Abstract: This work proposes to use core-shell structured spheres to evaluate whether it allows to individually optimize bulk and surface effects of a packing material, in order to optimize conversion and energy efficiency. Different core-shell materials have been prepared by spray coating, using dense spheres (as core) and powders (as shell) of SiO2, Al2O3, and BaTiO3. The materials are investigated for their performance in CO2 dissociation and compared against a benchmark consisting of a packed-bed reactor with the pure dense spheres, as well as an empty reactor. The results in terms of CO2 conversion and energy efficiency show various interactions between the core and shell material, depending on their combination. Al2O3 was found as the best core material under the applied conditions here, followed by BaTiO3 and SiO2, in agreement with their behaviour for the pure spheres. Applying a thin shell layer on the cores showed equal performance between the different shell materials. Increasing the layer thickness shifts this behaviour, and strong combination effects were observed depending on the specific material. Therefore, this method of core-shell spheres has the potential to allow tuning of the packing properties more closely to the application by designing an optimal combination of core and shell.

Abstract: Mcl1 is an important anti-apoptotic member of the Bcl2 family proteins that are upregulated in several cancer malignancies. The canonical binding groove (CBG) located at the surface of Mcl1 exhibits a critical role in binding partners selectively via the BH3-domain of pro-apoptotic Bcl2 family members that trigger the downregulation of Mcl1 function. There are several crystal structures of point-mutated pro-apoptotic Bim peptides in complex with Mcl1. However, the mechanistic effects of such point-mutations towards peptide binding and complex stability still remain unexplored. Here, the effects of the reported point mutations in Bim peptides and their binding mechanisms to Mcl1 were computationally evaluated using atomistic-level steered molecular dynamics (SMD) simulations. A range of external-forces and constant-velocities were applied to the Bim peptides to uncover the mechanistic basis of peptide dissociation from the CBG of Mcl1. Although the peptides showed similarities in their dissociation pathways, the peak rupture forces varied significantly. According to simulations results, the disruption of the conserved polar contacts at the complex interface causes a sequential release of the peptides from the CBG of Mcl1. Overall, the results obtained from the current study may provide valuable insights for the development of novel anti-cancer peptide-inhibitors that can downregulate Mcl1’s function.

Abstract: This paper benchmarks various epitaxial growth schemes based on n-type group-IV materials as viable source/drain candidates for Ge nMOS devices. Si:P grown at low temperature on Ge, gives an active carrier concentration as high as 3.5 x 10(20) cm(-3) and a contact resistivity down to 7.5 x 10(-9) Omega.cm(2). However, Si:P growth is highly defective due to large lattice mismatch between Si and Ge. Within the material stacks assessed, one option for Ge nMOS source/drain stressors would be to stack Si:P, deposited at contact level, on top of a selectively grown n-SiyGe1-x-ySnx at source/drain level, in line with the concept of Si passivation of n-Ge surfaces to achieve low contact resistivities as reported in literature (Martens et al. 2011 Appl. Phys. Lett., 98, 013 504). The saturation in active carrier concentration with increasing P (or As)-doping is the major bottleneck in achieving low contact resistivities for as-grown Ge or SiyGe1-x-ySnx. We focus on understanding various dopant deactivation mechanisms in P-doped Ge and Ge1-xSnx alloys. First principles simulation results suggest that P deactivation in Ge and Ge1-xSnx can be explained both by P-clustering and donor-vacancy complexes. Positron annihilation spectroscopy analysis, suggests that dopant deactivation in P-doped Ge and Ge1-xSnx is primarily due to the formation of P-n-V and SnmPn-V clusters. (C) 2020 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited.

Abstract: The penetration of reactive oxygen and nitrogen species (RONS) across the stratum corneum (SC) is a necessary and crucial process in many skin‐related plasma medical applications. To gain more insights into this penetration behavior, we combined experimental measurements of the permeability of dry and moist SC layers with computer simulations of model lipid membranes. We measured the permeation of relatively stable molecules, which are typically generated by plasma, namely H2O2, NO3−, and NO2−. Furthermore, we calculated the permeation free energy profiles of the major plasma‐generated RONS and their derivatives (i.e., H2O2, OH, HO2, O2, O3, NO, NO2, N2O4, HNO2, HNO3, NO2−, and NO3−) across native and oxidized SC lipid bilayers, to understand the mechanisms of RONS permeation across the SC. Our results indicate that hydrophobic RONS (i.e., NO, NO2, O2, O3, and N2O4) can translocate more easily across the SC lipid bilayer than hydrophilic RONS (i.e., H2O2, OH, HO2, HNO2, and HNO3) and ions (i.e., NO2− and NO3−) that experience much higher permeation barriers. The permeability of RONS through the SC skin lipids is enhanced when the skin is moist and the lipids are oxidized. These findings may help to understand the underlying mechanisms of plasma interaction with a biomaterial and to optimize the environmental parameters in practice in plasma medical applications.

Abstract: Plasma technology provides a sustainable, fossil-free method for N2 fixation, i.e., the conversion of inert atmospheric N2 into valuable substances, such as NOx or ammonia. In this work, we present a novel gliding arc plasmatron at atmospheric pressure for NOx production at different N2/O2 gas feed ratios, offering a promising NOx yield of 1.5% with an energy cost of 3.6 MJ/mol NOx produced. To explain the underlying mechanisms, we present a chemical kinetics model, validated by experiments, which provides insight into the NOx formation pathways and into the ambivalent role of the vibrational kinetics. This allows us to pinpoint the factors limiting the yield and energy cost, which can help to further improve the process.

Abstract: Mcl1 is a primary member of the Bcl–2 family—anti–apoptotic proteins (AAP)—that is overexpressed in several cancer pathologies. The apoptotic regulation is mediated through the binding of pro-apoptotic peptides (PAPs) (e.g., Bak and Bid) at the canonical hydrophobic binding groove (CBG) of Mcl1. Although all PAPs form amphipathic α-helices, their amino acid sequences vary to different degree. This sequence variation exhibits a central role in the binding partner selectivity towards different AAPs. Thus, constructing a novel peptide or small organic molecule with the ability to mimic the natural regulatory process of PAP is essential to inhibit various AAPs. Previously reported experimental binding free energies (BFEs) were utilized in the current investigation aimed to understand the mechanistic basis of different PAPs targeted to mMcl1. Molecular dynamics (MD) simulations used to estimate BFEs between mMcl1—PAP complexes using Molecular Mechanics-Generalized Born Solvent Accessible (MMGBSA) approach with multiple parameters. Predicted BFE values showed an excellent agreement with the experiment (R2 = 0.92). The van–der Waals (ΔGvdw) and electrostatic (ΔGele) energy terms found to be the main energy components that drive heterodimerization of mMcl1—PAP complexes. Finally, the dynamic network analysis predicted the allosteric signal transmission pathway involves more favorable energy contributing residues. In total, the results obtained from the current investigation may provide valuable insights for the synthesis of a novel peptide or small organic inhibitor targeting Mcl1.

Abstract: The combination of catalysis with non-thermal plasma is a promising alternative to thermal catalysis. A dielectric-barrier discharge reactor was used to study plasma-catalytic dry reforming of methane at ambient pressure and temperature and a fixed plasma power of 45 W. The effect of different catalytic packing materials was evaluated in terms of conversion, product selectivity, and energy efficiency. The conversion of CO2 (~22%) and CH4 (~33%) were found to be similar in plasma-only and when introducing packing materials in plasma. The main reason is the shorter residence time of the gas due to packing geometry, when compared at identical flow rates. H2, CO, C2-C4 hydrocarbons, and oxygenates were identified in the product gas. High selectivity towards H2 and CO were found for all catalysts and plasma-only, with a H2/CO molar ratio of ~0.9. The lowest syngas selectivity was obtained with Cu/Al2O3 (~66%), which instead, had the highest alcohol selectivity (~3.6%).

Abstract: The dielectric properties of confined water is of fundamental interest and is still controversial. For water confined in channels with height smaller than h = 8 angstrom, we found a commensurability effect and an extraordinary decrease in the out-of-plane dielectric constant down to the limit of the dielectric constant of optical water. Spatial resolved polarization density data obtained from molecular dynamics simulations are found to be antisymmetric across the channel and are used as input in a mean-field model for the dielectric constant as a function of the height of the channel for h > 15 angstrom. Our results are in excellent agreement with a recent experiment [L. Fumagalli et al., Science 360, 1339 (2018)].

Abstract: In this work, the effects of N-doping into the Co-doped single vacancy (Co-SV-G) and di-vacancy graphene flake (Co-dV-G) are investigated and compared toward direct oxidation of methane to methanol (DOMM) employing two different oxidants (N2O and O-2) using density functional theory (DFT) calculation. We found that DOMM on CoN3-G utilizing the N2O molecule as oxygen-donor proceeds via a two-step reaction with low activation energies. In addition, we found that although CoN3-G might be a good catalyst for methane conversion, it can also catalyze the oxidation of methanol to CO2 and H2O due to the required low activation barriers. Moreover, the adsorption behaviors of CHx (x = 0-4) species and dehydrogenation of CHx (x = 1-4) species on CoN3-G are investigated. We concluded that CoN3-G can be used as an efficient catalyst for DOMM and N-2O reduction at ambient conditions which may serve as a guide for fabricating effective C/N catalysts in energy-related devices.

Abstract: Plasma catalysis is gaining increasing interest for various gas conversion applications, such as CO2 conversion into value-added chemicals and fuels, CH4 activation into hydrogen, higher hydrocarbons or oxygenates, and NH3 synthesis. Other applications are already more established, such as for air pollution control, e.g. volatile organic compound remediation, particulate matter and NOx removal. In addition, plasma is also very promising for catalyst synthesis and treatment. Plasma catalysis clearly has benefits over ‘conventional’ catalysis, as outlined in the Introduction. However, a better insight into the underlying physical and chemical processes is crucial. This can be obtained by experiments applying diagnostics, studying both the chemical processes at the catalyst surface and the physicochemical mechanisms of plasma-catalyst interactions, as well as by computer modeling. The key challenge is to design cost-effective, highly active and stable catalysts tailored to the plasma environment. Therefore, insight from thermal catalysis as well as electro- and photocatalysis is crucial. All these aspects are covered in this Roadmap paper, written by specialists in their field, presenting the state-of-the-art, the current and future challenges, as well as the advances in science and technology needed to meet these challenges.

Abstract: Plasma has been studied for several years to convert CO2 into value-added products. If CO2 could be converted in the presence of H2O as a cheap H-source for making syngas and oxygenates, it would mimic natural photosynthesis. However, CO2/H2O plasmas have not yet been extensively studied, not by experiments, and certainly not computationally. Therefore, we present here a kinetic modelling study to obtain a greater understanding of the vibrational kinetics of a CO2/H2O microwave plasma. For this purpose, we first created an electron impact cross section set for H2O, using a swarm-derived method. We added the new cross section set and CO2/H2O-related chemistry to a pure CO2 model. While it was expected that H2O addition mainly causes quenching of the CO2 asymmetric mode vibrational levels due to the additional CO2/H2O vibrational-translational relaxation, our model shows that the modifications in the vibrational kinetics are mainly induced by the strong electron dissociative attachment to H2O molecules, causing a reduction in electron density, and the corresponding changes in the input of energy into the CO2 vibrational levels by electron impact processes.

Abstract: The requirements for new technologies to serve as anticancer agents go far beyond their toxicity potential. Novel applications also need to be safe on a molecular and patient level. In a broader sense, this also relates to cancer metastasis and inflammation. In a previous study, the toxicity of an atmospheric pressure argon plasma jet in four human pancreatic cancer cell lines was confirmed and plasma treatment did not promote metastasis in vitro and in ovo. Here, these results are extended by additional types of analysis and new models to validate and define on a molecular level the changes related to metastatic processes in pancreatic cancer cells following plasma treatment in vitro and in ovo. In solid tumors that were grown on the chorion-allantois membrane of fertilized chicken eggs (TUM-CAM), plasma treatment induced modest to profound apoptosis in the tissues. This, however, was not associated with a change in the expression levels of adhesion molecules, as shown using immunofluorescence of ultrathin tissue sections. Culturing of the cells detached from these solid tumors for 6d revealed a similar or smaller total growth area and expression of ZEB1, a transcription factor associated with cancer metastasis, in the plasma-treated pancreatic cancer tissues. Analysis of in vitro and in ovo supernatants of 13 different cytokines and chemokines revealed cell line-specific effects of the plasma treatment but a noticeable increase of, e.g., growth-promoting interleukin 10 was not observed. Moreover, markers of epithelial-to-mesenchymal transition (EMT), a metastasis-promoting cellular program, were investigated. Plasma-treated pancreatic cancer cells did not present an EMT-profile. Finally, a realistic 3D tumor spheroid co-culture model with pancreatic stellate cells was employed, and the invasive properties in a gel-like cellular matrix were investigated. Tumor outgrowth and spread was similar or decreased in the plasma conditions. Altogether, these results provide valuable insights into the effect of plasma treatment on metastasis-related properties of cancer cells and did not suggest EMT-promoting effects of this novel cancer therapy.

Abstract: The free energy surface (FES) for carbon segregation from nickel nanoparticles is obtained from advanced molecular dynamics simulations. A suitable reaction coordinate is developed that can distinguish dissolved carbon atoms from segregated dimers, chains and junctions on the nanoparticle surface. Because of the typically long segregation time scale (up to ms), metadynamics simulations along the developed reaction coordinate are used to construct FES over a wide range of temperatures and carbon concentrations. The FES revealed the relative stability of different stages in the segregation process, and free energy barriers and rates of the individual steps could then be calculated and decomposed into enthalpic and entropic contributions. As the carbon concentration in the nickel nanoparticle increases, segregated carbon becomes more stable in terms of both enthalpy and entropy. The activation free energy of the reaction also decreases with the increase of carbon concentration, which can be mainly attributed to entropic effects. These insights and the methodology developed to obtain them improve our understanding of carbon segregation process across materials science in general, and the nucleation and growth of carbon nanotube in particular.

Abstract: Atomistic simulation methods for the quantification of free energies are in wide use. These methods operate by sampling the probability density of a system along a small set of suitable collective variables (CVs), which is, in turn, expressed in the form of a free energy surface (FES). This definition of the FES can capture the relative stability of metastable states but not that of the transition state because the barrier height is not invariant to the choice of CVs. Free energy barriers therefore cannot be consistently computed from the FES. Here, we present a simple approach to calculate the gauge correction necessary to eliminate this inconsistency. Using our procedure, the standard FES as well as its gauge-corrected counterpart can be obtained by reweighing the same simulated trajectory at little additional cost. We apply the method to a number of systems—a particle solvated in a Lennard-Jones fluid, a Diels–Alder reaction, and crystallization of liquid sodium—to demonstrate its ability to produce consistent free energy barriers that correctly capture the kinetics of chemical or physical transformations, and discuss the additional demands it puts on the chosen CVs. Because the FES can be converged at relatively short (sub-ns) time scales, a free energy-based description of reaction kinetics is a particularly attractive option to study chemical processes at more expensive quantum mechanical levels of theory.

Abstract: The possibility of confinement effects inside a carbon nanotube provides new application opportunities, e.g., growth of novel carbon nanostructures. However, the understanding the precise role of catalystfeedstock in the nanostructure synthesis is still elusive. In our simulation-based study, we investigate the Ni-catalyzed growth mechanism of encapsulated carbon nanostructures, viz. double-wall carbon nanotube and graphene nanoribbon, from carbon and hydrocarbon growth precursors, respectively. Specifically, we find that the tube and ribbon growth is determined by a catalyst-vs-feedstock competition effect. We compare our results, i.e., growth mechanism and structure morphology with all available theoretical and experimental data. Our calculations show that all encapsulated nanostructures contain metal (catalyst) atoms and such structures are less stable than their pure counterparts. Therefore, we study the purification mechanism of these structures. In general, this study opens a possible route to the controllable synthesis of tubular and planar carbon nanostructures for today’s nanotechnology.