Publications

Abstract Surgical site infections (SSIs) are common postoperative occurrences due to contamination of the surgical wound or implanted medical devices with community or hospital-acquired microorganisms, as well as other endogenous opportunistic microbes. Despite numerous rules and guidelines applied to prevent these infections, SSI rates are considerably high, constituting a threat to the healthcare system in terms of morbidity, prolonged hospitalization, and death. Approximately 80% of human SSIs, including chronic wound infections, are related to biofilm-forming bacteria. Biofilm-associated SSIs are extremely difficult to treat with conventional antibiotics due to several tolerance mechanisms provided by the multidrug-resistant bacteria, usually arranged as polymicrobial communities. In this review, novel strategies to control, i.e., prevent and eradicate, biofilms in SSIs are presented and discussed, focusing mainly on two attractive approaches: the use of nanotechnology-based composites and natural plant-based products. An overview of new therapeutic agents and strategic approaches to control epidemic multidrug-resistant pathogenic microorganisms, particularly when biofilms are present, is provided alongside other combinatorial approaches as attempts to obtain synergistic effects with conventional antibiotics and restore their efficacy to treat biofilm-mediated SSIs. Some detection and real-time monitoring systems to improve biofilm control strategies and diagnosis of human infections are also discussed.

Abstract Covering: 2009 to 2021 Antimicrobial resistance is now rising to dangerously high levels in all parts of the world, threatening the treatment of an ever-increasing range of infectious diseases. This has becoming a serious public health problem, especially due to the emergence of multidrug-resistance among clinically important bacterial species and their ability to form biofilms. In addition, current anti-infective therapies have low efficacy in the treatment of biofilm-related infections, leading to recurrence, chronicity, and increased morbidity and mortality. Therefore, it is necessary to search for innovative strategies/antibacterial agents capable of overcoming the limitations of conventional antibiotics. Natural compounds, in particular those obtained from plants, have been exhibiting promising properties in this field. Plant secondary metabolites (phytochemicals) can act as antibiofilm agents through different mechanisms of action from the available antibiotics (inhibition of quorum-sensing, motility, adhesion, and reactive oxygen species production, among others). The combination of different phytochemicals and antibiotics have revealed synergistic or additive effects in biofilm control. This review aims to bring together the most relevant reports on the antibiofilm properties of phytochemicals, as well as insights into their structure and mechanistic action against bacterial pathogens, spanning December 2008 to December 2021.

Abstract The development of energy storage devices with better performance relies on the use of innovative materials and electrolytes, aiming to reduce the carbon footprint through the screening of low toxicity electrolytes and solvent-free electrode design protocols. The application of nanostructured carbon materials with high specific surface area, to prepare composite electrodes, is being considered as a promising starting point towards improving the power and energy efficiency of energy storage devices. Non-aqueous electrolytes synthesized using greener approaches with lower environmental impact make deep eutectic solvents (DES) promising alternatives for electrochemical energy storage and conversion applications. Accordingly, this work proposes a systematic study on the effect of the composition of DES containing a diol and an amide as HBD (hydrogen bond donor: 1,2-propylene glycol and urea), on the electrochemical performance of graphene and graphite composite electrodes/DES electrolyte interface. Glassy carbon (GC) was selected as the bare electrode material substrate to prepare the composite formulations since it provides an electrochemically reproducible surface. Gravimetric capacitance was measured for commercial graphene and commercial graphite/GC composite electrodes in contact with choline chloride, complexed with 1,2-propylene glycol, and urea as the HBD in 1:2 molar ratio. The electrochemical stability was followed by assessing the charge/discharge curves at 1, 2, and 4 A g−1. For comparison purposes, a parallel study was performed using commercial graphite. A four-fold increase in gravimetric capacitance was obtained when replacing commercial graphite (1.70 F g−1) by commercial graphene (6.19 F g−1) in contact with 1,2-propylene glycol-based DES. When using urea based DES no significant change in gravimetric capacitance was observed when commercial graphite is replaced by commercial graphene.

Abstract Hypothesis: The injection of air into the sample cell of an isothermal titration calorimeter containing a liquid provides a rich-in-information signal, with a periodic contribution arising from the creation, growing and release of bubbles. The identification and analysis of such contributions allow the accurate determination of the surface tension of the target liquid. Experiments: Air is introduced at a constant rate into the sample cell of the calorimeter containing either a pure liquid or a solution. The resulting calorimetric signal is analyzed by a new algorithm, which is implemented into a computational code. Findings: The thermal power generated by our experiments is often noisy, thus hiding the periodic signal arising from the bubbles' formation and release. The new algorithm was tested with a range of different types of calorimetric raw data, some of them apparently being just noise. In all cases, the contribution of the bubbles to the signal was isolated and the corresponding period was successfully determined in an automated way. It is also shown that two reference measurements suffice to calibrate the instrument at a given temperature, regardless the injection rate, allowing the direct determination of surface tension values for the liquid contained in the sample cell. (c) 2021 The Author(s). Published by Elsevier Inc. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

Abstract Fluorescence spectroscopy is used to characterize the partition of three second-generation D,L-alpha-cyclic peptides to two lipid model membranes. The peptides have proven antimicrobial activity, particularly against Gram positive bacteria, and the model membranes are formed of either with 1,2-dimyristoyl-sn-glycero-3-phospho- (1'- rac-glycerol) (DMPG) or its mixture with 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine (DMPE), at a molar ratio of (1:1). The peptide's intrinsic fluorescence was used in the Steady State and/or Time Resolved Fluorescence Spectroscopy experiments, showing that the peptides bind to the membranes, and the extent of their partition is thereof quantified. The peptide-induced membrane leakage was followed using an encapsulated fluorescent dye. Overall, the partition is mainly driven by electrostatics, but also involves hydrophobic interactions. The introduction of a hydrocarbon tail in one of the residues of the parent peptide, CPR, adjacent to the tryptophan (Trp) residue, significantly improves the partition of the modified peptides, CPRT10 and CPRT14, to both membrane systems. Further, we show that the length of the tail is the main distinguishing factor for the extension of the partition process. The parent peptide induces very limited leakage, at odds with the peptides with tail, that promote fast leakage, increasing in most cases with peptide concentration, and being almost complete for the highest peptide concentration and negatively charged membranes. Overall, the results help the unravelling of the antimicrobial action of these peptides and are well in line with their proven high antimicrobial activity.

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.