Silica Monolith for the Removal of Pollutants from Gas and Aqueous Phases

This study focused on the application of mesoporous silica monoliths for the removal of organic pollutants. The physico-chemical textural and surface properties of the monoliths were investigated. The homogeneity of the textural properties along the entire length of the monoliths was assessed, as well as the reproducibility of the synthesis method. The adsorption properties of the monoliths for gaseous toluene, as a model of Volatile Organic Compounds (VOCs), were evaluated and compared to those of a reference meso-structured silica powder (MCM-41) of commercial origin. Silica monoliths adsorbed comparable amounts of toluene with respect to MCM-41, with better performances at low pressure. Finally, considering their potential application in water phase, the adsorption properties of monoliths toward Rhodamine B, selected as a model molecule of water soluble pollutants, were studied together with their stability in water. After 24 h of contact, the silica monoliths were able to adsorb up to the 70% of 1.5 × 10⁻² mM Rhodamine B in water solution.     

The Fumarprotocetraric Acid Inhibits Tau Covalently,Avoiding Cytotoxicity of Aggregates in Cells

Neurodegenerative disorders, including Tauopathies that involve tau protein, base their pathological mechanism on forming proteinaceous aggregates, which has a deleterious effect on cells triggering an inflammatory response. Moreover, tau inhibitors can exert their mechanism of action through noncovalent and covalent interactions. Thus, Michael’s addition appears as a feasible type of interaction involving an α, β unsaturated carbonyl moiety to avoid pathological confirmation and further cytotoxicity. Moreover, we isolated three compounds from Antarctic lichens Cladonia cariosa and Himantormia lugubris: protolichesterinic acid (1), fumarprotocetraric acid (2), and lichesterinic acid (3). The maleimide cysteine labeling assay showed that compounds 1, 2, and 3 inhibit at 50 µM, but compounds 2 and 3 are statistically significant. Based on its inhibition capacity, we decided to test compound 2 further. Thus, our results suggest that compound 2 remodel soluble oligomers and diminish β sheet content, as demonstrated through ThT experiments. Hence, we added externally treated oligomers with compound 2 to demonstrate that they are harmless in cell culture. First, the morphology of cells in the presence of aggregates does not suffer evident changes compared to the control. Additionally, the externally added aggregates do not provoke a substantial LDH release compared to the control, indicating that treated oligomers do not provoke membrane damage in cell culture compared with aggregates alone. Thus, in the present work, we demonstrated that Michael’s acceptors found in lichens could serve as a scaffold to explore different mechanisms of action to turn tau aggregates into harmless species.     

Construction of the Lyapunov Spectrum in a Chaotic System Displaying Phase Synchronization

We consider a three-dimensional chaotic system consisting of the suspension of Arnold’s cat map coupled with a clock via a weak dissipative interaction. We show that the coupled system displays a synchronization phenomenon, in the sense that the relative phase between the suspension flow and the clock locks to a special value, thus making the motion fall onto a lower dimensional attractor. More specifically, we construct the attractive invariant manifold, of dimension smaller than three, using a convergent perturbative expansion. Moreover, we compute via convergent series the Lyapunov exponents, including notably the central one. The result generalizes a previous construction of the attractive invariant manifold in a similar but simpler model. The main novelty of the current construction relies in the computation of the Lyapunov spectrum, which consists of non-trivial analytic exponents. Some conjectures about a possible smoothening transition of the attractor as the coupling is increased are also discussed.     

On the Laplace Transform of the Lognormal Distribution

Integral transforms of the lognormal distribution are of great importance in statistics and probability, yet closed-form expressions do not exist. A wide variety of methods have been employed to provide approximations, both analytical and numerical. In this paper, we analyse a closed-form approximation \(\widetilde {\mathcal {L}}(\theta )\) of the Laplace transform \(\mathcal {L}(\theta )\) which is obtained via a modified version of Laplace’s method. This approximation, given in terms of the Lambert W(?) function, is tractable enough for applications. We prove that ~(??) is asymptotically equivalent to ?(??) as ?? → ∞. We apply this result to construct a reliable Monte Carlo estimator of ?(??) and prove it to be logarithmically efficient in the rare event sense as ?? → ∞.     

Mechanism Integrated Information

The Integrated Information Theory (IIT) of consciousness starts from essential phenomenological properties, which are then translated into postulates that any physical system must satisfy in order to specify the physical substrate of consciousness. We recently introduced an information measure (Barbosa et al., 2020) that captures three postulates of IIT—existence, intrinsicality and information—and is unique. Here we show that the new measure also satisfies the remaining postulates of IIT—integration and exclusion—and create the framework that identifies maximally irreducible mechanisms. These mechanisms can then form maximally irreducible systems, which in turn will specify the physical substrate of conscious experience.     

Arbitrary-Order Finite-Time Corrections for the Kramers–Moyal Operator

With the aim of improving the reconstruction of stochastic evolution equations from empirical time-series data, we derive a full representation of the generator of the Kramers–Moyal operator via a power-series expansion of the exponential operator. This expansion is necessary for deriving the different terms in a stochastic differential equation. With the full representation of this operator, we are able to separate finite-time corrections of the power-series expansion of arbitrary order into terms with and without derivatives of the Kramers–Moyal coefficients. We arrive at a closed-form solution expressed through conditional moments, which can be extracted directly from time-series data with a finite sampling intervals. We provide all finite-time correction terms for parametric and non-parametric estimation of the Kramers–Moyal coefficients for discontinuous processes which can be easily implemented—employing Bell polynomials—in time-series analyses of stochastic processes. With exemplary cases of insufficiently sampled diffusion and jump-diffusion processes, we demonstrate the advantages of our arbitrary-order finite-time corrections and their impact in distinguishing diffusion and jump-diffusion processes strictly from time-series data.     

On the Density of Transitive Tournaments

We prove that for every fixed k, the number of occurrences of the transitive tournament Tr_k of order k in a tournament  on n vertices is asymptotically minimized when  is random. In the opposite direction, we show that any sequence of tournaments  achieving this minimum for any fixed  is necessarily quasirandom. We present several other characterizations of quasirandom tournaments nicely complementing previously known results and relatively easily following from our proof techniques.     

Multiple straight-line fitting using a Bayes factor

This paper introduces a Bayesian approach to solve the problem of fitting multiple straight lines to a set of 2D points. Other approaches use many arbitrary parameters and threshold values, the proposed criterion uses only the parameters of the measurement errors. Models with multiple lines are useful in many applications, this paper analyzes the performance of the new approach to solve a classical problem in robotics: finding a map of lines from laser measurements. Tests show that the Bayesian approach obtains reliable models.     

Molecular Modelling and Simulations of Light-Harvesting Decanuclear Ru-Based Dendrimers for Artificial Photosynthesis

The structure of a decanuclear photo- and redox-active dendrimer based on Ru(II) polypyridine subunits, suitable as a light-harvesting multicomponent species for artificial photosynthesis, has been investigated by means of computer modelling. The compound has the general formula [Ru{(μ-dpp)Ru[(μ-dpp)Ru(bpy)₂]₂}₃](PF₆)₂₀ ( Ru10 ; bpy=2,2′-bipyridine; dpp=2,3-bis(2′-pyridyl)pyrazine). The stability of possible isomers of each monomer was investigated by performing classical molecular dynamics (MD) and quantum mechanics (QM) simulations on each monomer and comparing the results. The number of stable isomers is reduced to 36 with a prevalence of MER isomerism in the central core, as previously observed by NMR experiments. The simulations on decanuclear dendrimers suggest that the stability of the dendrimer is not linked to the stability of the individual monomers composing the dendrimer but rather governed by the steric constrains originated by the multimetallic assembly. Finally, the self-aggregation of Ru10 and the distribution of the counterions around the complexes is investigated using Molecular Dynamics both in implicit and explicit acetonitrile solution. In representative examples, with nine and four dendrimers, the calculated pair distribution function for the ruthenium centers suggests a self-aggregation mechanism in which the dendrimers are approaching in small blocks and then aggregate all together. Scanning transmission electron microscopy complements the investigation, supporting the formation of different aggregates at various concentrations.     

Multistep Continuous Flow Synthesis of Isolable NH2-Sulfinamidines via Nucleophilic Addition to Transient Sulfurdiimide

The growing interest in novel sulfur pharmacophores led to recent advances in the synthesis of some S(IV) and S(VI) motifs. However, preparation and isolation of uncommon primary sulfinamidines, the aza-analogues of sulfinamides, is highly desirable. Here we report a multistep continuous flow synthesis of poorly explored NH₂-sulfinamidines by nucleophilic attack of organometallic reagents to in situ prepared N-(trimethylsilyl)-N-trityl-λ⁴-sulfanediimine (Tr−N=S=N−TMS). The transformation can additionally be realized under mild conditions, at room temperature, via a highly chemoselective halogen-lithium exchange of aryl bromides and iodides with n-butyllithium. Moreover, the synthetic potential of the methodology was assessed by exploring further manipulations of the products and accessing novel S(IV) analogues of celecoxib, tasisulam, and relevant sulfinimidoylureas.