Desde os trabalhos de Clausius, Boltzmann e Gibbs, sabe-se que partículas que interagem através de potenciais de curto alcance alcançam, após um processo de relaxação, o estado final estacionário que corresponde ao equilíbrio termodinâmico [I]. Embora nenhuma prova exata exista para isso, na prática, verifica-se que os sistemas não-integráveis com uma energia fixa e um número finito de partículas (ensemble microcanônico, por exemplo) sempre relaxam para um estado estacionário que só depende de quantidades globais conservadas pela dinâmica: energia, momentum e momentum angular. Este estado estacionário corresponde ao estado de equilíbrio termodinâmico e não depende das especificidades da distribuição inicial de partículas. Este cenário muda drasticamente quando a interação entre as partículas passa a ser de longo alcance [2]. A descrição estatística e termodinâmica desses sistemas ainda é objeto de estudo. Contudo, o que se sabe é que esses sistemas têm como propriedade fundamental o fato de que, no limite termodinâmico o tempo de colisão diverge e o equilíbrio termodinâmico nunca é atingido [3]. Nesse trabalho analisamos do ponto de vista teórico e por simulação de dinâmica molecular o estado estacionário atingido por sistemas auto-gravitantes em uma, duas e três dimensões e plasmas não-neutros na dinâmica de um feixe de partículas carregadas. Analisamos ainda um modelo com transição de fases para o estado fora do equilíbrio (HMF). Em todos os casos a teoria proposta na tese mostrou-se consistente com os simulações numéricas empregadas. / Since the work of Clausius, Boltzmann and Gibbs, it is known that particles interacting by a short-range potential, after a relaxation process, reach a final stationary state that corresponds to thermodynamic equilibrium. Although no exact proof exists, in practice non-integrable systems with fixed energy and a finite number of particles (i.e., microcanonical ensemble) always relax to a stationary state that depends only on global quantities conserved by the dynamics: energy, momentum and angular momentum. This stationary state corresponds to the state of thermodynamic equilibrium and does not depend on the specifics of the initial particle distribution. This scenario changes drastically when the interaction between particles is longranged [2] The statistical and thermodynamic description of these systems is still an object of study. However, a fundamental property of these systems is the fact that, in the thermodynamic limit, the collision time diverges and thermodynamic equilibrium is never achieved [3].. In this thesis we analyse, from a theoretical point of view and using molecular dynamics simulations, the stationary state achieved by self-gravitating systems in one, two and three dimensions and non-neutral plasmas in the dynamics of charged particle beams. We also analyse a model with out-of-equilibrium phase transitions (HMF). In all these cases, the theory proposed in this thesis is shown to be consistent with the numerical simulations applied.

Les interactions gravitationnelles et électrostatiques sont deux exemples fondamentaux de systèmes en interaction de longue portée. Les propriétés d'équilibre de modèles simples en interaction de longue portée sont bien comprises et révèlent des comportemens exotiques: capacité spécifique négative et inéquivalence des ensembles statistiques par exemple.<p><p>La compréhension de l'évolution dynamique dans le cas de systèmes en interaction de longue portée représente encore actuellement un défi théorique. Des modèles simples présentent des propriétés telles que des transitions de phase hors d'équilibre ou des états quasi-stationnaires.<p><p>Le but de la présente thèse est d'étudier les propriétés dynamiques de systèmes en interaction de longue portée pour des modèles à une dimension. La description cinétique adéquate est donnée par l'équation de Vlasov. Une théorie statistique proposée par D. Lynden-Bell est appropriée pour prédire dans certaines situations l'aboutissement de la dynamique. Un outil de simulation pour l'équation de Vlasov complète cette approche.<p><p>Une étude détaillée de la transition de phase dans le Laser à Electrons Libres est présentée et la transition est analysée à l'aide de la théorie de Lynden-Bell.<p>Ensuite, la présence d'étirement et de repliement est étudiée dans le modèle Hamiltonian Mean-Field en analogie avec la dynamique des fluides.<p>Enfin, un système de pendules découplés dont les états asymptotiques sont similaires à ceux du modèle Hamiltonian Mean-Field est introduit. Son évolution asymptotique est prédite par la théorie de Lynden-Bell et par une approche exacte. Ce système présente une évolution initiale rapide similaire à la relaxation violente présente dans des modèles plus compliqués. De plus, une transition de phase hors d'équilibre est trouvée si une condition d'auto-consistence est imposée.<p><p>En résumé, la présente thèse comporte des résultats originaux liés à la présence d'états quasi-stationnaires et de transitions de phase hors d'équilibre dans des modèles unidimensionnels en interaction de longue portée.<p>Les résultats concernant le Laser à Electrons Libres offrent une perspective de réalisation expérimentale des phénomènes décrits dans cette thèse.<p><p>/<p><p>Gravitational and electrostatic interactions are fundamental examples of systems with long-range interactions.<p>Equilibrium properties of simple models with long-range interactions are well understood and exhibit exotic behaviors: negative specific heat and inequivalence of statistical ensembles for instance.<p><p>The understanding of the dynamical evolution in the case of long-range interacting systems still represents a theoretical challenge. Phenomena such as out-of-equilibrium phase transitions or quasi-stationary states have been found even in simple models.<p><p>The purpose of the present thesis is to investigate the dynamical properties of systems with long-range interactions, specializing on one-dimensional models. The appropriate kinetic description for these systems is the Vlasov equation. A statistical theory devised by D. Lynden-Bell is adequate to predict in some situations the outcome of the dynamics.<p>A complementary numerical simulation tool for the Vlasov equation is developed.<p><p>A detailed study of the out-of-equilibrium phase transition occuring in the Free-Electron Laser is performed and the transition is analyzed with the help of Lynden-Bell's theory.<p>Then, the presence of stretching and folding in phase space for the Hamiltonian Mean-Field model is studied and quantified from the point of view of fluid dynamics.<p>Finally, a system of uncoupled pendula for which the asymptotic states are similar to the ones of the Hamiltonian Mean-Field model is introduced. Its asymptotic evolution is predicted via both Lynden-Bell's theory and an exact computation. This system displays a fast initial evolution similar to the violent relaxation found for interacting systems. Moreover, an out-of-equilibrium phase transition is found if one imposes a self-consistent condition on the system.<p><p>In summary, the present thesis discusses original results related to the occurence of quasi-stationary states and out-of-equilibrium phase transitions in 1D models with long-range interaction.<p>The findings regarding the Free-Electron Laser are of importance in the perspective of experimental realizations of the aforementioned phenomena.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

La première partie de la thèse étudie le diagramme de phase d’une généralisation de la chaîne de Kitaev qui décrit un système fermionique avec un pairing p-wave à long rayon qui tombe avec la distance ℓ comme 1/ℓα. On a analysé les lignes critiques, les corrélations et le comportement de l’entropie d’entanglement avec la taille du système. Nous avons démontré l’existence de deux régimes massifs, (i) où les fonctions de corrélation tombent exponentiellement à de courtes distances et comme puissance à de longues distances (α > 1), (ii) où elles tombent à puissance seulement (α < 1). Dans la seconde région l’entropie d’intrication d’un sous-système diverge logarithmiquement. Remarquablement, sur les lignes critiques, le pairing à long rayon brise la symètrie conforme du modèle pour des α suffisamment petits. On a prouvé ça en calculant aussi l’évolution temporelle de l’entropie d’intrication après un quench. Dans la seconde partie de la thèse nous avons analysé la dynamique de l’entropie d’intrication du modèle d’Ising avec un champ magnétique qui dépend linéairement du temps avec de différentes vitesses. Nous avons un régime adiabatique (de basses vitesses) lorsque le système évolue selon son état fondamental instantané; un sudden quench (de hautes vitesses) lorsque le système est congelé dans son état initial; un régime intermédiaire où l’entropie croît linéairement et, ensuite, elle montre des oscillations du moment que le système se trouve dans une superposition des états excités de l’Hamiltonienne instantanée. Nous avons discuté aussi du mécanisme de Kibble-Zurek pour la transition entre la phase paramagnétique et antiferromagnétique. / In the first part of the thesis, we propose an exactly-solvable one-dimensional model for fermions with long-range p-wave pairing decaying with distance ℓ as a power law 1/ℓα. We studied the phase diagram by analyzing the critical lines, the decay of correlation functions and the scaling of the von Neumann entropy with the system size. We found two gapped regimes, where correlation functions decay (i) exponentially at short range and algebraically at long range (α > 1), (ii) purely algebraically (α < 1). In the latter the entanglement entropy is found to diverge logarithmically. Most interestingly, along the critical lines, long-range pairing breaks the conformal symmetry for sufficiently small α. This can be detected also via the dynamics of entanglement following a quench. In the second part of the thesis we studied the evolution in time of the entanglement entropy for the Ising model in a transverse field varying linearly in time with different velocities. We found different regimes: an adiabatic one (small velocities) when the system evolves according the instan- taneous ground state; a sudden quench (large velocities) when the system is essentially frozen to its initial state; and an intermediate one, where the entropy starts growing linearly but then displays oscillations (also as a function of the velocity). Finally, we discussed the Kibble-Zurek mechanism for the transition between the paramagnetic and the ordered phase

Chemicals offer a wide range of desired functions and are used in a variety of consumer goods and industrial sectors. The number of individual synthetic organic chemicals produced and the total global chemical production volume are increasing. The majority of these anthropogenic chemicals are not monitored in environmental matrices nor in the indoor environment even though some are associated with undesirable consequences and the range of possible chemical impacts is still far from being fully understood. Chemicals that remain in the environment for a long time and/or distribute over a large area have high exposure potential, and will present particularly acute challenges if a currently unknown undesirable effect is discovered.  This thesis describes the development of a set of in silico methods to identify and prioritize chemicals with high exposure potential that are currently not subject to national or international restrictions. In brief, we i) compiled databases of contaminants of potential concern, ii) established models to predict key properties to fill data gaps in the absence of experimental data, and iii) developed and applied methods to screen chemicals to identify those that should be assigned high priority for future study.  Paper I delivers screening-level models to predict partition ratios of organic chemicals between polymeric materials commonly found indoors, and both air and water. These models can be used in high-throughput exposure assessment studies, passive sampling experiments, and models of emissions, fate and transport of chemicals.  Paper II presents a scoring method to prioritize 464 organic chemicals of emerging Arctic concern for their potential to fit a set of four exposure-based hazard profiles. These four profiles represent persistent organic pollutants (POPs) regulated under the Stockholm Convention, very persistent and very bioaccumulative substances (vPvBs) regulated under REACH and for two novel and unregulated profiles derived from the planetary boundary threats framework; airborne persistent contaminants (APCs) and waterborne persistent contaminants (WPCs). APCs and WPCs are chemicals that are mobile in air and water, respectively, and that contaminate the environment in a poorly reversible manner due to their persistence. The prioritization method is based on a reference set of 148 chemicals that is used to contextualize the scoring results.  Paper III describes the prioritization of 8,648 chemicals that were reportedly produced in five OECD countries. Paper III elucidates the relationship between the elemental composition of these chemicals and the exposure-based hazard scores, and presents a strategy to disentangle overlaps among the four exposure hazard profiles by categorizing chemicals according to the spatial coverage of profiles they best fit.  Paper IV focuses on refining the prioritization method described in Papers II and III using a set of 5,600 hypothetical chemicals. The refined method is used to prioritize the chemicals from Papers II and III, and an additional 4,567 chemicals from the REACH database.  The in silico methods developed in this thesis can be applied to conduct screening-level exposure assessments using only chemical structures as a starting point. Substances prioritized as having high potential to be POPs, vPvB, APC, or WPC should be considered for more detailed study to unequivocally determine their identity and physicochemical properties. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.</p>

This work deals with studying a molecular mechanism of anticancer effect of a new platinum - based drug. The qualities of still unknow dinuclear platinum komplex (BBR3571-DACH) were parallelly studied together with clinically time-tested and used mononuclear platinum complex DACH. Earlier essays demostrated, that DNA is the critical target for the cytostatic activity of platinum compounds. Altered properties of DNA and binding characteristics of these two platinum compounds were monitored by several different bioanalytical methods (differential pulse polarography, UV-VIS spectrophotometry, fluorescence spectrophotometry, CD spectroscopy and electrophoresis) after modification of DNA by both of platinum complexes. For the compounds BBR3571-DACH and DACH it was determined that the DNA binding is rapid and bifunctional. The stabilizing effect on DNA was significant particularly after modification of DNA by dinuclear komplex, while denaturating effect wasn´t proved at all. The results also indicate that dinuclear platinum complex BBR3571-DACH probably does not participate on formation of long-range cross-links like other early studied polynuclear platinum complexes.

Questa tesi di dottorato studia l’interazione della cooperatività con il rumore in sistemi realistici, focalizzandosi principalmente sulla superradianza. Gli effetti cooperativi emergono dall’interazione collettiva di un insieme di elementi con un campo esterno. Esempi degni di nota sono la superconduttività, dove le coppie di Cooper elettroniche interagiscono con le vibrazioni reticolari, le eccitazioni di plasma, che sorgono dall'interazione collettiva degli elettroni in un metallo con il campo coulombiano, e la superradianza, ovvero quel processo di emissione spontanea cooperativa che sorge da un aggregato di emettitori identici. Gli effetti cooperativi sono tipicamente robusti al disordine e al rumore, cosa che li rende interessanti per delle applicazioni a dispositivi quantistici che possano operare a temperatura ambiente. In questo lavoro, inizialmente, introduciamo un formalismo di “master equations” che descrive l’accoppiamento collettivo di un aggregato di emettitori/assorbitori con il campo elettromagnetico, valido quando le dimensioni dell'aggregato sono sia maggiori che minori della lunghezza d’onda emessa/assorbita. Inoltre, il formalismo è valido per accoppiamento sia debole che forte con il campo elettromagnetico e, cosa più importante, permette di descrivere correttamente la superradianza in diversi regimi. In tale formalismo, studiamo l’interazione tra superradianza e rumore termico sia per nanotubi molecolari (di dimensioni minori della lunghezza d’onda associata alla transizione) che sono presenti nei complessi antenna fotosintetici dei Green Sulfur Bacteria, sia pure per superreticoli di quantum dots di nuova generazione, aventi dimensioni maggiori della lunghezza d’onda emessa. In entrambi i casi si dimostra che la coerenza può permanere in presenza di rumore termico alle temperature a cui questi sistemi sono stati analizzati sperimentalmente (temperatura ambiente per i nanotubi molecolari, e 6 K per i superreticoli di quantum dots). Nello specifico, nei nanotubi molecolari mostriamo che la macroscopica delocalizzazione coerente delle eccitazioni a temperatura ambiente, che copre centinaia di molecole, può essere considerata un effetto emergente che origina dall’effetto combinato della specifica disposizione geometrica delle molecole e della presenza di accoppiamenti tra subunità del cilindro, incrementati dagli effetti cooperativi. Questi risultati aprono la strada a nuovi modi per ingegnerizzare dei “quantum wires” robusti al rumore grazie alla cooperatività. Inoltre, la presente analisi di sistemi allo stato solido basati su superreticoli di “quantum dots” di perovskite (CsPbBr3) fornisce una base teorica in grado di comprendere recenti osservazioni di emissione superradiante. Sulla base della nostra teoria, suggeriamo che futuri esperimenti dove si utilizzino quantum dots più piccoli, potrebbe aumentare significativamente la robustezza del sistema al rumore termico, aprendo la strada verso la superradianza a temperatura ambiente in sistemi allo stato solido. Si considerano anche i complessi antenna dei Purple Bacteria, dove è ben risaputo che gli effetti cooperativi incrementano il trasferimento e l’accumulo di eccitazioni generate dalla luce assorbita. Mostriamo come queste proprietà possono essere sfruttate per creare un laser ispirato a sistemi biologici e basato su aggregati molecolari, dove la luce solare, benché debole, sarebbe utilizzata come sorgente di pompaggio. Il trasferimento efficiente di energia dentro questo sistema, all’atto pratico, focalizzerebbe l’eccitazione assorbita in direzione di un dimero molecolare, composto da una coppia di molecole interagenti, opportunamente scelte. L’orientazione dei momenti di dipolo di transizione in ciascun dimero è tale da concentrare tutta l’intensità del dipolo nel livello a più alta energia, lasciando lo stato eccitonico inferiore otticamente inattivo. Un dimero molecolare in tale configurazione, che è ideale per ottenere inversione di popolazione, è chiamato “H-dimer”. Tale H-dimer, nell’archittettura qui proposta per un laser ispirato a sistemi biologici, è posto al centro di un aggregato molecolare ispirato a sistemi biologici. Gli H-dimers, eccitati dagli aggregati molecolari circostanti, raggiungono inversione di popolazione e, dunque, possono emettere luce laser quando tali aggregati sono posti in una cavità ottica. Convertire l’energia incoerente fornita dal Sole in un fascio laser coerente supererebbe diverse limitazioni pratiche inerenti all’utilzzo della luce solare come sorgente di energia pulita. Per esempio, i fasci laser sono molto efficienti nell’avviare reazioni chimiche che convertono la luce solare in energia chimica. Inoltre, dal momento che i complessi fotosintetici batterici tendono ad operare nella regione spettrale del vicino infrarosso, la nostra proposta si presta in modo naturale a realizzare laser a infrarossi a corta lunghezza d’onda, i cui fasci viaggerebbero per lunghe distanze senza quasi perdere energia, quindi distribuendo in modo efficiente l’energia solare raccolta. Nella ricerca di un meccanismo comune alla cooperatività e alla sua robustezza, abbiamo confrontato il modello delle coppie di Cooper della superconduttività con la superradianza in singola eccitazione, mostrando molte somiglianze tra i due fenomeni: in particolare, i sistemi superradianti presentano una “gap” immaginaria nel piano complesso (ovvero, una segregazione tra i tempi di vita degli autostati del sistema) che, in modo simile alla gap superconduttiva, rende questi sistemi robusti al rumore statico. Più in generale, mostriamo che ogni interazione a lungo raggio tra i costituenti di un sistema induce effetti collettivi, manifestati da delle gap nello spettro eccitonico. Perciò, la nostra analisi successiva considera l’effetto delle interazioni a lungo raggio sul trasporto eccitonico lungo catene disordinate. Dimostriamo che la presenza di uno stato collettivo ben separato dagli altri stati influenza tutto lo spettro del sistema, generando dei regimi molto controintuitivi dove il trasporto è incrementato dal disordine o è indipendente da esso, e tali regimi si estendono su molti ordini di grandezza nell’intensità del disordine. Dimostriamo anche che una catena fortemente accoppiata a un modo del campo elettromagnetico in una cavità ottica è equivalente a una catena con interazione a lungo raggio, mostrandosi dunque molto promettente per esperimenti e applicazioni future. Nello specifico, mostriamo che catene molecolari realistiche, ioni intrappolati realizzati allo stato dell’arte e atomi di Rydberg sono tutti in grado di raggiungere l’intensità di interazione a lungo raggio tale per cui il trasporto sarebbe incrementato dal disordine o indipendente da esso, puntando alla realizzazione di un trasporto di energia senza dissipazione in “quantum wires” disordinati. / This Ph.D. thesis studies the interplay of cooperativity and noise in realistic systems, largely focusing on superradiance. Cooperative effects emerge from the collective interaction of an ensemble of elements to an external field. Notable examples are superconductivity, where the electron Cooper pairs interact with the lattice vibrations, plasmon excitations, arising from the collective interaction of electrons in a metal with the Coulomb field, and superradiance, that is a cooperative spontaneous emission process stemming from an aggregate of identical emitters. Cooperative effects are typically robust to disorder and noise, making them interesting for applications to quantum devices operating at room temperature. In this work, we first present a general master equation formalism that describes the collective coupling of an aggregate of emitters/absorbers to the electromagnetic field, valid both when the size of the aggregate is larger or smaller than the emitted/absorbed wavelength. Also, the formalism is valid both for weak and strong coupling of the emitters to the electromagnetic field and, most importantly, it allows to correctly describe superradiance in different regimes. Within such formalism, the interplay of superradiance and thermal noise is studied both for molecular nanotubes (of size smaller than the transition wavelength) that are present in the antenna complexes of photosynthetic Green Sulfur Bacteria, and also for novel solid state quantum dot superlattices, having size larger than the emitted wavelength. In both cases it is shown that coherence can persist in presence of thermal noise at the temperatures where these systems have been experimentally analyzed (room temperature for molecular nanotubes, and 6 K for quantum dot superlattices). Specifically, in natural molecular nanotubes we show that the macroscopic coherent delocalization of the excitation at room temperature, covering hundreds of molecules, can be considered an emergent effect originating from the combined effect of the specific geometric disposition of the molecules and the presence of cooperatively enhanced couplings between cylinder subunits. These results open the path to new ways of engineering quantum wires robust to noise thanks to cooperativity. Moreover, our analysis of solid state systems based on perovskite (CsPbBr3) quantum dot superlattices provides a theoretical framework able to explain recent observations of superradiant emission. Based on our theory, we suggest that further experiments, using smaller quantum dots, could significantly increase the robustness of the system to thermal noise, paving the way towards room-temperature superradiance in solid-state systems. We also considered the antenna complexes of Purple Bacteria, where cooperative effects are well known to boost the transfer and storage of photo-absorbed excitations. We show how these properties can be exploited to create a bio-inspired molecular aggregate laser medium, where natural sunlight, although weak, would be used as a pumping source. The efficient energy transfer within this system would effectively focus the absorbed excitation on a suitably chosen molecular dimer, composed by a pair of interacting molecules. The orientation of the molecule transition dipole moment in each dimer is such to concentrate all the dipole strength in the highest energy level, leaving the lower excitonic state dark. A molecular dimer in such configuration, which is ideal to achieve population inversion, is called H-dimer. Such an H-dimer in our proposed architecture for a bio-inspired laser medium, is placed at the center of the bio-inspired molecular aggregates. The H-dimers, pumped by the surrounding molecular aggregates, reach population inversion and, therefore, can lase when such aggregates are placed in an optical cavity. Turning the incoherent energy supply provided by the Sun into a coherent laser beam would overcome several of the practical limitations inherent in using sunlight as a source of clean energy. For example, laser beams are highly effective at driving chemical reactions which convert sunlight into chemical energy. Further, since bacterial photosynthetic complexes tend to operate in the near-infrared spectral region, our proposal naturally lends itself for realising short-wavelength infrared lasers which would allow their beams to travel nearly losslessly over large distances, thus efficiently distributing the collected sunlight energy. In search of a common mechanism to cooperativity and its robustness, we have compared the Cooper pair model of superconductivity and single-excitation superradiance, showing many similarities between the two: in particular, superradiant systems present an imaginary gap in the complex plane (that is, a segregation between the lifetimes of the system eigenstates) that, similarly to the superconducting gap, makes these systems robust to static disorder. More in general, we show that any long-range interaction between the constituents of a system generates collective behaviours, manifested by gaps in the excitonic spectrum. Therefore, our further analysis considers the effect of long-range interactions on excitation transport along disordered chains. We show that the presence of a gapped, collective state affects the whole spectrum of the system, generating quite counter-intuitive disorder-enhanced and disorder-independent transport regimes, that extend over many orders of magnitude of the disorder strength. We also prove that a chain strongly coupled to a cavity mode is equivalent to a long-range interacting chain, thus being very promising for future experiments and applications. Specifically, we show that realistic molecular chains, state-of-the-art trapped ions and Rydberg atoms are all able to reach the needed long-range interaction strength that would show disorder-enhanced or disorder-independent transport, aiming to the realization of dissipationless transport of energy in disordered quantum wires.

Methods of slab-geometry molecular dynamics computer simulation were tested, compared, and applied to the prediction of activity coefficients, interfacial electrochemistry characterization, and ion transport through a model biological channel-membrane structure. The charged-sheets, 2-D Ewald, corrected 3-D Ewald, and corrected particle-particle-particle-mesh (P3M) methods were compared for efficiency and applicability to slab-geometry electrolyte systems with discrete water molecules. The P3M method was preferred for long-range force calculation in the problems of interest and was used throughout. The osmotic molecular dynamics method (OMD) was applied to the prediction of liquid mixture activity coefficients for six binary systems: methanol/n-hexane, n-hexane/n-pentane, methanol/water, chloroform/acetone, n-hexane/chloroform, methanol/ chloroform. OMD requires the establishment of chemical potential equilibrium across a semi-permeable membrane that divides the simulation cell between a pure solvent chamber and a chamber containing a mixture of solvent and solute molecules in order to predict the permeable component activity coefficient at the mixture side composition according to a thermodynamic identity. Chemical potential equilibrium is expedited by periodic adjustment of the mixture side chamber volume in response to the observed solvent flux. The method was validated and shown to be able to predict activity coefficients within the limitations of the simple models used. The electrochemical double layer characteristics for a simple electrolyte with discrete water molecules near a charged electrode were examined as a function of ion concentration, electrode charge, and ion size. The fluid structure and charge buildup near the electrode, the voltage drop across the double layer, and the double layer capacitance were studied and were found to be in reasonable agreement with experimental findings. Applied voltage non-equilibrium molecular dynamics was used to calculate the current-voltage relationship for a model biological pore. Ten 10-nanosecond trajectories were computed in each of 10 different conditions of concentration and applied voltage. The channel-membrane structure was bathed in electrolyte including discrete water molecules so that solvation, entry, and exit effects could be studied. Fluid structure, ion dynamics, channel selectivity, and potential gradients were examined. This work represents the first such channel study that does not neglect the vital contributions of discrete water molecules.

Described in many studies as dangerous for the environment and potentially carcinogenic for humans, Chlorinated Paraffins (CPs) are easily widespread due to their substantial production and use in different products. Previous studies reported the presence of CPs in different plastic polymers. However, the impact of recycled content in plastic materials on the CPs levels hasn’t particularly been considered. Recycling plastics is becoming essential but the accumulative potential of pollutants, such as CPs, need investigations. The presence of CPs in both virgin and mixed recycled and virgin plastics was studied. Plastic pellets and plastic pieces from products made of three polymer types:Poly(methyl 2-methylpropenoate) (PMMA), Thermoplastic Rubber (TPR) and Thermoplastic Polyurethane (TPU) were analysed. A solid-liquid extraction assisted by ultrasonication was performed, followed by cleanup using silica. CPs in plastic extracts were analysed by Gas Chromatography Orbitrap High Resolution Mass Spectroscopy (GC-Orbitrap-HRMS). Because of the high volatility characteristic of long chain Chlorinated Paraffins (LCCPs), only short chain and medium chain Chlorinated Paraffins (SCCPs and MCCPs ) have been studied in this project. Interesting variations in the presence of SCCPs and MCCPs have been observed from one polymer type to another. In the results, we show that MCCPs were less frequently detected compared to SCCPs. A higher detection frequency of CPs was observed for samples containing recycled plastics. The results indicate that CPs are present in plastic polymers (TPU, PMMA and TPR) and that the content of recycled material has a direct impact on the levels of SCCPs and MCCPs.