The absolute yield of hydroxyl radicals per unit of deposited X‐ray energy is determined for the first time for irradiated aqueous solutions containing metal nanoparticles based on a “reference” protocol. Measurements are made as a function of dose rate and nanoparticle concentration. Possible mechanisms for hydroxyl radical production are considered in turn: energy deposition in the nanoparticles followed by its transport into the surrounding environment is unable to account for observed yield whereas energy deposition in the water followed by a catalytic‐like reaction at the water‐nanoparticle interface can account for the total yield and its dependence on dose rate and nanoparticle concentration. This finding is important because current models used to account for nanoparticle enhancement to radiobiological damage only consider the primary interaction with the nanoparticle, not with the surrounding media. Nothing about the new mechanism appears to be specific to gold, the main requirements being the formation of a structured water layer in the vicinity of the nanoparticle possibly through the interaction of its charge and the water dipoles. The massive hydroxyl radical production is relevant to a number of application fields, particularly nanomedicine since the hydroxyl radical is responsible for the majority of radiation‐induced DNA damage.
Gold nanoparticle radiosensitization represents a novel technique in enhancement of ionising radiation dose and its effect on biological systems. Variation between theoretical predictions and experimental measurement is significant enough that the mechanism leading to an increase in cell killing and DNA damage is still not clear. We present the first experimental results that take into account both the measured biodistribution of gold nanoparticles at the cellular level and the range of the product electrons responsible for energy deposition. Combining synchrotron-generated monoenergetic X-rays, intracellular gold particle imaging and DNA damage assays, has enabled a DNA damage model to be generated that includes the production of intermediate electrons. We can therefore show for the first time good agreement between the prediction of biological outcomes from both the Local Effect Model and a DNA damage model with experimentally observed cell killing and DNA damage induction via the combination of X-rays and GNPs. However, the requirement of two distinct models as indicated by this mechanistic study, one for short-term DNA damage and another for cell survival, indicates that, at least for nanoparticle enhancement, it is not safe to equate the lethal lesions invoked in the local effect model with DNA damage events.
We demonstrate an entirely new method of nanoparticle chemical synthesis based on liquid droplet irradiation with ultralow (<0.1 eV) energy electrons. While nanoparticle formation via high energy radiolysis or transmission electron microscopy-based electron bombardment is well-understood, we have developed a source of electrons with energies close to thermal which leads to a number of important and unique benefits. The charged species, including the growing nanoparticles, are held in an ultrathin surface reaction zone which enables extremely rapid precursor reduction. In a proof-of-principle demonstration, we obtain small-diameter Au nanoparticles (∼4 nm) with tight control of polydispersity, in under 150 μs. The precursor was almost completely reduced in this period, and the resultant nanoparticles were water-soluble and free of surfactant or additional ligand chemistry. Nanoparticle synthesis rates within the droplets were many orders of magnitude greater than equivalent rates reported for radiolysis, electron beam irradiation, or colloidal chemical synthesis where reaction times vary from seconds to hours. In our device, a stream of precursor loaded microdroplets, ∼15 μm in diameter, were transported rapidly through a cold atmospheric pressure plasma with a high charge concentration. A high electron flux, electron and nanoparticle confinement at the surface of the droplet, and the picoliter reactor volume are thought to be responsible for the remarkable enhancement in nanoparticle synthesis rates. While this approach exhibits considerable potential for scale-up of synthesis rates, it also offers the more immediate prospect of continuous on-demand delivery of high-quality nanomaterials directly to their point of use by avoiding the necessity of collection, recovery, and purification. A range of new applications can be envisaged, from theranostics and biomedical imaging in tissue to inline catalyst production for pollution remediation in automobiles.
Controlling gas temperature via continuous monitoring is essential in various plasma applications especially for biomedical treatments and nanomaterial synthesis but traditional techniques have limitations due to low accuracy, high cost or experimental complexity. We demonstrate continuous high-accuracy gas temperature measurements of low-temperature atmospheric pressure plasma jets using a small focal spot infrared sensor directed at the outer quartz wall of the plasma. The impact of heat transfer across the capillary tube was determined using calibration measurements of the inner wall temperature. Measured gas temperatures varied from 25 °C–50 °C, increasing with absorbed power and decreased gas flow. The introduction into the plasma of a stream (∼105 s−1) of microdroplets, in the size range 12 μm–15 μm, led to a reduction in gas temperature of up to 10 °C, for the same absorbed power. This is an important parameter in determining droplet evaporation and its impact on plasma chemistry.
Here is detailed a novel and low-cost experimental method for high-throughput automated fluid sample irradiation. The sample is delivered via syringe pump to a nozzle, where it is expressed in the form of a hanging droplet into the path of a beam of ionising radiation. The dose delivery is controlled by an upstream lead shutter, which allows the beam to reach the droplet for a user defined period of time. The droplet is then further expressed after irradiation until it falls into one well of a standard microplate. The entire system is automated and can be operated remotely using software designed in-house, allowing for use in environments deemed unsafe for the user (synchrotron beamlines, for example). Depending on the number of wells in the microplate, several droplets can be irradiated before any human interaction is necessary, and the user may choose up to 10 samples per microplate using an array of identical syringe pumps, the design of which is described here. The nozzles consistently produce droplets of 25.1 ± 0.5 μl.
We demonstrate a new gas-based OH• generation source using a low power RF-driven atmospheric pressure plasma configured to deliver the radical flux into the far effluent region, well away from interference from other plasma factors such as electric fields, currents, and UV radiation. Using He – H2O gas chemistry isolated from the laboratory air, the plasma generated flux contains OH• and other radicals including H•, O and HO2 as well as H2O2 which, along with OH•, was found to vary with H2O vapour content and absorbed power density. Peak flux values were 2.3 nmol s-1 and 0.23 nmol s-1 for H2O2 and OH• respectively at a distance of 50 mm from the plasma, with 790 ppmv H2O and a power density of ~ 108 W m-3. The maximum OH• flux density was 4.5 x 1019 m-2 s-1 falling to 1.7 x 1019 m-2 s-1 at 110 mm, equivalent to generation rates of 74 mM s-1 and 28 mM s-1. Despite high OH• recombination rates at the plasma exit, the escaping flux is still significant, indicating a viable delivery capability to downstream targets. Its performance with regard to OH• generation rates compares well with traditional OH• generation techniques such as radiolysis, advanced oxidation processes and enhanced Fenton-chemistry approaches where OH• production rates are sub-mM s-1. Delivering precisely quantifiable OH• fluxes provides new opportunities for scientific studies and technological opportunities in cell biology, atmospheric chemistry, protein unfolding and systematic dose studies for plasma-based and other OH• related potential medical treatments.
When microscopic-sized liquid droplets travel through a low temperature RF plasma [1] at atmospheric pressure a number of remarkable and unexpected effects have been observed. After a short flight time, ~0.1ms, there is evidence that chemical reactions induced by the plasma and gas flux proceed at a rate that is significantly faster that observed in plasma – bulk liquid studies and many orders of magnitude faster than in standard bulk chemistry.[2] We suspect this is due to the complex interplay between droplet charge, electric fields, both internal and external to the droplet, and high chemical fluxes arriving at the droplet surface. There exists a large potential to develop new plasma-liquid processes for medical, chemical, biological, environmental and materials applications, among others and we can highlight some unique features of the plasma – microdroplet system that may provide opportunities for exploitation, namely: (i) a controlled ambient environment, (ii) a large surface area to volume ratio, (iii) small volume, (iv) low droplet temperature, (v) in-flight chemical synthesis and encapsulation, and (iv) remote delivery. These features offer the possibility of delivering high fluxes of active chemical species and nanoparticles remotely and on demand for applications in, for example, plasma-medicine, agriculture and microreaction while keeping the plasma itself at a safe distance. We have measured reactive oxygen species (ROS) flux variation with distance, up to 150 mm beyond the plasma, along with its effect on bacterial cell viability, DNA and amino acids. We have investigated plasma interactions with single cells, each transported in its own droplet. We have used the individual droplets as chemical microreactors to produce nanoparticles in flight, at rates many orders of magnitude higher that via high energy radiolysis or chemical synthesis. These measurements form the basis for numerical simulation in the gas-plasma and liquid droplet phases. New measurement techniques, based on recently acquired facilities, are being investigated. These include mid-IR absorption studies of droplets and their environment in flight, using tunable supercontinuum and quantum cascade lasers, and freezing plasma-treated droplets in flight for in-situ transfer to XPS surface chemical analysis. Current theories of microparticle charging in a collisional plasma environment are very limited. While in-flight charge measurements represent a significant challenge, the relatively large size of the droplet (10 – 20 μm diameter) and the limited evaporation over the flight time, offer the prospect of using droplets as a spherical probe to develop enhanced collisional probe theories in the regime where the particle size is greater than Debye lengths or mean free paths. In-flight measurements indicate a minimum net charge of ~105 electrons, considerably higher than that obtained by other charging methods. Analytical – numerical and finite element simulations, in tandem with charge measurements, are being developed to better understand the droplet electrical environment and ultimately to link chemistry and charge in a consistent framework. References [1] PD Maguire et al., Appl. Phys. Lett. 106, 224101 (2015); http://dx.doi.org/10.1063/1.4922034 [2] PD Maguire et al., Nano Lett., 17, 1336–1343 (2017) http://dx.doi.org/10.1021/acs.nanolett.6b03440 Figure 1
When microscopic-sized liquid droplets travel through a low temperature RF plasma [1] at atmospheric pressure a number of remarkable and unexpected effects have been observed. After a short flight time, ~0.1ms, there is evidence that chemical reactions induced by the plasma and gas flux proceed at a rate that is significantly faster that observed in plasma – bulk liquid studies and many orders of magnitude faster than in standard bulk chemistry.[2] We suspect this is due to the complex interplay between droplet charge, electric fields, both internal and external to the droplet, and high chemical fluxes arriving at the droplet surface. There exists a large potential to develop new plasma-liquid processes for medical, chemical, biological, environmental and materials applications, among others and we can highlight some unique features of the plasma – microdroplet system that may provide opportunities for exploitation, namely: (i) a controlled ambient environment, (ii) a large surface area to volume ratio, (iii) small volume, (iv) low droplet temperature, (v) in-flight chemical synthesis and encapsulation, and (iv) remote delivery. These features offer the possibility of delivering high fluxes of active chemical species and nanoparticles remotely and on demand for applications in, for example, plasma-medicine, agriculture and microreaction while keeping the plasma itself at a safe distance. We have measured reactive oxygen species (ROS) flux variation with distance, up to 150 mm beyond the plasma, along with its effect on bacterial cell viability, DNA and amino acids. We have investigated plasma interactions with single cells, each transported in its own droplet. We have used the individual droplets as chemical microreactors to produce nanoparticles in flight, at rates many orders of magnitude higher that via high energy radiolysis or chemical synthesis. These measurements form the basis for numerical simulation in the gas-plasma and liquid droplet phases. New measurement techniques, based on recently acquired facilities, are being investigated. These include mid-IR absorption studies of droplets and their environment in flight, using tunable supercontinuum and quantum cascade lasers, and freezing plasma-treated droplets in flight for in-situ transfer to XPS surface chemical analysis. Current theories of microparticle charging in a collisional plasma environment are very limited. While in-flight charge measurements represent a significant challenge, the relatively large size of the droplet (10 – 20 μm diameter) and the limited evaporation over the flight time, offer the prospect of using droplets as a spherical probe to develop enhanced collisional probe theories in the regime where the particle size is greater than Debye lengths or mean free paths. In-flight measurements indicate a minimum net charge of 105 electrons, considerably higher than that obtained by other charging methods. Analytical – numerical and finite element simulations, in tandem with charge measurements, are being developed to better understand the droplet electrical environment and ultimately to link chemistry and charge in a consistent framework. References [1] PD Maguire et al., Appl. Phys. Lett. 106, 224101 (2015); http://dx.doi.org/10.1063/1.4922034 [2] PD Maguire et al., Nano Lett., 17, 1336–1343 (2017) http://dx.doi.org/10.1021/acs.nanolett.6b03440 Figure 1
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