CO2 Conversion in Nonuniform Discharges: Disentangling Dissociation and Recombination Mechanisms

Motivated by environmental applications such as synthetic fuel synthesis, plasma-driven conversion shows promise for efficient and scalable gas conversion of CO2 to CO. Both discharge contraction and turbulent transport have a significant impact on the plasma processing conditions, but are, nevertheless, poorly understood. This work combines experiments and modeling to investigate how these aspects influence the CO production and destruction mechanisms in the vortex-stabilized CO2 microwave plasma reactor. For this, a two-dimensional axisymmetric tubular chemical kinetics model of the reactor is developed, with careful consideration of the nonuniform nature of the plasma and the vortex-induced radial turbulent transport. Energy efficiency and conversion of the dissociation process show a good agreement with the numerical results over a broad pressure range from 80 to 600 mbar. The occurrence of an energy efficiency peak between 100 and 200 mbar is associated with a discharge mode transition. The net CO production rate is inhibited at low pressure by the plasma temperature, whereas recombination of CO to CO2 dominates at high pressure. Turbulence-induced cooling and dilution of plasma products limit the extent of the latter. The maxima in energy efficiency observed experimentally around 40% are related to limits imposed by production and recombination processes. Based on these insights, feasible approaches for optimization of the plasma dissociation process are discussed.</p

Implications of thermo-chemical instability on the contracted modes in CO2 microwave plasmas

Understanding and controlling contraction phenomena of plasmas in reactive flows is essential to optimize the discharge parameters for plasma processing applications such as fuel reforming and gas conversion. In this work, we describe the characteristic discharge modes in a CO2&nbsp;microwave plasma and assess the impact of wave coupling and thermal reactivity on the contraction dynamics. The plasma shape and gas temperature are obtained from the emission profile and the Doppler broadening of the 777 nm O(5S ←&nbsp;5P) oxygen triplet, respectively. Based on these observations, three distinct discharge modes are identified in the pressure range of 10 mbar to atmospheric pressure. We find that discharge contraction is suppressed by an absorption cut-off of the microwave field at the critical electron density, resulting in a homogeneous discharge mode below the critical transition pressure of 85 mbar. Further increase in the pressure leads to two contracted discharge modes, one emerging at a temperature of 3000 K to 4000 K and one at a temperature of 6000 K to 7000 K, which correspond to the thermal dissociation thresholds of CO2&nbsp;and CO respectively. The transition dynamics are explained by a thermo-chemical instability, which arises from the coupling of the thermal-ionization instability to heat transfer resulting from thermally driven endothermic CO2&nbsp;dissociation reactions. These results highlight the impact of thermal chemistry on the contraction dynamics of reactive molecular plasmas.</p

Characterization of the CO2 microwave plasma based on the phenomenon of skin-depth-limited contraction

The subatmospheric CO2 microwave plasma is known to contract to a narrow filament with rising pressure as result of a mode transition. This changing state of contraction is investigated in relation to its dielectric properties, in order to directly relate the discharge parameters to the discharge radius. The electron density and gas temperature are measured, respectively, by 168 GHz microwave interferometry and Doppler broadening of the 777 nm oxygen emission lines. The plasma is operated in steady state with 1400 W at 2.45 GHz, between 100 mbar and 400 mbar. Electron density values in the central region range from 1018 to 1020 m−3 between the discharge modes, while the gas temperature increases from 3000 K to 6500 K, in good agreement with previously reported values. Based on the dielectric properties of the discharge in relation to the plasma radius, it is found that the discharge column constitutes a radius of a single skin depth. Implications of these insights on the conditions of previously reported CO2 dissociation experiments are discussed.</p

Numerical model for the determination of the reduced electric field in a CO2 microwave plasma derived by the principle of impedance matching

Three dimensional electromagnetic modelling of a free-standing CO2 microwave plasma has been performed, by describing the plasma as a dielectric medium. The relative permittivity and conductivity of the medium are parametrised. The waveguide geometry from experiment, including the tuner, is put into the model, knowing that this corresponds to maximum power transfer of the microwave generator to the plasma under plasma impedance matching conditions. Two CO2 plasma discharge regimes, differing mainly in pressure, input power and temperature, have been studied. The model\u27s validity has been checked through study of materials of known conductivity. From measurements of the neutral gas temperature and the plasma electron density profile, the reduced electric field is determined. From the parametrisation of the dielectric properties, a range for the effective electron-neutral collision frequency for momentum transfer is estimated. The results for the reduced electric field and the range of the electron neutral collision frequency obtained, are consistent as verified by simulations using BOLSIG+. In addition, from this comparison it is possible to narrow down the range of the collision frequencies, and to estimate the electron temperature. The reduced electric field lies between 80 and 180 Td for the relatively low pressure, low input power, the so-called \u27diffuse\u27 regime. For the relatively high pressure, high input power (\u27contracted\u27) regime it lies between 10 and 60 Td. The normalised collision frequency lies between 1.6 and 2.3 for the diffuse regime, while for the contracted regime it lies between 2 and 3. The electron temperature ranges from 2 to 3 eV for the diffuse regime, and from 0.5 to 1 eV for the contracted regime. Related content: 10.1088/1361-6595/ab1ca1</p

Insight into contraction dynamics of microwave plasmas for CO2 conversion from plasma chemistry modelling

This work addresses plasma chemistry in the core of a vortex-stabilized microwave discharge for CO2 conversion numerically, focusing on the pressure-dependent contraction dynamics of this plasma. A zero-dimensional model is presented for experimental conditions in a pressure range between 60 and 300 mbar and a temperature range between 3000 and 6500 K. Monte Carlo Flux simulations, which describe electron kinetics, are self-consistently coupled to the plasma chemistry model. The simulation results show that an increase in pressure is accompanied by a transition in neutral composition in the plasma core: from a significant amount of CO2 and O2 at low pressures to a O/CO/C mixture at high pressures, the composition being determined mostly by thermal equilibrium and by transport processes. The change of temperature and composition with pressure lead to higher ionisation coefficient and more atomic ion composition in the plasma core. These changes result in an increase in ionisation degree in the plasma core from 10-5 to 10-4. These factors are shown to be fundamental to drive contraction in the CO2 microwave discharge.</p

Mutation analysis of P73 and TP53 in Merkel cell carcinoma

The p73 gene has been mapped to 1p36.33, a region which is frequently deleted in a wide variety of neoplasms including tumours of neuroectodermal origin. The p73 protein shows structural and functional homology to p53. For these reasons, p73 was considered as a positional and functional candidate tumour suppressor gene. Thus far, mutation analysis has provided no evidence for involvement of p73 in oligodendrogliomas, lung carcinoma, oesophageal carcinoma, prostatic carcinoma and hepatocellular carcinoma. In neuroblastoma, two mutations have been observed in a series of 140 tumours. In view of the occurrence of 1p deletions in Merkel cell carcinoma (MCC) and the location of p73 we decided to search for mutations in the p73 gene in five MCC cell lines and ten MCC tumours to test potential tumour suppressor function for this gene in MCC. In view of the possible complementary functions of p73 and TP53 we also examined the status of the TP53 gene. Sequence analysis of the entire coding region of the p73 gene revealed previously reported polymorphisms in four MCCs. In one MCC tumour, a mis-sense mutation located in the NH2-terminal transactivation region of the p73 gene was found. These results show that p73, analogous to neuroblastoma, is infrequently mutated in MCC. This is also the first report in which the role of TP53 in MCC has been investigated by sequencing the entire coding region of TP53. TP53 mis-sense mutations and one non-sense mutation were detected in three of 15 examined MCCs, suggesting that TP53 mutations may play a role in the pathogenesis or progression of a subset of MCCs. Moreover, typical UVB induced C to T mutations were found in one MCC cell line thus providing further evidence for sun-exposure in the aetiology of this rare skin cancer. © 2000 Cancer Research Campaig

Visually guided inspiration breath-hold facilitated with nasal high flow therapy in locally advanced lung cancer

Background and purpose Reducing breathing motion in radiotherapy (RT) is an attractive strategy to reduce margins and better spare normal tissues. The objective of this prospective study (NCT03729661) was to investigate the feasibility of irradiation of non-small cell lung cancer (NSCLC) with visually guided moderate deep inspiration breath-hold (IBH) using nasal high-flow therapy (NHFT). Material and methods Locally advanced NSCLC patients undergoing photon RT were given NHFT with heated humidified air (flow: 40 L/min with 80% oxygen) through a nasal cannula. IBH was monitored by optical surface tracking (OST) with visual feedback. At a training session, patients had to hold their breath as long as possible, without and with NHFT. For the daily cone beam CT (CBCT) and RT treatment in IBH, patients were instructed to keep their BH as long as it felt comfortable. OST was used to analyze stability and reproducibility of the BH, and CBCT to analyze daily tumor position. Subjective tolerance was measured with a questionnaire at 3 time points. Results Of 10 included patients, 9 were treated with RT. Seven (78%) completed the treatment with NHFT as planned. At the training session, the mean BH length without NHFT was 39 s (range 15-86 s), and with NHFT 78 s (range 29-223 s) (p = .005). NHFT prolonged the BH duration by a mean factor of 2.1 (range 1.1-3.9s). The mean overall stability and reproducibility were within 1 mm. Subjective tolerance was very good with the majority of patients having no or minor discomfort caused by the devices. The mean inter-fraction tumor position variability was 1.8 mm (-1.1-8.1 mm;SD 2.4 mm). Conclusion NHFT for RT treatment of NSCLC in BH is feasible, well tolerated and significantly increases the breath-hold duration. Visually guided BH with OST is stable and reproducible. We therefore consider this an attractive patient-friendly approach to treat lung cancer patients with RT in BH

LICC: L-BLP25 in patients with colorectal carcinoma after curative resection of hepatic metastases--a randomized, placebo-controlled, multicenter, multinational, double-blinded phase II trial

Background: 15-20% of all patients initially diagnosed with colorectal cancer develop metastatic disease and surgical resection remains the only potentially curative treatment available. Current 5-year survival following R0-resection of liver metastases is 28-39%, but recurrence eventually occurs in up to 70%. To date, adjuvant chemotherapy has not improved clinical outcomes significantly. The primary objective of the ongoing LICC trial (L-BLP25 In Colorectal Cancer) is to determine whether L-BLP25, an active cancer immunotherapy, extends recurrence-free survival (RFS) time over placebo in colorectal cancer patients following R0/R1 resection of hepatic metastases. L-BLP25 targets MUC1 glycoprotein, which is highly expressed in hepatic metastases from colorectal cancer. In a phase IIB trial, L-BLP25 has shown acceptable tolerability and a trend towards longer survival in patients with stage IIIB locoregional NSCLC. Methods: This is a multinational, phase II, multicenter, randomized, double-blind, placebo-controlled trial with a sample size of 159 patients from 20 centers in 3 countries. Patients with stage IV colorectal adenocarcinoma limited to liver metastases are included. Following curative-intent complete resection of the primary tumor and of all synchronous/metachronous metastases, eligible patients are randomized 2:1 to receive either L-BLP25 or placebo. Those allocated to L-BLP25 receive a single dose of 300 mg/m2 cyclophosphamide (CP) 3 days before first L-BLP25 dose, then primary treatment with s.c. L-BLP25 930 mug once weekly for 8 weeks, followed by s.c. L-BLP25 930 mug maintenance doses at 6-week (years 1&2) and 12-week (year 3) intervals unless recurrence occurs. In the control arm, CP is replaced by saline solution and L-BLP25 by placebo. Primary endpoint is the comparison of recurrence-free survival (RFS) time between groups. Secondary endpoints are overall survival (OS) time, safety, tolerability, RFS/OS in MUC-1 positive cancers. Exploratory immune response analyses are planned. The primary endpoint will be assessed in Q3 2016. Follow-up will end Q3 2017. Interim analyses are not planned. Discussion: The design and implementation of such a vaccination study in colorectal cancer is feasible. The study will provide recurrence-free and overall survival rates of groups in an unbiased fashion. Trial Registration EudraCT Number 2011-000218-2