Jingkun Jiang

Role of Surface Area, Primary Particle Size, and Crystal Phase on Titanium Dioxide Nanoparticle Dispersion Properties

Characterizing nanoparticle dispersions and understanding the effect of parameters that alter dispersion properties are important for both environmental applications and toxicity investigations. The role of particle surface area, primary particle size, and crystal phase on TiO2 nanoparticle dispersion properties is reported. Hydrodynamic size, zeta potential, and isoelectric point (IEP) of ten laboratory synthesized TiO2 samples, and one commercial Degussa TiO2 sample (P25) dispersed in different solutions were characterized. Solution ionic strength and pH affect titania dispersion properties. The effect of monovalent (NaCl) and divalent (MgCl2) inert electrolytes on dispersion properties was quantified through their contribution to ionic strength. Increasing titania particle surface area resulted in a decrease in solution pH. At fixed pH, increasing the particle surface area enhanced the collision frequency between particles and led to a higher degree of agglomeration. In addition to the synthesis method, TiO2 isoelectric point was found to be dependent on particle size. As anatase TiO2 primary particle size increased from 6 nm to 104 nm, its IEP decreased from 6.0 to 3.8 that also results in changes in dispersion zeta potential and hydrodynamic size. In contrast to particle size, TiO2 nanoparticle IEP was found to be insensitive to particle crystal structure.

Does nanoparticle activity depend upon size and crystal phase

A method to investigate the dependence of the physicochemical properties of nanoparticles (e.g., size, surface area and crystal phase) on their oxidant generating capacity is proposed and demonstrated for TiO2 nanoparticles. Gas phase synthesis methods that allow for strict control of size and crystal phase were used to prepare TiO2 nanoparticles. The reactive oxygen species (ROS) generating capacity of these particles was then measured. The size dependent ROS activity was established using TiO2 nanoparticles of nine different sizes (4–195 nm) but the same crystal phase. For a fixed total surface area, an S-shaped curve for ROS generation per unit surface area was observed as a function of particle size. The highest ROS activity per unit area was observed for 30 nm particles, and observed to be constant above 30 nm. There was a decrease in activity per unit area as size decreased from 30–10 nm; and again constant for particles smaller than 10 nm. The correlation between crystal phase and oxidant capacity was established using TiO2 nanoparticles of 11 different crystal phase combinations but similar size. The ability of different crystal phases of TiO2 nanoparticles to generate ROS was highest for amorphous, followed by anatase, and then anatase/rutile mixtures, and lowest for rutile samples. Based on evaluation of the entire dataset, important dose metrics for ROS generation are established. The implications of these ROS studies on biological and toxicological studies using nanomaterials are discussed.

Hard/soft magnetic heterostructures: model exchange-spring magnets

An overview is provided of research on exchange-spring coupled magnetic films and multilayers, including fabrication methods, and the characterization and modeling of the magnetization reversal processes. For coupled hard/soft bilayers and multilayers the deposition process provides nanometer-scale control of thicknesses and magnetic anisotropy. Such magnetic heterostructures provide model systems for studying the exchange hardening mechanism. Recent work on epitaxial SmCo/Fe and SmCo/Co bilayers and superlattices that display many of the characteristic features of exchange-spring magnets is highlighted. Comparison of the experimental results with numerical simulations indicates that the exchange-spring behavior can be understood from the intrinsic parameters of the hard and soft layers. The simulations are extended to realistically estimate the ultimate gain in performance that can potentially be realized in permanent magnets based on the exchange-spring principle.

Concept of Assessing Nanoparticle Hazards Considering Nanoparticle Dosemetric and Chemical/Biological Response Metrics

Engineered nanoparticles (NP) are being developed and incorporated in a number of commercial products, raising the potential of human exposure during manufacture, use, and disposal. Although data concerning the potential toxicity of some NP have been reported, validated simple assays are lacking for predicting their in vivo toxicity. The aim of this study was to evaluate new response metrics based on chemical and biological activity of NP for screening assays that can be used to predict NP toxicity in vivo. Two cell-free and two cell-based assays were evaluated for their power in predicting in vivo toxicity of eight distinct particle types with widely differing physicochemical characteristics. The cell-free systems comprised fluorescence- and electron spin resonance-based assays of oxidant activity. The cell-based systems also used electron spin resonance (ESR) as well as luciferase reporter activity to rank the different particle types in comparison to benchmark particles of low and high activity. In vivo experiments evaluated acute pulmonary inflammatory responses in rats. Endpoints in all assays were related to oxidative stress and responses were expressed per unit NP surface area to compare the results of different assays. Results indicated that NP are capable of producing reactive species, which in biological systems lead to oxidative stress. Copper NP had the greatest activity in all assays, while TiO2 and gold NP generally were the least reactive. Differences in the ranking of NP activity among the assays were found when comparisons were based on measured responses. However, expressing the chemical (cell-free) and biological (cells; in vivo) activity per unit particle surface area showed that all in vitro assays correlated significantly with in vivo results, with the cellular assays correlating the best. Data from this study indicate that it is possible to predict acute in vivo inflammatory potential of NP with cell-free and cellular assays by using NP surface area-based dose and response metrics, but that a cellular component is required to achieve a higher degree of predictive power.

Inhalable microorganisms in Beijing's PM2.5 and PM10 pollutants during a severe smog event.

Particulate matter (PM) air pollution poses a formidable public health threat to the city of Beijing. Among the various hazards of PM pollutants, microorganisms in PM2.5 and PM10 are thought to be responsible for various allergies and for the spread of respiratory diseases. While the physical and chemical properties of PM pollutants have been extensively studied, much less is known about the inhalable microorganisms. Most existing data on airborne microbial communities using 16S or 18S rRNA gene sequencing to categorize bacteria or fungi into the family or genus levels do not provide information on their allergenic and pathogenic potentials. Here we employed metagenomic methods to analyze the microbial composition of Beijing’s PM pollutants during a severe January smog event. We show that with sufficient sequencing depth, airborne microbes including bacteria, archaea, fungi, and dsDNA viruses can be identified at the species level. Our results suggested that the majority of the inhalable microorganisms were soil-associated and nonpathogenic to human. Nevertheless, the sequences of several respiratory microbial allergens and pathogens were identified and their relative abundance appeared to have increased with increased concentrations of PM pollution. Our findings may serve as an important reference for environmental scientists, health workers, and city planners.

Validation of an LDH assay for assessing nanoparticle toxicity.

Studies showed that certain cytotoxicity assays were not suitable for assessing nanoparticle (NP) toxicity. We evaluated a lactate dehydrogenase (LDH) assay for assessing copper (Cu-40, 40nm), silver (Ag-35, 35nm; Ag-40, 40nm), and titanium dioxide (TiO(2)-25, 25nm) NPs by examining their potential to inactivate LDH and interference with β-nicotinamide adenine dinucleotide (NADH), a substrate for the assay. We also performed a dissolution assay for some of the NPs. We found that the copper NPs, because of their high dissolution rate, could interfere with the LDH assay by inactivating LDH. Ag-35 could also inactivate LDH probably because of the carbon matrix used to cage the particles during synthesis. TiO(2)-25 NPs were found to adsorb LDH molecules. In conclusion, NP interference with the LDH assay depends on the type of NPs and the suitability of the assay for assessing NP toxicity should be examined case by case.

Long-term trend of haze pollution and impact of particulate matter in the Yangtze River Delta, China.

Haze pollution caused by heavy particulate matter (PM) loading brings significant damage in eastern China. Long-term monitoring from 1980 to 2011 and 1-year field measurement in 2011-2012 are used for investigating visibility variation and the impact of PM pollution for the Yangtze River Delta (YRD). It was found that visual range in the YRD endured a sharp reduction from 13.2 km to 10.5 km during 1980-2000. Average mass extinction efficiency (MEE) for inhalable PM (PM10) is 2.25 m(2)/g in 2001-2011, and extinction coefficient due to PM10 is 207 Mm(-1), accounting for 36.2% of total extinction coefficient. MEE of PM2.5 and PM2.5-10 are 4.08 m(2)/g and 0.58 m(2)/g, respectively. Extinction coefficient due to PM2.5 and PM2.5-10 is 198 Mm(-1) (39.6%) and 20 Mm(-1) (4.0%) in 2011-2012. Maximum daily concentration of PM10 and PM2.5 is estimated to be 63 μg/m(3) (RH: 73%) and 38 μg/m(3) (RH: 70%) to keep visual range above 10 km. Fine particulate matter is the key factor for haze pollution improvement in the YRD area.

Anisotropy dependence of irreversible switching in Fe∕SmCo and FeNi∕FePt exchange spring magnet films

Magnetization reversal in exchange-spring magnet films has been investigated by a first-order reversal curve sFORCd technique and vector magnetometry. In Fe/epitaxial-SmCo films, the reversal proceeds by a reversible rotation of the Fe soft layer, followed by an irreversible switching of the SmCo hard layer. The switching fields are clearly manifested by separate steps in both longitudinal and transverse hysteresis loops, as well as sharp boundaries in the FORC distribution. In FeNi/ polycrystalline-FePt films, particularly with thin FeNi, the switching fields are masked by the smooth and step-free major loop. However, the FORC diagram still displays a distinct onset of irreversible switching and transverse hysteresis loops exhibit a pair of peaks, whose amplitude is larger than the maximum possible contribution from the FeNi layer alone. This suggests that the FeNi and FePt layers reverse in a continuous process via a vertical spiral. The successive versus continuous rotation of the soft/hard layer system is primarily due to the different crystal structure of the hard layer, which results in different anisotropies.

Electrical Mobility Spectrometer Using a Diethylene Glycol Condensation Particle Counter for Measurement of Aerosol Size Distributions Down to 1 nm

We report a new scanning mobility particle spectrometer (SMPS) for measuring number size distributions of particles down to ∼1 nm mobility diameter. This SMPS includes an aerosol charger, a TSI 3085 nano differential mobility analyzer (nanoDMA), an ultrafine condensation particle counter (UCPC) using diethylene glycol (DEG) as the working fluid, and a conventional butanol CPC (the “booster”) to detect the small droplets leaving the DEG UCPC. The response of the DEG UCPC to negatively charged sodium chloride particles with mobility diameters ranging from 1–6 nm was measured. The sensitivity of the DEG UCPC to particle composition was also studied by comparing its response to positively charged 1.47 and 1.70 nm tetra-alkyl ammonium ions, sodium chloride, and silver particles. A high resolution differential mobility analyzer was used to generate the test particles. These results show that the response of this UCPC to sub-2 nm particles is sensitive to particle composition. The applicability of the new SMPS for atmospheric measurement was demonstrated during the Nucleation and Cloud Condensation Nuclei (NCCN) field campaign (Atlanta, Georgia, summer 2009). We operated the instrument at saturator and condenser temperatures that allowed the efficient detection of sodium chloride particles but not of air ions having the same mobility. We found that particles as small as 1 nm were detected during nucleation events but not at other times. Factors affecting size distribution measurements, including aerosol charging in the 1–10 nm size range, are discussed. For the charger used in this study, bipolar charging was found to be more effective for sub-2 nm particles than unipolar charging. No ion induced nucleation inside the charger was observed during the NCCN campaign.

Enhanced sulfate formation during China's severe winter haze episode in January 2013 missing from current models

A regional haze with daily PM2.5 (fine particulate matters with diameters less than 2.5 µm) exceeding 500 µg/m3 lasted for several days in January 2013 over North China, offering an opportunity to evaluate models. Observations show that inorganic aerosols (sulfate, nitrate, and ammonium) are the largest contributor to PM2.5 during the haze period, while sulfate shows the largest enhancement ratio of 5.4 from the clean to haze period. The nested-grid GEOS-Chem model reproduces the distribution of PM2.5 and simulates up to 364 µg/m3 of daily maximum PM2.5. Yet on average, the model is a factor of 3 and 4 lower in PM2.5 and fails to capture the large sulfate enhancement from the clean to haze period. A doubling of SO2 emissions over North China, along with daily meteorology corrections, would be required to reconcile model results with surface SO2 observations, but it is not sufficient to explain the model discrepancy in sulfate. Heterogeneous uptake of SO2 on deliquesced aerosols is proposed as an additional source of sulfate under high-relative humidity conditions during the haze period. Parameterizing this process in the model improves the simulated spatial distribution and results in a 70% increase of sulfate enhancement ratio and a 120% increase in sulfate fraction in PM2.5. Combined adjustments in emissions, meteorology, and sulfate chemistry lead to higher sulfate by a factor of 3 and 50% higher PM2.5, significantly reducing the models low bias during the haze.