by the nucleation and surface growth of carbon nanostructures in the nearby region and oxidation of formed carbon nanostructures near the flame tip.

Wafer-Scale Uniform Synthesis of 2D Transition Metal Dichalcogenides Single Crystals via Chemical Vapor Deposition

ConspectusTwo-dimensional (2D) semiconducting transition metal dichalcogenides (TMDCs), most with a formula of MX2 (M = Mo, W; X = S, Se, etc.), have emerged as ultrathin channel materials in next-generation electronics, due to their atomic thickness, tunable bandgap, and relatively high carrier mobility, etc. To propel their practical applications in integrated circuits, large-scale preparation of large-domain MX2 single crystals and single-crystal films is significantly important. Among all the synthetic methods, chemical vapor deposition (CVD) has shown great promise for the controllable syntheses of large-area uniform 2D materials with electronic-grade quality and reasonable cost. So far, intensive efforts have been devoted to the controllable growth of MX2 single crystals with large sizes, controlled thicknesses, fast growth rates, and unidirectional orientations. However, due to the complexity of the precursor species (mostly like solid powders) and their gradient feeding distributions along the gas flow direction, it is still a huge challenge to synthesize large-area MX2 samples with centimeter-scale uniformity, which inevitably hinders their practical applications in industry. More significantly, due to the noncentrosymmetric structures of MX2, antiparallel domains and twin grain boundaries usually evolved on most substrates (e.g., mica, C-sapphire). These defective grain boundaries usually exhibit metallic characteristics and serve as conducting channels, seriously impairing the electrical and optical properties of related devices.This review thereby focuses on the recent progresses on the CVD syntheses of large-scale uniform, large-domain MX2 flakes and single-crystal films, primarily on the single-crystal insulating substrates, amorphous insulating substrates and single-crystal metal substrates. Some promising growth strategies toward improving the thickness uniformity, domain size and crystal quality of MX2 are highlighted, through modulating the key parameters in the CVD processes, such as precursor type, substrate category/crystallinity or growth promoter. The key mechanisms that directing the uniform orientations of individual domains and their merging toward single-crystal films are also highlighted. Besides, the applications of the 2D MX2 in high-performance electronic devices are also discussed. Finally, the current challenges for the wafer-scale syntheses of MX2 single crystals and their applications are prospected. The potential opportunities in this field are also proposed in terms of the wafer-scale production and thickness control of 2D MX2, epitaxial growth of wafer-scale MX2 single-crystals, damage-free, and easy-processing transfer of wafer-scale MX2, as well as the high-performance electronics/optoelectronics based on wafer-scale MX2. We believe this review can provide a basic guidance for the controllable growth of wafer-scale MX2 single crystals, and inspire more researchers to design innovative synthesis routes to promote their practical applications in new-generation electronic devices.

Effects of ambient CO2 and H2O on soot processes in n-dodecane spray combustion using large eddy simulation

In this study, large eddy simulations, coupled a two-equation soot model, are performed to investigate the effects of ambient carbon dioxide (CO2) and water (H2O) additions on the soot formation and oxidation processes in an n-dodecane spray flame. In the soot model, acetylene (C2H2) is soot precursor and surface growth species, while hydroxyl radical (OH) and oxygen (O2) are soot oxidizers. The effect of ambient CO2 and H2O additions on soot formation/oxidation can be separated into thermal and chemical effects. For the thermal effects, the ambient CO2 and H2O additions increase C2H2 but reduce OH formation by lowering the flame temperature. This leads to a higher soot mass formed. On the contrary to the thermal effects, the ambient CO2 and H2O additions reduce the soot formation due to their chemical effects. The reaction CH2∗+CO2↔CH2O+CO is found to be responsible for reducing C2H2 formation. The ambient H2O addition results in a higher OH but lower the C2H2 mass formed owing to the reverse reactions H2+OH↔H2O+H and OH+OH↔H2O+O. Furthermore, the chemical effects is more significant than the thermal effects under the tested conditions. This leads to a lower soot mass formed when adding ambient CO2 and H2O.

New insights into the biomineralization of mercury selenide nanoparticles through stable isotope analysis in giant petrel tissues

Tiemannite (HgSe) is considered the end-product of methylmercury (MeHg) demethylation in vertebrates. The biomineralization of HgSe nanoparticles (NPs) is understood to be an efficient MeHg detoxification mechanism; however, the process has not yet been fully elucidated. In order to contribute to the understanding of complex Hg metabolism and HgSe NPs formation, the Hg isotopic signatures of 40 samples of 11 giant petrels were measured. This seabird species is one of the largest avian scavengers in the Southern Ocean, highly exposed to MeHg through their diet, reaching Hg concentrations in the liver up to more than 900 µg g-1. This work constitutes the first species-specific isotopic measurement (δ202Hg, Δ199Hg) of HgSe NPs in seabirds and the largest characterization of this compound in biota. Similar δ202Hg values specifically associated to HgSe (δ202HgHgSe) and tissues (δ202Hgbulk) dominated by inorganic Hg species were found, suggesting that no isotopic fractionation is induced during the biomineralization step from the precursor (demethylated) species. In contrast, the largest variations between δ202Hgbulk and δ202HgHgSe were observed in muscle and brain tissues. This could be attributed to the higher fraction of Hg present as MeHg in these tissues. Hg-biomolecules screening highlights the importance of the isotopic characterization of these (unknown) complexes.

Relationship of Cultivated Grain Amaranth Species and Wild Relative Accessions.

Amaranthus is a genus of C4 dicotyledonous herbaceous plants, and three New World species have been domesticated to produce grain crops with light colored seed which are classified as pseudo-cereals rich in protein and minerals. A core collection of grain amaranths and immediate precursor species has been established, representing the closest related species. The goal of this study was to evaluate the genetic diversity in that collection of cultivated and wild species, using competitive allele single nucleotide polymorphism markers. A secondary objective was to determine the relationships among the three cultivated species and non-domesticated Amaranthus, while a third objective was to evaluate the utility of the markers in detecting diversity in the 276 genotypes. The markers were found to be highly variable with an average polymorphism information content of 0.365. All markers were bi-allelic; and the major allele frequency ranged from 0.388 to 0.871. Population structure analysis of the cultigens revealed the presence of two sub populations. Phylogeny confirmed that the two Mesoamerican species, Amaranthus cruentus and Amaranthus hypochondriacus, were related and distant from the South American species Amaranthus caudatus, which in turn was very closely clustered with Amaranthus quitensis, even though this is considered a weedy relative. The first pair of species were likely to have inter-crossed, while the latter two likely exist in a wild-cultivated hybrid state. In conclusion, the results of this SNP study provided insights on amaranth cultivars and their relationship to wild species, the probable domestication events leading to the cultivars, and possible crop breeding or germplasm conservation strategies.

Morphological insights associated to instantaneous nucleation and growth in Cr(III) electrodeposition on nickel in aqueous media

In this work, experimental evidence of instantaneous nucleation and growth transients were observed for Cr(0) electrodeposits in aqueous electrolytes, using Cr(III) as precursor species in a double potential step process. This progression occurs via a Cr(II) intermediate, which should be stabilized in aqueous media to afford its proper reduction. This mechanism is rarely observed in aqueous media due to rapid onset of hydrogen evolution and adsorption due to both the acidity and chemical composition of the electrolytic medium employed. Using this approach to prepare a potentiostatically controlled electrodeposit, afforded functional coating on a substrate which is employed for industrial applications (Ni). The morphological features observed from microscopic analysis of the surfaces allowed considering that such instantaneously formed nuclei are important in determining the grain size of the final coating and as such could be controlled in a more significant way with this potentiostatic technique, providing an alternative to the galvanostatic classic approach.

High-Resolution Fluorescence Spectra of Airborne Biogenic Secondary Organic Aerosols: Comparisons to Primary Biological Aerosol Particles and Implications for Single-Particle Measurements.

Aqueous extracts of biogenic secondary organic aerosols (BSOAs) have been found to exhibit fluorescence that may interfere with the laser/light-induced fluorescence (LIF) detection of primary biological aerosol particles (PBAPs). In this study, we quantified the interference of BSOAs to PBAPs by directly measuring airborne BSOA particles, rather than aqueous extracts. BSOAs were generated by the reaction of d-limonene (LIM) or α-pinene (PIN) and ozone (O3) with or without ammonia in a chamber under controlled conditions. With an excitation wavelength of 355 nm, BSOAs exhibited peak emissions at 464–475 nm, while fungal spores exhibited peak emissions at 460–483 nm; the fluorescence intensity of BSOAs with diameters of 0.7 μm was in the same order of magnitude as that of fungal spores with diameters of 3 μm. The number fraction of 0.7 μm BSOAs that exhibited fluorescence above the threshold was in the range of 1.9–15.9%, depending on the species of precursors, relative humidity (RH), and ammonia. Similarly, the number fraction of 3 μm fungal spores that exhibited fluorescence above the threshold was 4.9–36.2%, depending on the species of fungal spores. Normalized fluorescence by particle volumes suggests that BSOAs exhibited fluorescence in the same order of magnitude as pollen and 10–100 times higher than that of fungal spores. A comparison with ambient particles suggests that BSOAs caused significant interference to ambient fine particles (15 of 16 ambient fine particle measurements likely detected BSOAs) and the interference was smaller for ambient coarse particles (4 of 16 ambient coarse particle measurements likely detected BSOAs) when using LIF instruments.

Synthesis of Sodium Alginate-Silver Nanocomposites Using Plasma Activated Water and Cold Atmospheric Plasma Treatment.

In this study, sodium alginate (SA)-based, eco-friendly nanocomposites films were synthesized for potential food packaging applications using silver nitrate (AgNO3) as the metal precursor, reactive nitrogen and oxygen species (RNOS) created within plasma activated water (PAW), or through cold plasma treatment (CP) as reducing agent and SA as stabilizing agent. The formation of silver nanoparticles (AgNPs) was confirmed via the absorption peaks observed between 440 and 450 nm in UV-vis spectroscopy. The tensile strength (TS) and tensile modulus (TM) of the nanocomposite films were significantly higher than those of the SA films. An increase in the TS was also observed as the AgNP concentration was increased from 1 to 5 mM. The storage modulus (G’) of the nanocomposite solution was higher than that of the SA solution. The synthesis of AgNPs resulted both in a higher solution viscosity and a more marked shear-thinning effect. The synthesized AgNPs showed antimicrobial activity against both Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria. The AgNPs were spherical in shape with an average size of 22 nm.