Insight into CO2 dissociation in plasmas from numerical solution of a vibrational diffusion equation

The dissociation of CO2 molecules in plasmas is a subject of enormous importance for fundamental studies and the recent interest in carbon capture and carbon-neutral fuels. The vibrational excitation of the CO2 molecule plays an important role in the process. The complexity of the present state-to-state (STS) models makes it difficult to find out the key parameters. In this paper we propose as an alternative a numerical method based on the diffusion formalism developed in the past for analytical studies. The non-linear Fokker-Planck equation is solved by the time-dependent diffusion Monte Carlo method. Transport quantities are calculated from STS rate coefficients. The asymmetric stretching mode of CO2 is used as a test case. We show that the method reproduces the STS results or a Treanor distribution depending on the choice of the boundary conditions. A positive drift, whose energy onset is determined by the vibrational to translational temperature ratio, brings molecules from mid-energy range to dissociation. The high-energy fall of the distribution is observed even neglecting VT processes which are normally believed to be its cause. Our study explains several puzzling features of previous studies, provides new insights into the control of the dissociation rate and a much sought compression of the required data for modeling

H2 and HD Direct Photodissociation in the Chemistry of the Primordial Universe

In this work, we calculate the thermal contribution to the rate coefficients for the processes of photodissociation of H2 and HD molecules. A comparison between direct and indirect rate coefficients is reported for molecular hydrogen. The rate coefficients are calculated including all vibrational levels of both molecules. Interpolation expressions for all processes are provided as a function of temperature. The resulting total rates for these processes are contextualized by direct numerical calculations based on a standard chemical network for the primordial universe

Energy partitioning in N2 microwave discharges: integrated Fokker-Planck approach to vibrational kinetics and comparison with experiments

This work investigates energy transfers between electrons, vibrational and translational degrees of freedom and their effect on dissociation mechanisms in a N2 microwave plasma in the pressure range between 50 and 400 mbar. A novel self-consistent 0D plasma chemistry model describing vibrational kinetics via the vibrational energy equation and the Fokker–Planck approach is developed. It is used to simulate conditions achieved experimentally, providing good agreement with measured values of vibrational and gas temperature and electron density. Above 100 mbar, energy efficiency of dissociation increases with power density, due to the significant contribution of collisions between vibrationally excited N2 and electronically excited molecules. Energy transfer to vibrations is maximum at low power density and low pressure due to reduced gas heating

Intelligenza artificiale e sicurezza: opportunità, rischi e raccomandazioni

L'IA (o intelligenza artificiale) è una disciplina in forte espansione negli ultimi anni e lo sarà sempre più nel prossimo futuro: tuttavia è dal 1956 che l’IA studia l’emulazione dell’intelligenza da parte delle macchine, intese come software e in certi casi hardware. L’IA è nata dall’idea di costruire macchine che - ispirandosi ai processi legati all’intelligenza umana - siano in grado di risolvere problemi complessi, per i quali solitamente si ritiene che sia necessario un qualche tipo di ragionamento intelligente. La principale area di ricerca e applicazione attuale dell’IA è il machine learning (algoritmi che imparano e si adattano in base ai dati che ricevono), che negli ultimi anni ha trovato ampie applicazioni grazie alle reti neurali (modelli matematici composti da neuroni artificiali) che a loro volta hanno consentito la nascita del deep learning (reti neurali di maggiore complessità). Appartengono al mondo dell’IA anche i sistemi esperti, la visione artificiale, il riconoscimento vocale, l’elaborazione del linguaggio naturale, la robotica avanzata e alcune soluzioni di cybersecurity. Quando si parla di IA c'è chi ne è entusiasta pensando alle opportunità, altri sono preoccupati poiché temono tecnologie futuristiche di un mondo in cui i robot sostituiranno l'uomo, gli toglieranno il lavoro e decideranno al suo posto. In realtà l'IA è ampiamente utilizzata già oggi in molti campi, ad esempio nei cellulari, negli oggetti smart (IoT), nelle industry 4.0, per le smart city, nei sistemi di sicurezza informatica, nei sistemi di guida autonoma (drive o parking assistant), nei chat bot di vari siti web; questi sono solo alcuni esempi basati tutti su algoritmi tipici dell’intelligenza artificiale. Grazie all'IA le aziende possono avere svariati vantaggi nel fornire servizi avanzati, personalizzati, prevedere trend, anticipare le scelte degli utenti, ecc. Ma non è tutto oro quel che luccica: ci sono talvolta problemi tecnici, interrogativi etici, rischi di sicurezza, norme e legislazioni non del tutto chiare. Le organizzazioni che già adottano soluzioni basate sull’IA, o quelle che intendono farlo, potrebbero beneficiare di questa pubblicazione per approfondirne le opportunità, i rischi e le relative contromisure. La Community for Security del Clusit si augura che questa pubblicazione possa fornire ai lettori un utile quadro d’insieme di una realtà, come l’intelligenza artificiale, che ci accompagnerà sempre più nella vita personale, sociale e lavorativa.AI (or artificial intelligence) is a booming discipline in recent years and will be increasingly so in the near future.However, it is since 1956 that AI has been studying the emulation of intelligence by machines, understood as software and in some cases hardware. AI arose from the idea of building machines that-inspired by processes related to human intelligence-are able to solve complex problems, for which it is usually believed that some kind of intelligent reasoning is required. The main current area of AI research and application is machine learning (algorithms that learn and adapt based on the data they receive), which has found wide applications in recent years thanks to neural networks (mathematical models composed of artificial neurons), which in turn have enabled the emergence of deep learning (neural networks of greater complexity). Also belonging to the AI world are expert systems, computer vision, speech recognition, natural language processing, advanced robotics and some cybersecurity solutions. When it comes to AI there are those who are enthusiastic about it thinking of the opportunities, others are concerned as they fear futuristic technologies of a world where robots will replace humans, take away their jobs and make decisions for them. In reality, AI is already widely used in many fields, for example, in cell phones, smart objects (IoT), industries 4.0, for smart cities, cybersecurity systems, autonomous driving systems (drive or parking assistant), chat bots on various websites; these are just a few examples all based on typical artificial intelligence algorithms. Thanks to AI, companies can have a variety of advantages in providing advanced, personalized services, predicting trends, anticipating user choices, etc. But not all that glitters is gold: there are sometimes technical problems, ethical questions, security risks, and standards and legislation that are not entirely clear. Organizations already adopting AI-based solutions, or those planning to do so, could benefit from this publication to learn more about the opportunities, risks, and related countermeasures. Clusit's Community for Security hopes that this publication will provide readers with a useful overview of a reality, such as artificial intelligence, that will increasingly accompany us in our personal, social and working lives

Iron Behaving Badly: Inappropriate Iron Chelation as a Major Contributor to the Aetiology of Vascular and Other Progressive Inflammatory and Degenerative Diseases

The production of peroxide and superoxide is an inevitable consequence of aerobic metabolism, and while these particular "reactive oxygen species" (ROSs) can exhibit a number of biological effects, they are not of themselves excessively reactive and thus they are not especially damaging at physiological concentrations. However, their reactions with poorly liganded iron species can lead to the catalytic production of the very reactive and dangerous hydroxyl radical, which is exceptionally damaging, and a major cause of chronic inflammation. We review the considerable and wide-ranging evidence for the involvement of this combination of (su)peroxide and poorly liganded iron in a large number of physiological and indeed pathological processes and inflammatory disorders, especially those involving the progressive degradation of cellular and organismal performance. These diseases share a great many similarities and thus might be considered to have a common cause (i.e. iron-catalysed free radical and especially hydroxyl radical generation). The studies reviewed include those focused on a series of cardiovascular, metabolic and neurological diseases, where iron can be found at the sites of plaques and lesions, as well as studies showing the significance of iron to aging and longevity. The effective chelation of iron by natural or synthetic ligands is thus of major physiological (and potentially therapeutic) importance. As systems properties, we need to recognise that physiological observables have multiple molecular causes, and studying them in isolation leads to inconsistent patterns of apparent causality when it is the simultaneous combination of multiple factors that is responsible. This explains, for instance, the decidedly mixed effects of antioxidants that have been observed, etc...Comment: 159 pages, including 9 Figs and 2184 reference

A new class of glycomimetic drugs to prevent free fatty acid-induced endothelial dysfunction

Background: Carbohydrates play a major role in cell signaling in many biological processes. We have developed a set of glycomimetic drugs that mimic the structure of carbohydrates and represent a novel source of therapeutics for endothelial dysfunction, a key initiating factor in cardiovascular complications. Purpose: Our objective was to determine the protective effects of small molecule glycomimetics against free fatty acid­induced endothelial dysfunction, focusing on nitric oxide (NO) and oxidative stress pathways. Methods: Four glycomimetics were synthesized by the stepwise transformation of 2,5­dihydroxybenzoic acid to a range of 2,5­substituted benzoic acid derivatives, incorporating the key sulfate groups to mimic the interactions of heparan sulfate. Endothelial function was assessed using acetylcholine­induced, endotheliumdependent relaxation in mouse thoracic aortic rings using wire myography. Human umbilical vein endothelial cell (HUVEC) behavior was evaluated in the presence or absence of the free fatty acid, palmitate, with or without glycomimetics (1µM). DAF­2 and H2DCF­DA assays were used to determine nitric oxide (NO) and reactive oxygen species (ROS) production, respectively. Lipid peroxidation colorimetric and antioxidant enzyme activity assays were also carried out. RT­PCR and western blotting were utilized to measure Akt, eNOS, Nrf­2, NQO­1 and HO­1 expression. Results: Ex vivo endothelium­dependent relaxation was significantly improved by the glycomimetics under palmitate­induced oxidative stress. In vitro studies showed that the glycomimetics protected HUVECs against the palmitate­induced oxidative stress and enhanced NO production. We demonstrate that the protective effects of pre­incubation with glycomimetics occurred via upregulation of Akt/eNOS signaling, activation of the Nrf2/ARE pathway, and suppression of ROS­induced lipid peroxidation. Conclusion: We have developed a novel set of small molecule glycomimetics that protect against free fatty acidinduced endothelial dysfunction and thus, represent a new category of therapeutic drugs to target endothelial damage, the first line of defense against cardiovascular disease

Insight into CO\u3csub\u3e2\u3c/sub\u3e dissociation in plasma from numerical solution of a vibrational diffusion equation

\u3cp\u3eDissociation of CO\u3csub\u3e2\u3c/sub\u3e molecules in plasma is a subject of enormous importance for fundamental studies and in view of the recent interest in carbon capture and carbon-neutral fuels. Vibrational excitation of the CO\u3csub\u3e2\u3c/sub\u3e molecule plays an important role in the process. The complexity of the present state-to-state (STS) models makes it difficult to find the key parameters. In this paper we propose, as an alternative, a numerical method based on the diffusion formalism developed in the past for analytical studies. The nonlinear Fokker-Planck equation is solved by the time-dependent diffusion Monte Carlo method. Transport quantities are calculated from STS rate coefficients. The asymmetric stretching mode of CO\u3csub\u3e2\u3c/sub\u3e is used as a test case. We show that the method reproduces the STS results or a Treanor distribution depending on the choice of the boundary conditions. A positive drift, whose energy onset is determined by the vibrational to translational temperature ratio, brings molecules from mid-energy range to dissociation. Vibrational-translational energy transfers have negligible effect at the gas temperature considered in this study. The possibility of describing dissociation kinetics as a transport process provides insight toward the goal of achieving efficient CO\u3csub\u3e2\u3c/sub\u3e conversion. (Graph Presented).\u3c/p\u3

A Modified Fokker-Planck Approach for a Complete Description of Vibrational Kinetics in a N2 Plasma Chemistry Model

The Fokker-Planck (FP) approach for the description of vibrational kinetics is extended in order to include multiquanta transitions and time dependent solutions. Due to the importance of vibrational ladder climbing for the optimization of plasma-assisted nitrogen fixation, nitrogen is used as a test case with a comprehensive set of elementary processes affecting the vibrational distribution function (VDF). The inclusion of the vibrational energy equation is shown to be the best way to model transient conditions in a plasma reactor using the FP approach. Results are benchmarked against results from the widely employed state-to-state (STS) approach for a wide parameters range. STS and FP solutions agree within ∼10% for the lowest vibrational levels, while time dependent VDFs are in agreement with the STS solution within a ∼ 5% error. Using the FP approach offers the possibility to parametrize drift and diffusion coefficients in energy space as a function of vibrational and gas temperature, providing intuitive and immediate insights into energy transport within the vibrational manifold