Publications

Abstract Gemini surfactants have been extensively used for in vitro gene delivery. Amino acid-derived gemini surfactants combine the special aggregation properties characteristic of the gemini surfactants with high biocompatibility and biodegradability. In this work, novel serine-derived gemini surfactants, differing in alkyl chain lengths and in the linker group bridging the spacer to the headgroups (amine, amide and ester), were evaluated for their ability to mediate gene delivery either per se or in combination with helper lipids. Gemini surfactant-based DNA complexes were characterized in terms of hydrodynamic diameter, surface charge, stability in aqueous buffer and ability to protect DNA. Efficient formulations, able to transfect up to 50% of the cells without causing toxicity, were found at very low surfactant/DNA charge ratios (1/1-2/1). The most efficient complexes presented sizes suitable for intravenous administration and negative surface charge, a feature known to preclude potentially adverse interactions with serum components. This work brings forward a new family of gemini surfactants with great potential as gene delivery systems.

Abstract Species with three-membered rings and the amide linkage are well studied. A quick perusal of the literature with SciFinder finds some 50 000 references to cyclopropanes and almost 300 000 references to amides. In the current paper, we discuss the structure and energetics of two understudied three-membered ring amides, 1,2-oxaziridine-3-one (5) (simultaneously describable as the simplest cyclic carbamate and simplest hydroxamate) and aziridine-2,3-dione (7) (simultaneously describable as the simplest imide and simplest alpha-ketoamide), with but 5 and nearly 10 references, respectively, for these two classes of compounds. Neither 1,2-oxaziridine-3-one (5) nor aziridine-2,3-dione (7), nor any derivative thereof, has been isolated. Calculational theory ameliorates the paucity of experimental information. The current study reports our computational findings for these and related species (e.g., enols and imidols) where we have used the G3(MP2)//B3LYP method.

Abstract Development of new and better performing energy storage devices rely on the use of innovative materials. The combination of nanostructured materials with high specific area, such as graphene, and conventional electrode materials such as Glassy Carbon (GC) and the use of the composite electrode in ionic liquids (IL) are considered to be a promising strategy for improved energy storage devices. Following our previous studies of electrochemical interfaces involving 1-butyl-3-methylimidazolium (tris(pentafluoroethyl) trifluorophosphate) ([C4MIM][FAP]) ionic liquid and Hg, Au, Pt and GC we extended the search for better electrochemical performance by preparing GC electrode surfaces modified with different carbon materials (reduced graphene oxide, reduced graphite oxide and graphite). Cyclic voltammetry of these electrode surfaces in [C4MIM][FAP] ionic liquid shows a 100 fold increase in the capacitive current of the composite electrode when compared with plain GC electrode.

Abstract This work aims at studying the efficacy of a series of novel biocompatible, serine-based surfactants as chemical permeation enhancers for two different local anesthetics, tetracaine and ropivacaine, combining an experimental and computational approach. The surfactants consist of gemini molecules structurally related, but with variations in headgroup charge (nonionic vs. cationic) and in the hydrocarbon chain lengths (main and spacer chains). In vitro permeation and molecular dynamics studies combined with cytotoxicity profiles were performed to investigate the permeation of both drugs, probe skin integrity, and rationalize the interactions at molecular level. Results show that these enhancers do not have significant deleterious effects on the skin structure and do not cause relevant changes on cell viability. Permeation across the skin is clearly improved using some of the selected serine-based gemini surfactants, namely the cationic ones with long alkyl chains and shorter spacer. This is noteworthy in the case of ropivacaine hydrochloride, which is not easily administered through the stratum corneum. Molecular dynamics results provide a mechanistic view of the surfactant action on lipid membranes that essentially corroborate the experimental observations. Overall, this study suggests the viability of these serine-based surfactants as suitable and promising delivery agents in pharmaceutical formulations. (C) 2015 Published by Elsevier B.V.

Abstract Naproxen-imprinted xerogels in the microspherical and nanospherical forms were prepared by W/O ernulsion and microemulsion, respectively. The work evolved from a sal-gel mixture previously reported for bulk synthesis. It was relatively simple to convert the original sol-gel mixture to one amenable to emulsion technique. The microspheres thus produced presented mean diameter of 3.7 mu m, surface area ranging 220-340 m(2)/g, selectivity factor 4.3 (against ibuprofen) and imprinting factor 61. A superior capacity (9.4 mu mol/g) was found, when comparing with imprints obtained from similar pre-gelification mixtures. However, slow mass transfer kinetics was deduced from column efficiency results. Concerning the nanospherical format, which constituted the first example of the production of molecularly imprinted xerogels in that format by microemulsion technique, adapting the sol-gel mixture was troublesome. In the end, nanoparticles with diameter in the order of 10 nm were finally obtained, exhibiting good indications of an efficient molecular imprinting process. Future refinements are necessary to solve serious aggregation issues, before moving to more accurate characterization of the binding characteristics or to real applications of the nanospheres.

Abstract The multifunctional alkoxysilane precursor, 2,6-bis(propyl-trimethoxysilylurelene)pyridine (DPS) was designed and synthesized, envisaging a multiple hydrogen-bond interaction in the molecular imprinting of the drug aminoglutethimide (AGT). Imprinted xerogels were obtained in bulk and spherical formats. The spherical format was achieved by pore-filling onto spherical mesoporous silica, as a straightforward technique to generate the spherical format. The bulk gels presented better selectivity for the template against its glutarimide (GLU) analogue (selectivity factor: bulk 13.4; spherical 4.6), and good capacity (bulk 5521 mu mol/L; spherical 2679 mu mol/L) and imprinting factor parameters (bulk 11.3; spherical 1.4). On the other hand, the microspherical format exhibited better dynamic properties associated to chromatographic efficiency (theoretical plates: bulk 6.8; spherical 75) and mass transfer, due mainly to the existence of a mesoporous network, lacking in the bulk material. The performance of the imprinted xerogels was not as remarkable as that of their acrylic counterparts, previously described. Overall it was demonstrated that the use of designed new "breeds" of organo-alkoxysilanes may be a strategy to achieve satisfactory imprints by the sol-gel processes. DPS may in principle be applied even more effectively to other templates bearing better-matching spatially compatible acceptor-donor-acceptor arrays.

Abstract The binding strength of dispersants to the surface of carbon nanotubes is of crucial importance for the efficiency of the dispersion process and for potential applications, yet data are scarce on this subject. Here we present the results of diffusion NMR experiments in dispersions of single-walled carbon nanotubes (SWNTs) prepared by either the polymer Pluronics F127 or the protein bovine serum albumin (BSA). The experiments detect the amount of F127 molecules adsorbed onto the SWNT surface. This quantity is recorded (i) in F127-SWNT dispersions to which BSA molecules are added and (ii) in BSA-SWNT dispersions to which F127 molecules are added. The data clearly show that F127 replaces BSA adsorbed at the SWNT surface, while BSA leaves the adsorbed F127 coverage intact. Consequently, F127 binds to the nanotube surface more strongly than BSA. Hence, we provide a way to categorize dispersants by adsorption strength. We also provide evidence showing that the nanotubes dispersed by BSA form loose aggregates where a large part of the surface is not in direct contact with the surrounding liquid. The results are discussed in relation to previous findings in the literature.