@article{wapshott-stehli_myers_quesada_grunden_stapelmann_2022, title={Plasma-driven biocatalysis: In situ hydrogen peroxide production with an atmospheric pressure plasma jet increases the performance of OleT(JE) when compared to adding the same molar amount of hydrogen peroxide in bolus}, volume={2}, ISSN={["1612-8869"]}, url={https://doi.org/10.1002/ppap.202100160}, DOI={10.1002/ppap.202100160}, abstractNote={Abstract Enzymes like fatty acid peroxygenase OleT JE are desirable enzymes for the industry. While they require inexpensive hydrogen peroxide for activity, the same hydrogen peroxide also causes overoxidation of their reactive heme center. Here, we generate hydrogen peroxide slowly in situ using the Cooperation in Science and Technology (COST)‐Jet, an atmospheric pressure plasma jet, to avoid overoxidizing OleT JE . The COST‐Jet was operated in helium with a water admixture to provide hydrogen peroxide for OleT JE activity. This helium/water admixture produced the highest enzyme turnover numbers after 2 min of treatment. These turnover numbers were even superior to using an equimolar amount of hydrogen peroxide to treat the enzymes exogenously, showing that this plasma source can provide a reliable amount of reaction mediator to support OleT JE activity.}, journal={PLASMA PROCESSES AND POLYMERS}, publisher={Wiley}, author={Wapshott-Stehli, Hannah L. and Myers, Brayden G. and Quesada, Maria J. Herrera and Grunden, Amy and Stapelmann, Katharina}, year={2022}, month={Feb} }
 @article{myers_barnat_stapelmann_2021, title={Atomic oxygen density determination in the effluent of the COST reference source using in situ effective lifetime measurements in the presence of a liquid interface}, volume={54}, ISSN={["1361-6463"]}, url={https://doi.org/10.1088/1361-6463/ac1cb5}, DOI={10.1088/1361-6463/ac1cb5}, abstractNote={Abstract Spatially resolved, absolute densities of atomic oxygen are measured for several helium-based admixtures in the effluent of the COST Reference Microplasma Jet using two-photon absorption laser induced fluorescence (TALIF). Admixtures investigated include a helium-only admixture, four helium/oxygen admixtures (0.1 <?CDATA $\%$?> <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mi mathvariant="normal">%</mml:mi> </mml:math> , 0.5 <?CDATA $\%$?> <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mi mathvariant="normal">%</mml:mi> </mml:math> , 0.6 <?CDATA $\%$?> <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mi mathvariant="normal">%</mml:mi> </mml:math> , and 1.0 <?CDATA $\%$?> <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mi mathvariant="normal">%</mml:mi> </mml:math> oxygen), and a helium/water admixture (2500 ppm water), chosen to coincide with previously published characterizations of plasma-treated liquid. The atomic oxygen TALIF signal is calibrated for density using the noble gas xenon, which possesses a very similar two-photon excitation and fluorescence scheme. Measurements are conducted for the jet operating in ambient air with both an open effluent and a liquid surface present, allowing for comparison with liquid phase measurements conducted under similar conditions. The presence of a water surface does not appear to alter the background chemistry in the effluent but reduces O densities close to the liquid interface when compared to a similar distance from the nozzle in an open effluent case. This may be the result of a reduction in flow velocity caused by the liquid obstructing the gas flow. Additionally, measurements near the liquid surface revealed a region of atomic oxygen well outside of where the core of the effluent impinges on the liquid. This is likely relevant for applications as it considerably expands the surface area subject to O absorption. Critically, in situ measurements of the effective lifetimes of the laser-excited 3p 3 P J state of atomic oxygen were recorded in the effluent by employing a picosecond (ps) laser and a nanosecond (ns) ICCD. By experimentally determining the contribution from collisional quenching via the in situ effective lifetime measurements, significant improvements in the accuracy of the atomic oxygen density calibration were made, with differences of approximately 30 <?CDATA $\%$?> <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mi mathvariant="normal">%</mml:mi> </mml:math> from existing methods of estimating quenching rates at atmospheric pressure. Finally, spatially resolved atomic oxygen densities allow for an investigation of O formation and extinction pathways in the effluent and a comparison between admixtures.}, number={45}, journal={JOURNAL OF PHYSICS D-APPLIED PHYSICS}, publisher={IOP Publishing}, author={Myers, Brayden and Barnat, Edward and Stapelmann, Katharina}, year={2021}, month={Nov} }
 @article{stapelmann_myers_quesada_lenker_ranieri_2021, title={Following O and OH in He/O-2 and He/H2O gas mixtures-from the gas phase through the liquid phase to modifications on a biological sample}, volume={54}, ISSN={["1361-6463"]}, url={https://doi.org/10.1088/1361-6463/ac18ec}, DOI={10.1088/1361-6463/ac18ec}, abstractNote={Abstract Applied cold atmospheric plasma allows for the controlled delivery of reactive oxygen and nitrogen species tailored for specific applications. Through the manipulation of the plasma parameters, feed gases, and careful consideration of the environment surrounding the treatment target, selective chemistries that preferentially influence the target can be produced and delivered. To demonstrate this, the COST reference microscale atmospheric pressure plasma jet is used to study the generation and transport of O and <?CDATA $^\cdot$?> <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:msup> <mml:mrow /> <mml:mo>⋅</mml:mo> </mml:msup> </mml:mrow> </mml:math> OH from the gas phase through the liquid to the biological model target cysteine. Relative and absolute species densities of <?CDATA $^\cdot$?> <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:msup> <mml:mrow /> <mml:mo>⋅</mml:mo> </mml:msup> </mml:mrow> </mml:math> OH and O are measured in the gas phase through laser induced fluorescence (LIF) and two-photon absorption LIF respectively. The transport of these species is followed into the liquid phase by hydrogen peroxide quantification and visualized by a fluorescence assay. Modifications to the model biological sample cysteine exposed to <?CDATA $^\cdot$?> <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:msup> <mml:mrow /> <mml:mo>⋅</mml:mo> </mml:msup> </mml:mrow> </mml:math> OH and H 2 O 2 dominated chemistry (He/H 2 O (0.25%)) and O dominated chemistry (He/O 2 (0.6%)) is measured by FTIR spectroscopy. The origin of these species that modify cysteine is considered through the use of heavy water (H <?CDATA $_2^{18}$?> <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:msubsup> <mml:mrow /> <mml:mn>2</mml:mn> <mml:mrow> <mml:mn>18</mml:mn> </mml:mrow> </mml:msubsup> </mml:mrow> </mml:math> O) and mass spectrometry. It is found that the reaction pathways differ significantly for He/O 2 and He/H 2 O. Hydrogen peroxide is formed mainly in the liquid phase in the presence of a substrate for He/O 2 whereas for He/H 2 O it forms in the gas phase. The liquid chemistry resulting from the He/O 2 admixture mainly targets the sulfur moiety of cysteine for oxidation up to irreversible oxidation states, while He/H 2 O treatment leads preferentially to reversible oxidation products. The more O or OH/H 2 O 2 dominated chemistry produced by the two gas admixtures studied offers the possibility to select species for target modification.}, number={43}, journal={JOURNAL OF PHYSICS D-APPLIED PHYSICS}, publisher={IOP Publishing}, author={Stapelmann, Katharina and Myers, Brayden and Quesada, Maria Herrera and Lenker, Eleanor and Ranieri, Pietro J.}, year={2021}, month={Oct} }
 @article{myers_ranieri_smirnova_hewitt_peterson_quesada_lenker_stapelmann_2021, title={Measuring plasma-generated center dot OH and O atoms in liquid using EPR spectroscopy and the non-selectivity of the HTA assay}, volume={54}, ISSN={["1361-6463"]}, url={https://doi.org/10.1088/1361-6463/abd9a6}, DOI={10.1088/1361-6463/abd9a6}, abstractNote={Abstract Plasma-generated hydroxyl radicals ( · OH) and oxygen atoms (O) produced by the COST reference plasma jet, a micro-scaled atmospheric pressure plasma jet, were investigated using a variety of experimental techniques. Several gas admixtures were studied to distinguish the contributions of the two reactive oxygen species. Large discrepancies between inferred aqueous · OH densities were noted when using a 2-hydroxyterephthalic acid (HTA) fluorescence assay and electron paramagnetic resonance (EPR) measurements with the spin trap 5,5-dimethyl-1-pyrroline N -oxide—especially when oxygen was present in the feed gas. A series of follow-up experiments including optical emission spectroscopy, H 2 O 2 quantification, and EPR measurements of atomic oxygen using the spin trap 2,2,6,6-tetramethylpiperidine, revealed that the inconsistencies between the measured aqueous · OH were likely due to the propensity of atomic oxygen to hydroxylate TA in a manner indistinguishable from · OH. This renders the HTA assay non-selective when both · OH radicals and atomic oxygen are present, which we report for all three gas admixtures in our experiments. Additionally, considerable degradation of both HTA and the spin adducts measured using EPR spectroscopy was apparent, meaning actual radical densities in the plasma-treated liquid may be considerably higher than implied. Degradation rates compared favorably to previously measured gas phase densities of atomic oxygen in the predecessor of the COST jet and reported degradation of other chemical probes. These results show the prolific role of atomic oxygen in plasma-induced liquid chemistry and caution against diagnostic techniques that are unable to account for it.}, number={14}, journal={JOURNAL OF PHYSICS D-APPLIED PHYSICS}, publisher={IOP Publishing}, author={Myers, B. and Ranieri, P. and Smirnova, T. and Hewitt, P. and Peterson, D. and Quesada, M. Herrera and Lenker, E. and Stapelmann, K.}, year={2021}, month={Apr} }