Reactive polycyclic aromatic hydrocarbon dimerization drives soot nucleation.

Nucleation is an important, yet poorly understood step in soot formation. Here, the importance of reactive PAH dimerization in reducing soot nucleation reversibility is investigated by simulating soot formation in a so-called "nucleation" flame (P. Desgroux et al., Combust. Flame, 2017, 184, 153-166). There, inception of soot particles is prolonged at minimal subsequent growth. With only reversible PAH dimerization, the simulated soot concentration is negligible. Accounting however for PAH chemical bond formation after physical dimerization, stabilizes dimers by covalent bonds and increases the soot concentration by four orders of magnitude, in good agreement with Laser Induced Incandescence measurements. In particular, dimers of benzene with benzene, phenylacetylene, naphthalene, toluene, acenaphthylene and cyclopentapyrene make significant contributions to the total soot concentration. The abundance of dimers with small PAHs highlights the dominant role of PAH concentration over their size and dispersion forces on dimer formation. Higher collision factors are used for irreversible dimerization models using larger PAHs because of their lower concentrations and not their larger dispersion forces leading to reduced reversibility and more stable dimers. The qualitative trend of main peaks agrees well with stochastic simulations and aerosol mass spectra measured in the above "nucleation" as well as premixed flames highlighting the abundance of PAHs with five-membered rings and substituted aliphatic chains in incipient soot. The predicted number of trimers is very low, i.e. less than 3% of the total soot nuclei formed, indicating that covalently bonded PAH dimers can be the main contributors to soot nucleation.

Correction: Reactive polycyclic aromatic hydrocarbon dimerization drives soot nucleation.

Correction for 'Reactive polycyclic aromatic hydrocarbon dimerization drives soot nucleation' by M. R. Kholghy et al., Phys. Chem. Chem. Phys., 2018, 20, 10926-10938.

Noninvasive Body Fat Burn Monitoring from Exhaled Acetone with Si-doped WO3-sensing Nanoparticles.

Obesity is a global health threat on the rise, and its prevalence continues to grow. Yet suitable biomedical sensors to monitor body fat burn rates in situ, to guide physical activity or dietary interventions toward efficient weight loss, are missing. Here, we introduce a compact and inexpensive breath acetone sensor based on Si-doped WO3 nanoparticles that can accurately follow body fat burn rates in real time. We tested this sensor on 20 volunteers during exercise and rest and measured their individual breath acetone concentrations in good agreement with benchtop proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS). During exercise, this sensor reveals clearly the onset and progression of increasing breath acetone levels that indicate intensified body fat metabolism, as validated by parallel venous blood ß-hydroxybutyrate (BOHB) measurements. Most importantly, we found that the body fat metabolism was especially pronounced for most volunteers during fasting for 3 h after exercise, with strong variation between subjects, and this was displayed correctly by the sensor in real-time. As a result, this simple breath acetone sensor enables easily applicable and hand-held body fat burn monitoring for personalized and immediate feedback on workout effectiveness that can guide dieting as well.

Coagulation of Agglomerates Consisting of Polydisperse Primary Particles.

The ballistic agglomeration of polydisperse particles is investigated by an event-driven (ED) method and compared to the coagulation of spherical particles and agglomerates consisting of monodisperse primary particles (PPs). It is shown for the first time to our knowledge that increasing the width or polydispersity of the PP size distribution initially accelerates the coagulation rate of their agglomerates but delays the attainment of their asymptotic fractal-like structure and self-preserving size distribution (SPSD) without altering them, provided that sufficiently large numbers of PPs are employed. For example, the standard asymptotic mass fractal dimension, Df, of 1.91 is attained when clusters are formed containing, on average, about 15 monodisperse PPs, consistent with fractal theory and the literature. In contrast, when polydisperse PPs with a geometric standard deviation of 3 are employed, about 500 PPs are needed to attain that Df. Even though the same asymptotic Df and mass-mobility exponent, Dfm, are attained regardless of PP polydispersity, the asymptotic prefactors or lacunarities of Df and Dfm increase with PP polydispersity. For monodisperse PPs, the average agglomerate radius of gyration, rg, becomes larger than the mobility radius, rm, when agglomerates consist of more than 15 PPs. Increasing PP polydispersity increases that number of PPs similarly to the above for the attainment of the asymptotic Df or Dfm. The agglomeration kinetics are quantified by the overall collision frequency function. When the SPSD is attained, the collision frequency is independent of PP polydispersity. Accounting for the SPSD polydispersity in the overall agglomerate collision frequency is in good agreement with that frequency from detailed ED simulations once the SPSD is reached. Most importantly, the coagulation of agglomerates is described well by a monodisperse model for agglomerate and PP sizes, whereas the detailed agglomerate size distribution can be obtained by scaling the average agglomerate size to the SPSD.

Rapid synthesis of flexible conductive polymer nanocomposite films.

Polymer nanocomposite films with nanoparticle-specific properties are sought out in novel functional materials and miniaturized devices for electronic and biomedical applications. Sensors, capacitors, actuators, displays, circuit boards, solar cells, electromagnetic shields and medical electrodes rely on flexible, electrically conductive layers or films. Scalable synthesis of such nanocomposite films, however, remains a challenge. Here, flame aerosol deposition of metallic nanosliver onto bare or polymer-coated glass substrates followed by polymer spin-coating on them leads to rapid synthesis of flexible, free-standing, electrically conductive nanocomposite films. Their electrical conductivity is determined during their preparation and depends on substrate composition and nanosilver deposition duration. Accordingly, thin (<500 nm) and flexible nanocomposite films are made having conductivity equivalent to metals (e.g. 5  × 10(4) S cm(-1)), even during repetitive bending.

Design of Aerosol Particle Coating: Thickness, Texture and Efficiency.

Core-shell particles preserve the performance (e.g. magnetic, plasmonic or opacifying) of a core material while modifying its surface with a shell that facilitates (e.g. by blocking its reactivity) their incorporation into a host liquid or polymer matrix. Here coating of titania (core) aerosol particles with thin silica shells (films or layers) is investigated at non-isothermal conditions by a trimodal aerosol dynamics model, accounting for SiO2 generation by gas phase and surface oxidation of hexamethyldisiloxane (HMDSO) vapor, coagulation and sintering. After TiO2 particles have reached their final primary particle size (e.g. upon completion of sintering during their flame synthesis), coating starts by uniformly mixing them with HMDSO vapor that is oxidized either in the gas phase or on the particles' surface resulting in SiO2 aerosols or deposits, respectively. Sintering of SiO2 deposited onto the core TiO2 particles takes place transforming rough into smooth coating shells depending on process conditions. The core-shell characteristics (thickness, texture and efficiency) are calculated for two limiting cases of coating shells: perfectly smooth (e.g. hermetic) and fractal-like. At constant TiO2 core particle production rate, the influence of coating weight fraction, surface oxidation and core particle size on coating shell characteristics is investigated and compared to pertinent experimental data through coating diagrams. With an optimal temperature profile for complete precursor conversion, the TiO2 aerosol and SiO2-precursor (HMDSO) vapor concentrations have the strongest influence on product coating shell characteristics.

Development and optimization of iron- and zinc-containing nanostructured powders for nutritional applications.

Reducing the size of low-solubility iron (Fe)-containing compounds to nanoscale has the potential to improve their bioavailability. Because Fe and zinc (Zn) deficiencies often coexist in populations, combined Fe/Zn-containing nanostructured compounds may be useful for nutritional applications. Such compounds are developed here and their solubility in dilute acid, a reliable indicator of iron bioavailability in humans, and sensory qualities in sensitive food matrices are investigated. Phosphates and oxides of Fe and atomically mixed Fe/Zn-containing (primarily ZnFe2O4) nanostructured powders were produced by flame spray pyrolysis (FSP). Chemical composition and surface area were systematically controlled by varying precursor concentration and feed rate during powder synthesis to increase solubility to the level of ferrous sulfate at maximum Fe and Zn content. Solubility of the nanostructured compounds was dependent on their particle size and crystallinity. The new nanostructured powders produced minimal color changes when added to dairy products containing chocolate or fruit compared to the changes produced when ferrous sulfate or ferrous fumarate were added to these foods. Flame-made Fe- and Fe/Zn-containing nanostructured powders have solubilities comparable to ferrous and Zn sulfate but may produce fewer color changes when added to difficult-to-fortify foods. Thus, these powders are promising for food fortification and other nutritional applications.

Highly selective detection of methanol over ethanol by a handheld gas sensor.

Methanol poisoning causes blindness, organ failure or even death when recognized too late. Currently, there is no methanol detector for quick diagnosis by breath analysis or for screening of laced beverages. Typically, chemical sensors cannot distinguish methanol from the much higher ethanol background. Here, we present an inexpensive and handheld sensor for highly selective methanol detection. It consists of a separation column (Tenax) separating methanol from interferants like ethanol, acetone or hydrogen, as in gas chromatography, and a chemoresistive gas sensor (Pd-doped SnO2 nanoparticles) to quantify the methanol concentration. This way, methanol is measured within 2 min from 1 to 1000 ppm without interference of much higher ethanol levels (up to 62,000 ppm). As a proof-of-concept, we reliably measure methanol concentrations in spiked breath samples and liquor. This could enable the realization of highly selective sensors in emerging applications such as breath analysis or air quality monitoring.

Selective sensing of isoprene by Ti-doped ZnO for breath diagnostics.

Exhaled isoprene could enable non-invasive monitoring of cholesterol-lowering therapies. Here, we report an isoprene-selective sensor at high relative humidity (RH) for the first time (to our knowledge). It is made of nanostructured, chemo-resistive Ti-doped ZnO particles (10-20 nm crystal size) produced by flame spray pyrolysis (FSP) and directly deposited in one step onto compact sensor substrates forming highly porous films. The constituent particles consist of stable Ti-doped ZnO solid solutions for Ti levels up to 10 mol% apparently by substitutional incorporation of Ti4+ into the ZnO wurtzite lattice and dominant presence at the particle surface. These Ti4+ point defects strongly enhance the isoprene sensitivity (>15 times higher than pure ZnO) and turn ZnO isoprene-selective, while also improving its thermal stability. In situ infrared spectroscopy confirms that Ti4+ intensifies the surface interaction of Ti-doped ZnO with isoprene by providing additional sites for chemisorbed hydroxyl species. In fact, at an optimal Ti content of 2.5 mol%, this sensor shows superior isoprene responses compared to acetone, NH3 and ethanol at 90% RH. Most notably, breath-relevant isoprene concentrations can be detected accurately down to 5 ppb with high (>10) signal-to-noise ratio. As a result, an inexpensive isoprene detector has been developed that could be easily incorporated into a portable breath analyzer for non-invasive monitoring of metabolic disorders (e.g. cholesterol).

Perfluorocarbon compound aerosols for delivery to the lung as potential 19F magnetic resonance reporters of regional pulmonary pO2.

RATIONALE AND OBJECTIVES: Perfluorocarbon (PFC) aerosols present the opportunity for simultaneous analysis of lung structure and pulmonary oxygenation patterns. The authors investigated techniques to nebulize neat liquid PFCs for inhalation as a new method of PFC administration and tested the hypothesis that PFC aerosols may be developed for efficient delivery to the lung in an experimental rat model allowing the potential for sequential monitoring of pulmonary status via quantitative fluorine-19 (19F) magnetic resonance (MR) partial pressure of oxygen (pO2) imaging. METHODS: Pneumatic aerosol generators were configured to produce a neat liquid PFC perfluorotributylamine (FC-43) aerosol. Perfluorocarbon inhalation breathing protocols for the rat model included: spontaneous direct breathing from an aerosol chamber, and use of a tracheotomy tube to bypass nasal breathing. The PFC aerosol delivery into the rat lung was documented through 19F MR imaging in correlation with high-resolution anatomic proton MR images. Theoretical model calculations for PFC mass deposition were compared with experimental results. RESULTS: The pneumatic generator produced a PFC aerosol droplet within the theoretically targeted range (geometric mean particle diameter of 1.2 microns; concentration of approximately 4 x 10(7) droplets per cm3). No measurable aerosol reached the lungs during spontaneous breathing because of the efficient filtering capabilities of the turbinated nasal passages. With tracheotomy, aerosol depositions within the lung were achieved in mass quantities consistent with theoretical expectations; however, the distribution patterns were nonuniform and unpredictable. Oxygen-enhanced 19F imaging was demonstrated. CONCLUSIONS: Perfluorocarbon aerosols of controlled size distribution can be produced at sufficient concentration with pneumatic generators for distribution to the terminal pulmonary architecture and visualization using 19F MR imaging. The potential exists for in vivo oxygen-sensitive imaging in the pulmonary system and development of sophisticated experimental animal models of systemic oxygen transport as a function of pulmonary status.

Correlations between blood glucose and breath components from portable gas sensors and PTR-TOF-MS.

Acetone is one of the most abundant volatile compounds in the human breath and might be important for monitoring diabetic patients. Here, a portable acetone sensor consisting of flame-made, nanostructured, Si-doped WO3 sensing films was used to analyse the end tidal fraction of the breath (collected in Tedlar bags) from eight healthy volunteers after overnight fasting (morning) and after lunch (afternoon). After breath sampling, the gaseous components were also analysed by proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS), and each person's blood glucose level was measured. The portable sensor accurately detected the presence of acetone with fast response/recovery times (<12 s) and a high signal-to-noise ratio. Statistical analysis of the relationship between the PTR-TOF-MS measurements of breath gases (e.g., acetone, isoprene, ethanol and methanol), sensor response and the blood glucose level was performed for both sampling periods. The best correlations were found after overnight fasting (morning): in particular, between blood glucose level and breath acetone (Pearson's 0.98 and Spearman's 0.93). Whereas the portable sensor response correlated best with the blood glucose (Pearson's 0.96 and Spearman's 0.81) and breath acetone (Pearson's 0.92 and Spearman's 0.69).

The Structure of Agglomerates consisting of Polydisperse Particles.

Agglomeration is encountered in many natural or industrial processes, like growth of aerosol particles in the atmosphere and during material synthesis or even flocculation of suspensions, granulation, crystallization and with colloidal particle processing. These particles collide by different mechanisms and stick together forming irregular or fractal-like agglomerates. Typically, the structure of these agglomerates is characterized with the fractal dimension, Df , and pre-exponential factor, kn , of simulated agglomerates of monodisperse primary particles (PP) for ballistic or diffusion-limited particle-cluster and cluster-cluster collision mechanisms. Here, the effect of PP polydispersity on Df and kn is investigated with agglomerates consisting of 16 - 1024 PP with closely controlled size distribution (geometric standard deviation, σ g = 1-3). These simulations are in excellent agreement with the classic structure (Df and kn ) of agglomerates consisting of monodisperse PPs made by four different collision mechanisms as well as with agglomerates of bi-, tri-disperse and normally distributed PPs. Broadening the PP size distribution of agglomerates decreases monotonically their Df and for sufficiently broad PP distributions (σ g > 2.5) the Df reaches about 1.5 and kn about 1 regardless of collision mechanism. Furthermore with increasing PP polydispersity, the corresponding projected area exponent, Dα , and pre-exponential factor, ka , decrease monotonically from their standard values for agglomerates with monodisperse PPs. So Df as well as Dα and ka can be an indication for PP polydispersity in mass-mobility and light scattering measurements, if the dominant agglomeration mechanism is known, like diffusion-limited and/or ballistic cluster-cluster coagulation in aerosols.

Mass-mobility characterization of flame-made ZrO2 aerosols: primary particle diameter and extent of aggregation.

Gas-borne nanoparticles undergoing coagulation and sintering form irregular or fractal-like structures affecting their transport, light scattering, effective surface area, and density. Here, zirconia (ZrO(2)) nanoparticles are generated by scalable spray combustion, and their mobility diameter and mass are obtained nearly in situ by differential mobility analyzer (DMA) and aerosol particle mass (APM) measurements. Using these data, the density of ZrO(2) and a power law between mobility and primary particle diameters, the structure of fractal-like particles is determined (mass-mobility exponent, prefactor and average number, and surface area mean diameter of primary particles, d(va)). The d(va) determined by DMA-APM measurements and this power law is in good agreement with the d(va) obtained by ex situ nitrogen adsorption and microscopic analysis. Using this combination of measurements and above power law, the effect of flame spray process parameters (e.g., precursor solution and oxygen flow rate as well as zirconium concentration) on fractal-like particle structure characteristics is investigated in detail. This reveals that predominantly agglomerates (physically-bonded particles) and aggregates (chemically- or sinter-bonded particles) of nanoparticles are formed at low and high particle concentrations, respectively.

Design of Gas-phase Synthesis of Core-Shell Particles by Computational Fluid - Aerosol Dynamics.

Core-shell particles preserve the bulk properties (e.g. magnetic, optical) of the core while its surface is modified by a shell material. Continuous aerosol coating of core TiO2 nanoparticles with nanothin silicon dioxide shells by jet injection of hexamethyldisiloxane precursor vapor downstream of titania particle formation is elucidated by combining computational fluid and aerosol dynamics. The effect of inlet coating vapor concentration and mixing intensity on product shell thickness distribution is presented. Rapid mixing of the core aerosol with the shell precursor vapor facilitates efficient synthesis of hermetically coated core-shell nanoparticles. The predicted extent of hermetic coating shells is compared to the measured photocatalytic oxidation of isopropanol by such particles as hermetic SiO2 shells prevent the photocatalytic activity of titania. Finally the performance of a simpler, plug-flow coating model is assessed by comparisons to the present detailed CFD model in terms of coating efficiency and silica average shell thickness and texture.

Sintering Rate and Mechanism of TiO2 Nanoparticles by Molecular Dynamics.

Titania is the dominant white pigment and photocatalytic material, a key component of sunscreens and has promising applications in photovoltaics and sensors of organic vapors. The growth of TiO2 nanoparticles by sintering, the critical step during their large scale manufacture and processing, is elucidated and quantified by molecular dynamics. Highly mobile ions from the particle surface fill in the initially concave space between nanoparticles (surface diffusion) forming the final, fully-coalesced, spherical-like particle with minimal displacement of inner Ti and O ions (grain boundary diffusion) revealing also the significance and sequence of these two sintering mechanisms of TiO2. A sintering rate for TiO2 nanoparticles is extracted that is much faster than that in the literature but nicely converges to it for increasing particle size.

Fragmentation and restructuring of soft-agglomerates under shear.

Soft-agglomerate restructuring, break-up (or fragmentation) and relaxation are studied in a simple shear flow by a discrete element method (DEM). The agglomerates, held together by van der Waals forces, rotate in the shear flow and are stretched into nearly linear structures (fractal dimension approaches unity) until they fracture at their weakest point resulting in lognormally-shaped fragment size distributions asymptotically. Individual fragments relax in the flow towards more compact agglomerates than the parent ones. The evolution of the average number of particles per fragment is described by generalized scaling laws between shear rate, onset (time-lag) of fragmentation, asymptotic fragment mass and size consistent with experimental and theoretical studies in the literature. The initial effective fractal dimension of the agglomerates influences the final one of the fragments.

Brownian coagulation at high concentration.

Particle growth by Brownian coagulation at high concentration in the continuum regime is investigated by solving the Langevin dynamics (LD) equations for each particle trajectory of polydisperse suspensions. By monitoring the LD attainment of the self-preserving size distribution (SPSD), it is shown that the classic Smoluchowski collision frequency function is accurate for dilute particle volume fractions, phis, below 0.1%. At higher phis, coagulation is about 4 and 10 times faster than for the classic theory at phis = 10 and 20%, respectively. For complete particle coalescence upon collision, SPSDs develop even in highly concentrated suspensions (up to phis = 35%), as with dilute ones, but are broadened with increasing phis. At high particle concentration, an overall coagulation rate is proposed that reduces to the classic one at low concentration. Detailed collision frequency functions are also obtained at various phis values. Fractal-like agglomerates undergoing coagulation at constant fractal dimension attain an SPSD only temporarily because their effective volume fraction continuously increases, approaching gelation in the absence of restructuring or fragmentation.

High concentration agglomerate dynamics at high temperatures.

The dynamics of agglomerate aerosols are investigated at high solids concentrations that are typical in industrial scale manufacture of fine particles (precursor mole fraction larger than 10 mol %). In particular, formation and growth of fumed silica at such concentrations by chemical reaction, coagulation, and sintering is simulated at nonisothermal conditions and compared to limited experimental data and commercial product specifications. Using recent chemical kinetics for silica formation by SiCl4 hydrolysis and neglecting aerosol polydispersity, the evolution of the diameter of primary particles (specific surface area, SSA), hard- and soft-agglomerates, along with agglomerate effective volume fraction (volume occupied by agglomerate) is investigated. Classic Smoluchowski theory is fundamentally limited for description of soft-agglomerate Brownian coagulation at high solids concentrations. In fact, these high concentrations affect little the primary particle diameter (or SSA) but dominate the soft-agglomerate diameter, structure, and volume fraction, leading to gelation consistent with experimental data. This indicates that restructuring and fragmentation should affect product particle characteristics during high-temperature synthesis of nanostructured particles at high concentrations in aerosol flow reactors.