Publications

Abstract A novel formulation of cationic liposomes was studied by mixing dipalmitoylphosphatidylcholine (DPPC) with tetradecyltrimethylammonium bromide gemini surfactants with different alkane spacer groups lengths attached to their ammonium head-groups. The physicochemical characterization of the cationic liposomes was obtained by combining experimental results from differential scanning microcalorimetry (DSC) with molecular dynamic simulations, in order to understand their structural configuration. An adapted Ising model was used to interpret the results in terms of cooperativity of the phase transitions. The gemini surfactants partition into the lipid bilayer of DPPC liposomes, and the induced changes in colloidal stability and phase transition were analyzed in detail.The DPPC liposomes became positively charged upon gemini surfactant partition, showing increased colloidal stability. Our results show signif-icant differences in structural configuration between gemini surfactants with short and long spacer lengths. While gemini with shorter spacers allocate within the lipid bilayer with both headgroups in the same layer, geminis with longer spacers unexpectedly intercalate in the lipid membrane in a partic-ular zig-zag configuration, with each headgroup located at a different side of the bilayer, altering the cou-pling degree parameters of the membrane's phase transition.The extraordinary increase of colloidal stability of DPPC liposomes with gemini surfactants at very low molar ratio and the possibility to tune the physicochemical properties of the membrane by control de spacer length of the geminis opens new possibilities for cationic liposomal formulations with potential applications in vaccines, drug/gene delivery or biosensing.(c) 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http:// creativecommons.org/licenses/by/4.0/).

Abstract Ionic liquids (ILs) have been widely used for energy storage and conversion devices due to their negligible vapor pressure, high thermal stability, and outstanding interfacial properties. Notably, the interfacial nanostructure and the wettability of thin ionic liquid films on solid surfaces are of utmost relevance in nanosurface science and technology. Herein, a reproducible physical vapor deposition methodology was used to fabricate thin films of four alkylimidazolium bis(trifluoromethylsulfonyl)imide ILs. The effect of the cation alkyl chain length on the wettability of ILs was explored on different surfaces: gold (Au); silver (Ag); indium-tin oxide (ITO). High-resolution scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to evaluate the morphology of the produced micro- and nanodroplets and films. SEM and AFM results revealed an island growth for all the ILs deposited on ITO and Ag surfaces, with a lower minimum free area to promote nucleation (MFAN) in Ag and higher wettability for ILs having larger non-polar domains. The low wettability of ITO by the studied ILs was highlighted. For long-chain ILs, nucleation and growth mechanisms were strongly conditioned by coalescence processes. The results also supported the higher affinity of the ILs to the Au surface. The increase in the length of the cation alkyl chain was found to promote a better film adhesion inducing a 2D growth and higher wetting ability.

Abstract This study investigates the nucleation and growth of micro-/nanodroplets of triflate-based ionic liquids (ILs) fabricated by vapor deposition on different surfaces: indium tin oxide (ITO); silver (Ag); gold (Au). The ILs studied are constituted by the alkylimidazolium cation and the triflate anion-[CnC1 im][OTF] series. One of the key issues that determine the potential applications of ILs is the wettability of surfaces. Herein, the wetting behavior was evaluated by changing the cation alkyl chain length (C-2 to C-10). A reproducible control of the deposition rate was conducted employing Knudsen cells, and the thin-film morphology was evaluated by high-resolution scanning electron microscopy (SEM). The study reported here for the [C(n)C(1)im][OTF] series agrees with recent data for the [C(n)C(1)im][NTf2] congeners, highlighting the higher wettability of the solid substrates to long-chain alkylimidazolium cations. Compared to [NTf2], the [OTF] series evidenced an even more pronounced wetting ability on Au and coalescence processes of droplets highly intense on ITO. Higher homogeneity and film cohesion were found for cationic groups associated with larger alkyl side chains. An island growth was observed on both Ag and ITO substrates independently of the cation alkyl chain length. The Ag surface promoted the formation of smaller-size droplets. A quantitative analysis of the number of microdroplets formed on Ag and ITO revealed a trend shift around [C(6)C(1)im][OTF], emphasizing the effect of the nanostructuration intensification due to the formation of nonpolar continuous domains.

Abstract Host defense peptides (HDPs) are short cationic peptides that play a key role in the innate immune response of all living organisms. Their action mechanism does not depend on the presence of protein receptors, but on their ability to target and disrupt the membranes of a wide range of pathogenic and pathologic cells which are recognized by their specific compositions, typically with a relatively high concentration of anionic lipids. Lipid profile singularities have been found in cancer, inflammation, bacteria, viral infections, and even in senescent cells, enabling the possibility to use them as therapeutic targets and/or diagnostic biomarkers. Molecular dynamics (MD) simulations are extraordinarily well suited to explore how HDPs interact with membrane models, providing a large amount of qualitative and quantitative information that, nowadays, cannot be assessed by wet-lab methods at the same level of temporal and spatial resolution. Here, we present SuPepMem, an open-access repository containing MD simulations of different natural and artificial peptides with potential membrane lysis activity, interacting with membrane models of healthy mammal, bacteria, viruses, cancer or senescent cells. In addition to a description of the HDPs and the target systems, SuPepMem provides both the input files necessary to run the simulations and also the results of some selected analyses, including structural and MD-based quantitative descriptors. These descriptors are expected to be useful to train machine learning algorithms that could contribute to design new therapeutic peptides. Tools for comparative analysis between different HDPs and model membranes, as well as to restrict the queries to structural and time-averaged properties are also available. SuPepMem is a living project, that will continuously grow with more simulations including peptides of different sequences, MD simulations with different number of peptide units, more membrane models and also several resolution levels. The database is open to MD simulations from other users (after quality check by the SuPepMem team). SuPepMem is freely available under https://supepmem.com/. (C) 2022 The Authors. Published by Elsevier B.V. on behalf of Research Network of Computational and Structural Biotechnology.

Abstract Carbamic-carbonic anhydrides are elusive species that have been only indirectly detected under controlled conditions. This functional group is transiently formed during the reaction of secondary amines with anhydrides in the presence of nucleophilic catalysts such as 4-(dimethylamino)pyridine. In this work, the synthesis and isolation of two carbamic-carbonic anhydrides are reported, including the first-ever solid-state structure of this functional group. The remarkable stability of these chiral carbamic-carbonic anhydrides allowed their study by NMR, HRMS, FTIR-ATR, and thermal analysis techniques (DSC and TGA). A thorough analysis of the bonding situation by computational studies hints that the origin of this unusual stability relies on n -> sigma* stabilizing orbital interactions hampering the occurrence of decarboxylation.

Abstract In this investigation, a hybrid-biocomposite "ZnO-Bentonite/Chitosan" was synthesized using inexpensive and environmentally friendly materials (Bentonitechitosan) and (ZnO). It was used as a photocatalyst for water remediation. The structural, optical, thermal, and morphological properties of the synthesized hybrid-biocomposite were investigated using XRD, FTIR spectroscopy, UV-vis diffuse reflectance spectroscopy, TGA, XPS, and SEM-EDS. The thermal measurements showed that the decomposition of CS was postponed progressively by adding PB and ZnO, and the thermal stability of the synthesized hybrid-biocomposite was improved. The characterization results highlighted strong interactions between the C-O, C=O, -NH2, and OH groups of chitosan and the alumina-silica sheets of bentonite on the one side, and between the functional groups of chitosan (-NH2, OH) and ZnO on the other side. The photocatalytic efficiency of the prepared hybrid-biocomposite was assessed in the presence of Methyl Orange (MO). The experiments carried out in the dark showed that the MO removal increased in the presence of Zn-PB/CS hybrid-biocomposite (86.1%) by comparison with PB (75.8%) and CS (65.4%) materials. The photocatalytic experiments carried out under visible light showed that the MO removal increased 268 times in the presence of Zn-PB/CS by comparison withZnO.The holes trapping experiments indicated that they are the main oxidative active species involved in the MO degradation under both UV-A and visible light irradiations.