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Identification of Porphyrin-Silica Composite Nanoparticles using Atmospheric Solids Analysis Probe Mass Spectrometry

MRS Advances

Karler, Casey; Parchert, Kylea J.; Ricken, James B.; Carson, Bryan C.; Mowry, Curtis D.; Fan, Hongyou F.; Ye, Dongmei Y.

Porphyrins are vital pigments involved in biological energy transduction processes. Their abilities to absorb light, then convert it to energy, have raised the interest of using porphyrin nanoparticles as photosensitizers in photodynamic therapy. A recent study showed that self- assembled porphyrin-silica composite nanoparticles can selectively destroy tumor cells, but detection of the cellular uptake of porphyrin-silica composite nanoparticles was limited to imaging microscopy. Here we developed a novel method to rapidly identify porphyrin-silica composite nanoparticles using Atmospheric Solids Analysis Probe-Mass Spectrometry (ASAP-MS). ASAP-MS can directly analyze complex mixtures without the need for sample preparation. Porphyrin-silica composite nanoparticles were vaporized using heated nitrogen desolvation gas, and their thermo-profiles were examined to identify distinct mass- to-charge (M/Z) signatures. HeLa cells were incubated in growth media containing the nanoparticles, and after sufficient washing to remove residual nanoparticles, the cell suspension was loaded onto the end of ASAP glass capillary probe. Upon heating, HeLa cells were degraded and porphyrin-silica composite nanoparticles were released. Vaporized nanoparticles were ionized and detected by MS. The cellular uptake of porphyrin-silica composite nanoparticles was identified using this ASAP-MS method.

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Atmospheric solids analysis probe mass spectrometry for the rapid identification of pollens and semi-quantification of flavonoid fingerprints

Rapid communications in mass spectrometry : RCM

Xiao, Xiaoyin; Miller, Lance L.; Parchert, Kylea J.; Hayes, Dulce C.; Hochrein, James M.

RATIONALE: From allergies to plant reproduction, pollens have important impacts on the health of human and plant populations, yet identification of pollen grains remains difficult and time-consuming. Low-volatility flavonoids generated from pollens cannot be easily characterized and quantified with current analytical techniques. METHODS: Here we present the novel use of atmospheric solids analysis probe mass spectrometry (ASAP-MS) for the characterization of flavonoids in pollens. Flavonoid patterns were generated for pollens collected from different plant types (trees and bushes) in addition to bee pollens from distinct geographic regions. Standard flavonoids (kaempferol and rhamnazin) and those produced from pollens were compared and assessed with ASAP-MS using low-energy collision MS/MS. Results for a semi-quantitative method for assessing the amount of a flavonoid in pollens are also presented. RESULTS: Flavonoid patterns for pollen samples were distinct with variability in the number and relative abundance of flavonoids in each sample. Pollens contained 2-5 flavonoids, and all but Kochia scoparia contained kaempferol or kaempferol isomers. We establish this method as a reliable and applicable technique for analyzing low-volatility compounds with minimal sample preparation. Standard curves were generated using 0.2-5 μg of kaempferol; from these experiments, it was estimated that there is approximately 2 mg of kaempferol present in 1 g of P. nigra italica pollen. CONCLUSIONS: Pollens can be characterized with a simple flavonoid pattern rather than analyzing the whole product pattern or the products-temperature profiles. ASAP-MS is a rapid analytical technique that can be used to distinguish between plant pollens and between bee pollens originating from different regions. Copyright © 2016 John Wiley & Sons, Ltd.

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First-principles flocculation as the key to low energy algal biofuels processing

Hewson, John C.; Mondy, L.A.; Murton, Jaclyn K.; O'Hern, Timothy J.; Parchert, Kylea J.; Pohl, Phillip I.; Williams, Cecelia V.; Wyatt, Nicholas B.; Barringer, David A.; Pierce, Flint P.; Brady, Patrick V.; Dwyer, Brian P.; Grillet, Anne M.; Hankins, M.G.; Hughes, Lindsey G.; Lechman, Jeremy B.

This document summarizes a three year Laboratory Directed Research and Development (LDRD) program effort to improve our understanding of algal flocculation with a key to overcoming harvesting as a techno-economic barrier to algal biofuels. Flocculation is limited by the concentrations of deprotonated functional groups on the algal cell surface. Favorable charged groups on the surfaces of precipitates that form in solution and the interaction of both with ions in the water can favor flocculation. Measurements of algae cell-surface functional groups are reported and related to the quantity of flocculant required. Deprotonation of surface groups and complexation of surface groups with ions from the growth media are predicted in the context of PHREEQC. The understanding of surface chemistry is linked to boundaries of effective flocculation. We show that the phase-space of effective flocculation can be expanded by more frequent alga-alga or floc-floc collisions. The collision frequency is dependent on the floc structure, described in the fractal sense. The fractal floc structure is shown to depend on the rate of shear mixing. We present both experimental measurements of the floc structure variation and simulations using LAMMPS (Large-scale Atomic/Molecular Massively Parallel Simulator). Both show a densification of the flocs with increasing shear. The LAMMPS results show a combined change in the fractal dimension and a change in the coordination number leading to stronger flocs.

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12 Results
12 Results