Synthesis and properties of Poly(L-lactide)-b-poly (L-phenylalanine) hybrid copolymers

Hybrid materials constituted by peptides and synthetic polymers have nowadays a great interest since they can combine the properties and functions of each constitutive block, being also possible to modify the final characteristics by using different topologies. Poly(L-lactide-b-L-phenylalanine) copolymers with various block lengths were synthesized by sequential ring-opening polymerization of L-lactide and the N-carboxyanhydride of L-phenylalanine. The resulting block copolymers were characterized by NMR spectrometry, IR spectroscopy, gel permeation chromatography, MALDI-TOF and UV-vis, revealing the successful incorporation of the polyphenylalanine (PPhe) peptide into the previously formed poly(L-lactide) (PLLA) polymer chain. X-ray diffraction and DSC data also suggested that the copolymers were phase-separated in domains containing either crystalline PLLA or PPhe phases. A peculiar thermal behavior was also found by thermogravimetric analysis when polyphenylalanine blocks were incorporated into polylactide.Peer ReviewedPostprint (published version

p-probabilistic k-anonymous microaggregation for the anonymization of surveys with uncertain participation

We develop a probabilistic variant of k-anonymous microaggregation which we term p-probabilistic resorting to a statistical model of respondent participation in order to aggregate quasi-identifiers in such a manner that k-anonymity is concordantly enforced with a parametric probabilistic guarantee. Succinctly owing the possibility that some respondents may not finally participate, sufficiently larger cells are created striving to satisfy k-anonymity with probability at least p. The microaggregation function is designed before the respondents submit their confidential data. More precisely, a specification of the function is sent to them which they may verify and apply to their quasi-identifying demographic variables prior to submitting the microaggregated data along with the confidential attributes to an authorized repository. We propose a number of metrics to assess the performance of our probabilistic approach in terms of anonymity and distortion which we proceed to investigate theoretically in depth and empirically with synthetic and standardized data. We stress that in addition to constituting a functional extension of traditional microaggregation, thereby broadening its applicability to the anonymization of statistical databases in a wide variety of contexts, the relaxation of trust assumptions is arguably expected to have a considerable impact on user acceptance and ultimately on data utility through mere availability.Peer ReviewedPostprint (author's final draft

Smart systems related to polypeptide sequences

Increasing interest for the application of polypeptide-based smart systems in the biomedical field has developed due to the advantages given by the peptidic sequence. This is due to characteristics of these systems, which include: biocompatibility, potential control of degradation, capability to provide a rich repertoire of biologically specific interactions, feasibility to self-assemble, possibility to combine different functionalities, and capability to give an environmentally responsive behavior. Recently, applications concerning the development of these systems are receiving greater attention since a targeted and programmable release of drugs (e.g. anti-cancer agents) can be achieved. Block copolymers are discussed due to their capability to render differently assembled architectures. Hybrid systems based on silica nanoparticles are also discussed. In both cases, the selected systems must be able to undergo fast changes in properties like solubility, shape, and dissociation or swelling capabilities. This review is structured in different chapters which explain the most recent advances on smart systems depending on the stimuli to which they are sensitive. Amphiphilic block copolymers based on polyanionic or polycationic peptides are, for example, typically employed for obtaining pH-responsive systems. Elastin-like polypeptides are usually used as thermoresponsive polymers, but performance can be increased by using techniques which utilize layer-by-layer electrostatic self-assembly. This approach offers a great potential to create multilayered systems, including nanocapsules, with different functionality. Recent strategies developed to get redox-, magnetic-, ultrasound-, enzyme-, light-and electric-responsive systems are extensively discussed. Finally, some indications concerning the possibilities of multi-responsive systems are discussed.Postprint (published version

Effects of hydroxyapatite (0001) Ca2+/Mg2+ substitution on adsorbed D-ribose ring puckering

Advanced Molecular Dynamics (MD) simulation protocols have been used to assess the ring puckering of cyclic D-ribose when the sugar is adsorbed on the most stable (0001) facet of calcium hydroxyapatite (HAp). In addition, sugar¿mineral interactions, which are crucial for transfection processes and prebiotic chemistry, have been studied for systems in which the Ca2+ ions of the above mentioned HAp facet were totally or partially replaced by Mg2+. The latter replacement is spatially and quantitatively limited and has been found to cause important alterations in the conformational behavior of D-ribose that are similar to those suffered in hairpin RNA from A to B helical structures. Accordingly, replacement of Ca2+ by Mg2+ has a dramatic effect on the functionality of the nucleic acid. These changes have been related to both the substitution site on the surface and the amount of ions. Our results show that when replacement by Mg2+ occurs in OH--coordinated Ca2+ ions, Mg2+¿D-ribose interactions are strong enough to prevent the interactions between the hydroxyl groups of the sugar and the remaining Ca2+ ions.Peer ReviewedPostprint (published version

Nylons with applications in energy generators, 3D printing and biomedicine

Linear polyamides, known as nylons, are a class of synthetic polymers with a wide range of applications due to their outstanding properties, such as chemical and thermal resistance or mechanical strength. These polymers have been used in various fields: from common and domestic applications, such as socks and fishing nets, to industrial gears or water purification membranes. By their durability, flexibility and wear resistance, nylons are now being used in addictive manufacturing technology as a good material choice to produce sophisticated devices with precise and complex geometric shapes. Furthermore, the emergence of triboelectric nanogenerators and the development of biomaterials have highlighted the versatility and utility of these materials. Due to their ability to enhance triboelectric performance and the range of applications, nylons show a potential use as tribo-positive materials. Because of the easy control of their shape, they can be subsequently integrated into nanogenerators. The use of nylons has also extended into the field of biomaterials, where their biocompatibility, mechanical strength and versatility have paved the way for groundbreaking advances in medical devices as dental implants, catheters and non-absorbable surgical sutures. By means of 3D bioprinting, nylons have been used to develop scaffolds, joint implants and drug carriers with tailored properties for various biomedical applications. The present paper aims to collect evidence of these recently specific applications of nylons by reviewing the literature produced in recent decades, with a special focus on the newer technologies in the field of energy harvesting and biomedicine.Peer ReviewedPostprint (published version

Injection molding and characterization of microtextures on polycarbonate using laser textured inserts

The purpose of this paper is to demonstrate the easy manufacturing and quick characterization of several microtextured functional surfaces on two transparent thermoplastics of general interest for several industrial sectors. Microtextured polymeric surfaces with special optical, tribological and easy-cleaning properties were manufactured via isothermal injection-molding using laser-microtextured steel mold inserts. For that purpose, conventional injection molding of two chosen amorphous transparent polymers (polycarbonate, PC, and polymethyl methacrylate, PMMA) utilizing laser-microtextured steel inserts was carried out, and a detailed morphological and functional characterization of the injected specimens was conducted later on. We also report on the suitable process conditions for the injection molding of these specimens using design of experiment (DOE) techniques. The analysis of the degree of replication (DR%) on the injected samples shows that mold temperature and injection speed are the most relevant parameters to obtain a successful replication and confirm the viability of conventional injection molding as a processing technique to obtain microtextured functional surfaces in amorphous transparent thermoplastics. The success of the procedure is further checked by the confirmation of the obtained surface functionalities by various standard and self-developed methods.Peer ReviewedPostprint (published version

Temperature induced structural changes in even-odd nylons with long polymethylene segments

Structural transitions of nylons 8 9 and 12 9 heating and cooling processes were investigated using calorimetric, spectroscopic during and real time X-ray diffraction data. These even-odd nylons had three polymorphic forms related to structures where hydrogen bonds were established in two planar directions. Heating processes showed a first structural transition at low temperature where the two strong reflections related to the packing mode of the low temperature structure (form I) disappeared instead of moving together and merging into a single reflection, as observed for conventional even-even nylons. The high temperature structure corresponded to a typical pseudohexagonal packing (form III) attained after the named Brill transition temperature. Structural transitions were not completely reversible since an intermediate structure (form II) became clearly predominant at room temperature in subsequent cooling processes. A single spherulitic morphology with negative birefringence and a flat-on edge-on lamellar disposition was obtained when the two studied polyamides crystallized from the melt state. Kinetic analyses indicated that both nylons crystallized according to a single regime and a thermal nucleation. Results also pointed out a secondary nucleation constant for nylon 12 9 higher than that for nylon 8 9, suggesting greater difficulty in crystallizing when the amide content decreased. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 2494–2506Peer ReviewedPostprint (author's final draft

Electrospun scaffolds of polylactide with a different enantiomeric content and loaded with anti-inflammatory and antibacterial drugs

Polylactide (PLA) electrospun microfibers were prepared and loaded with triclosan (TCS), ketoprofen (KTP), or their combination to obtain multifunctional scaffolds with bactericide and anti-inflammatory properties. Continuous and porous fibers with diameters in the micrometer scale and a unimodal distribution were successfully attained using a dual-electrospinning technique. Dual drug-loaded scaffolds showed a peculiar release that was in contrast to the single drug-loaded systems, which suggested the establishment of intermolecular interactions that delayed TCS and KTP release. Antimicrobial activity of all TCS-loaded electrospun scaffolds was demonstrated against E. coli and M. luteus bacteria; and furthermore, KTP-loaded samples slightly showed bactericide activity. Biocompatibility of scaffolds was evaluated by adhesion and proliferation assays, and interestingly, the dual drug-load systems were able to support high TCS doses without adverse effects.Peer ReviewedPostprint (author's final draft

Sustainable synthesis of amino acids by catalytic fixation of molecular dinitrogen and carbon dioxide

The industrial process of nitrogen fixation is complex and results in a huge economic and environmental impact. It requires a catalyst and high temperature and pressure to induce the rupture of the strong N–N bond and subsequent hydrogenation. On the other hand, carbon dioxide removal from the atmosphere has become a priority objective due to the high amount of global carbon dioxide emissions (i.e. 36 200 million tons in 2015). In this work, we fix nitrogen from N2 and carbon from CO2 and CH4 to obtain both glycine and alanine (D/L racemic mixture), the two simplest amino acids. The synthesis, catalyzed by polarized hydroxyapatite under UV light irradiation and conducted in an inert reaction chamber, starts from a simple gas mixture containing N2, CO2, CH4 and H2O and uses mild reaction conditions. At atmospheric pressure and 95 °C, the glycine and alanine molar yields with respect to CH4 or CO2 are about 1.9% and 1.6%, respectively, but they grow to 3.4% and 2.4%, when the pressure increases to 6 bar and the temperature is maintained at 95 °C. Besides, the minimum temperature required for the successful production of detectable amounts of amino acids is 75 °C. Accordingly, an artificial photosynthetic process has been developed by using an electrophotocatalyst based on hydroxyapatite thermally and electrically stimulated and coated with zirconyl chloride and a phosphonate. The synthesis of amino acids by direct fixation of nitrogen and carbon from gas mixtures opens new avenues regarding the nitrogen fixation for industrial purposes and the recycling of carbon dioxide.Peer ReviewedPostprint (published version

Electrically polarized hydroxyapatite: influence of the polarization process on the microstructure and properties

Semipermanently polarized hydroxyapatite, named SP/HAp(w), is obtained by applying a constant dc electric field of 1–10 kV/cm at 300–850 °C to the samples previously sintered in water vapor, while permanently polarized hydroxyapatite, PP/HAp(a), is produced by applying a dc electric field of 3 kV/cm at 1000 °C to the samples sintered in air. SP/HAp(w) has been used for biomedical applications, while PP/HAp(a) has been proved to be a valuable catalyst for N2 and CO2 fixation. In this work, structural differences between SP/HAp(w) and PP/HAp(a) have been ascertained using Raman microscopy, wide-angle X-ray diffraction, scanning electronic microscopy, high-resolution transmission electron microscopy, and grazing incidence X-ray diffraction. Results prove the existence of crystal distortion in the form of amorphous calcium phosphate and ß-tricalcium phosphate (ß-TCP) phases close to the surface because of the atmosphere used in the sintering process. The existence of an amorphous layer in the surface and the phase transition through ß-TCP of SP/HAp(w) are the structural factors responsible for the differences with respect to PP/HAp(a). Moreover, a superstructure has been identified in PP/HAp(a) samples, which could be another structural factor associated with enhanced conductivity, permanent polarization, and catalytic activity of this materialPeer ReviewedPostprint (author's final draft