Bioactivity and Antibacterial Analysis of Plasticized PLA Electrospun Fibers Reinforced with MgO and Mg(OH)2 Nanoparticles.

In this work, we focused on the bioactivity and antibacterial behavior of PLA-based electrospun fibers, efibers, reinforced with both MgO and Mg(OH)2 nanoparticles, NPs. The evolution of PLA-based efibers was followed in terms of morphology, FTIR, XRD, and visual appearance. The bioactivity was discussed in terms of hydroxyapatite growth after 28 days, considered as T28, of immersion in simulated body fluid, SBF. In particular, the biomineralization process evidenced after immersion in SBF started at T14 in both systems. The number of precipitated crystals increased by increasing the amount of both NPs. The chemical composition of the precipitated crystals was also characterized in terms of the Ca/P molar ratio after T28 of immersion in SBF, indicating the presence of hydroxyapatite on the surface of both reinforced efibers. Moreover, a reduction in the average diameter of the PLA-based efibers was observed, reaching a maximum reduction of 46 and 60% in the average diameter of neat PLA and PLA:OLA efibers, respectively, after 28 days of immersion in SBF. The antibacterial behavior of the MgO and Mg(OH)2 NPs in the PLA-based electrospun fibers was tested against Escherichia coli, E. coli, as the Gram-negative bacteria, and Staphylococcus aureus, S. aureus, as the Gram-positive bacteria, obtaining the best antibacterial activity against the Gram-negative bacteria E. coli of 21 ± 2% and 34 ± 6% for the highest concentration of MgO and Mg(OH)2 NPs, respectively.

Development of Antioxidant and Antimicrobial Membranes Based on Functionalized and Crosslinked Chitosan for Tissue Regeneration.

Tissue engineering is an interdisciplinary field that develops new methods to enhance the regeneration of damaged tissues, including those of wounds. Polymer systems containing bioactive molecules can play an important role in accelerating tissue regeneration, mitigating inflammation process, and fighting bacterial infection. Chitosan (CS) has attracted much attention regarding its use in wound healing system fabrication thanks to its biocompatibility, biodegradability, and the presence of functional groups in its structure. In this work, bioactive chitosan-based membranes were obtained by both chemical and physical modifications of the polymer with glycidyl methacrylate and glycerol (GLY), respectively. The most suitable GLY concentration to obtain wound healing systems with good elongation at break, a good water vapor transmission rate (WVTR), and good wettability values was 20% (w/w). Afterwards, the membranes were crosslinked with different concentrations of ethylene glycol dimethacrylate (EGDMA). By using a concentration of 0.05 mM EGDMA, membranes with a contact angle and WVTR values suitable for the application were obtained. To make the system bioactive, 3,4-dihydrocinnamic acid (HCAF) was introduced into the membranes, either by imbibition or chemical reaction, using laccase as a catalyst. Thermal and mechanical analyses confirmed the formation of a cohesive network, which limited the plasticizing effect of GLY, particularly when HCAF was chemically bound. The HCAF-imbibed membrane showed a good antioxidant and antimicrobial activity, highlighting the potential of this system for the treatment of wound healing.

Synergistic Combination of Antimicrobial Peptides and Cationic Polyitaconates in Multifunctional PLA Fibers.

Combining different antimicrobial agents has emerged as a promising strategy to enhance efficacy and address resistance evolution. In this study, we investigated the synergistic antimicrobial effect of a cationic biobased polymer and the antimicrobial peptide (AMP) temporin L, with the goal of developing multifunctional electrospun fibers for potential biomedical applications, particularly in wound dressing. A clickable polymer with pendent alkyne groups was synthesized by using a biobased itaconic acid building block. Subsequently, the polymer was functionalized through click chemistry with thiazolium groups derived from vitamin B1 (PTTIQ), as well as a combination of thiazolium and AMP temporin L, resulting in a conjugate polymer-peptide (PTTIQ-AMP). The individual and combined effects of the cationic PTTIQ, Temporin L, and PTTIQ-AMP were evaluated against Gram-positive and Gram-negative bacteria as well as Candida species. The results demonstrated that most combinations exhibited an indifferent effect, whereas the covalently conjugated PTTIQ-AMP displayed an antagonistic effect, potentially attributed to the aggregation process. Both antimicrobial compounds, PTTIQ and temporin L, were incorporated into poly(lactic acid) electrospun fibers using the supercritical solvent impregnation method. This approach yielded fibers with improved antibacterial performance, as a result of the potent activity exerted by the AMP and the nonleaching nature of the cationic polymer, thereby enhancing long-term effectiveness.

Straightforward Enzymatic Methacrylation of Poly(Glycerol Adipate) for Potential Applications as UV Curing Systems.

Enzymatic one-pot synthesis procedures in a one-step and two-step monomers addition were developed to obtain poly(glycerol adipate) macromers with methacrylate end-functional groups under the presence of 1 and 3 wt% of Candida antarctica lipase B (CALB). Glycerol, divinyl adipate, and vinyl methacrylate were enzymatically reacted (vinyl methacrylate was either present from the beginning in the monomers solution or slowly dropped after 6 h of reaction) in tetrahydrofuran (THF) at 40 °C over 48 h. Macromers with a methacrylate end groups fraction of ≈52% in a simple one-pot one-step procedure were obtained with molecular weights (Mn) of ≈7500-7900 g/mol. The obtained products under the one-pot one-step and two steps synthesis procedures carried out using 1 and 3 wt% of a CALB enzymatic catalyst were profusely characterized by NMR (1H and 13C), MALDI-TOF MS, and SEC. The methacrylate functional macromers obtained with the different procedures and 1 wt% of CALB were combined with an Irgacure® 369 initiator to undergo homopolymerization under UV irradiation for 10 and 30 min, in order to test their potential to obtain amorphous networks within minutes with similar properties to those typically obtained by complex acrylation/methacrylation procedures, which need multiple purification steps and harsh reagents such as acyl chlorides. To the best of our knowledge, this is the first time that it has been demonstrated that the obtention of methacrylate-functional predominantly linear macromers based on poly(glycerol adipate) is able to be UV crosslinked in a simple one-step procedure.

Antimicrobial Activity and Crystallization Features in Bio-Based Composites of PLLA and MCM-41 Particles Either Pristine or Functionalized with Confined Ag Nanowires.

Composites based on an L-rich poly(lactic acid) (PLLA) and MCM-41, either neat or modified with a silver (MCM-41@Ag), are achieved by solvent casting, being next processed by compression molding. Ag is mainly embedded as nanowires within the hybrid MCM-41@Ag particles, enabling its antimicrobial character. In these composites, the PLLA thermal stability, nucleation efficiency, and mechanical response are dependent on the MCM-41 nature and, to a lesser extent, on its content. Thus, differences in transitions of the PLLA matrix are noticed during cooling at 10 °C/min and in the subsequent heating when composites with neat or modified MCM-41 are compared. A very remarkable nucleation effect is played by pristine MCM-41, being inferior when MCM-41@Ag is incorporated into the PLLA. Wide angle X-ray scattering (WAXS) measurements using synchrotron radiation and performed under variable-temperature conditions in the composites containing MCM-41@Ag indicate that during cold crystallization, the disordered α' polymorph is initially formed, but it rapidly transforms into ordered α crystals. A long spacing peak, clearly seen in pure PLLA, appears as a small shoulder in PLLAMCM@Ag4 and is undetectable in PLLAMCM@Ag9 and PLLAMCM@Ag20. Furthermore, an increase in MH with the silica content is found in the two sets of composites, the higher MH values being observed in the family of PLLA and MCM-41@Ag. Finally, remarkable antimicrobial features are noticeable in the composites with MCM-41@Ag since this modified silica transfers its biocidal characteristics into the PLLA composites.

Photocured Poly(Mannitol Sebacate) with Functional Methacrylic Monomer: Analysis of Physical, Chemical, and Biological Properties.

In this work, we described the formation of polymeric networks with potential antimicrobial character based on an acrylate oligomer, poly(mannitol sebacate) (PMS), and an enzymatically synthesized methacrylic monomer with thiazole groups (MTA). Networks with different content of MTA were prepared, and further physico-chemically characterized by microhardness, water contact angle measurements, and differential scanning calorimetry. Monomer incorporation into the networks and subsequent quaternization to provide thiazolium moieties affected the mechanical behavior and the surface wettability of the networks. Moreover, the introduction of permanent cationic charges in the network surface could give antimicrobial activity to them. Therefore, the antibacterial behavior and the hemotoxicity were analyzed against Gram-positive and Gram-negative bacteria and red blood cells, respectively.

Centrifugal Force-Spinning to Obtain Multifunctional Fibers of PLA Reinforced with Functionalized Silver Nanoparticles.

The design and development of multifunctional fibers awakened great interest in biomaterials and food packaging materials. One way to achieve these materials is by incorporating functionalized nanoparticles into matrices obtained by spinning techniques. Here, a procedure for obtaining functionalized silver nanoparticles through a green protocol, using chitosan as a reducing agent, was implemented. These nanoparticles were incorporated into PLA solutions to study the production of multifunctional polymeric fibers by centrifugal force-spinning. Multifunctional PLA-based microfibers were obtained with nanoparticle concentrations varying from 0 to 3.5 wt%. The effect of the incorporation of nanoparticles and the method of preparation of the fibers on the morphology, thermomechanical properties, biodisintegration, and antimicrobial behavior, was investigated. The best balance in terms of thermomechanical behavior was obtained for the lowest amount of nanoparticles, that is 1 wt%. Furthermore, functionalized silver nanoparticles confer antibacterial activity to the PLA fibers, with a percentage of killing bacteria between 65 and 90%. All the samples turned out to be disintegrable under composting conditions. Additionally, the suitability of the centrifugal force-spinning technique for producing shape-memory fiber mats was tested. Results demonstrate that with 2 wt% of nanoparticles a good thermally activated shape-memory effect, with high values of fixity and recovery ratios, is obtained. The results obtained show interesting properties of the nanocomposites to be applied as biomaterials.

Molecularly Imprinted Polymers Based on Chitosan for 2,4-Dichlorophenoxyacetic Acid Removal.

The development of low-cost and eco-friendly materials for the removal of pollutants from water is one of the main modern challenges. For this purpose, molecularly imprinted polymers were prepared under optimized conditions starting from chitosan (CS), chemically or ionically modified with glycidyl methacrylate (GMA) or itaconic acid (ITA), respectively. 2,4-Dichlorophenoxyacetic acid (2,4-D) was used as a template, obtaining the CS_GMA and CS_ITA series. The influence of the template concentration on the MIPs' (molecularly imprinted polymers) morphology, thermal behaviour and swelling ability, as well as on the 2,4-D removal capacity, were analyzed. The amount of the template used for the imprinting, together with the different permeability of the matrices, were the key factors driving the analyte uptake process. Despite the good performance shown by the non-imprinted CS_GMA sample, the best results were obtained when CS_GMA was imprinted with the highest amount (5%) of template (CS_GMA_5). This system was also more efficient when consecutive adsorption experiments were carried out. In addition, CS_GMA_5 had a desorption efficiency of 90-100% when a low pesticide concentration was used. These findings suggest that the presence of imprinted cavities could be useful in improving the performance of sorbent materials making CS_GMA_5 a possible candidate for 2,4-D removal.

Adsorption Analysis of Exopolymeric Substances as a Tool for the Materials Selection of Photobioreactors Manufacture.

An improved method that allows the robust characterization of surfaces is necessary to accurately predict the biofouling formation on construction materials of photobioreactors (PBR). Exopolymeric substances (EPS), such as proteins and polysaccharides, have been demonstrated to present a similar behavior to cells in terms of surface adhesion. In this work, these EPS were used to optimize parameters, such as EPS concentration or adsorption time, to evaluate accurately the adsorption capacity of surfaces and, with it, predict the biofouling formation in contact with microalgae cultures. Once the method was optimized, the characterization of seven commercial polymeric surfaces was submitted to different abrasive particles sizes, which modified the roughness of the samples, as well as protein and polysaccharide lawns, which were prepared and carried out in order to evaluate the characteristics of these substances. The characterization consisted of the determination of surface free energy, water adhesion tension, and critical tension determined from the measurement of the contact angle, roughness, surface zeta potential, and the EPS adhesion capacity of each material. This will be useful to understand the behavior of the surface in the function of its characteristics and the interaction with the solutions of EPS, concluding that the hydrophobic and smooth surfaces present good anti-biofouling characteristics.

The Incorporation of Low-Molecular Weight Poly(Mannitol Sebacate)s on PLA Electrospun Fibers: Effects on the Mechanical Properties and Surface Chemistry.

We offer a report on the synthesis of low-molecular weight biobased poly(mannitol sebacate) (PMS) and its functionalization with acrylate groups (PMSAc). These synthesized polyesters were blended at a low level (10 wt%) with poly (lactic acid) PLA to prepare aligned fibers by electrospinning, coupled with a rotatory collector. The obtained fibers were extensively studied by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and wide-angle X-ray diffraction (WAXS), employing synchrotron radiation. The incorporation of the PMSs on the PLA fibers did not significantly affect the fiber diameters, whereas the alignment was almost maintained. The crystallinity and thermal properties were also slightly modified with the addition of PMSs, and an increase in the degree of crystallinity and in the glass transition temperature of the blend compared to PLA was observed. Remarkably, the PLA/PMSs fibers were more ductile due to the elastomeric character of PMS, with higher values of elongation at break and tensile strengths, and a smaller Young modulus in comparison with the PLA fibers. These modifications of the properties were more noticeable in the case of the acrylated PMS, which also provided readily available functional groups at the surface for further chemical reactions, such as the Michael addition or crosslinking processes.

Influence of abiotic conditions on the biofouling formation of flagellated microalgae culture.

This work analyses the adhesion of flagellated microalgae to seven surfaces that have different water adhesion tension characteristics. Chlamydomonas reinhardtii and Isochrysis galbana, were cultivated in batch and fed-batch mode at four nitrogen/phosphorus (N/P) ratios (from 1.29 to 70) and subjected to four irradiance levels (50, 100, 200 and 400 µE·s-1·m-2) at 23 °C. Cell adhesion was greater in C. reinhardtii and a higher biomass concentration was obtained for this strain, reaching 2 g·L-1 compared to 1 g·L-1 for I. galbana. The adhesion of cells and exopolymeric substances was measured upon the batch and the first fed-batch reaching the stationary growth phase, observing a direct correlation between them and inversely to biomass generation in the cultures. The protein adhesion data for the different materials are comparable to those for cell adhesion coinciding with minimums of Baier's theory and Vogler. It is observed displacements in the curves as a function of the irradiance level.

Antibacterial Polymers Based on Poly(2-hydroxyethyl methacrylate) and Thiazolium Groups with Hydrolytically Labile Linkages Leading to Inactive and Low Cytotoxic Compounds.

Herein, we develop a well-defined antibacterial polymer based on poly(2-hydroxyethyl methacrylate) (PHEMA) and a derivative of vitamin B1, easily degradable into inactive and biocompatible compounds. Hence, thiazole moiety was attached to HEMA monomer through a carbonate pH-sensitive linkage and the resulting monomer was polymerized via reversible addition-fragmentation chain transfer (RAFT) polymerization. N-alkylation reaction of the thiazole groups leads to cationic polymer with thiazolium groups. This polymer exhibits excellent antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA) with an MIC value of 78 µg mL-1, whereas its degradation product, thiazolium small molecule, was found to be inactive. Hemotoxicity studies confirm the negligible cytotoxicity of the degradation product in comparison with the original antibacterial polymer. The degradation of the polymer at physiological pH was found to be progressive and slow, thus the cationic polymer is expected to maintain its antibacterial characteristics at physiological conditions for a relative long period of time before its degradation. This degradation minimizes antimicrobial pollution in the environment and side effects in the body after eradicating bacterial infection.

Development of Highly Crystalline Polylactic Acid with ß-Crystalline Phase from the Induced Alignment of Electrospun Fibers.

Polylactic acid (PLA) is one of the known synthetic polymers with potential piezoelectric activity but this property is directly related to both the crystalline structure and crystalline degree. Depending on the process conditions, PLA can crystallize in three different forms: α-, ß-, and γ- form, with ß-crystalline phase being the piezoelectric one. To obtain this crystalline structure, transformation of α to ß is required. To do so, the strategies followed so far consisted in annealing or/and stretching of previously obtained PLA in the form of films or fibers, that is, additional post-processing steps. In this work, we are able to obtain PLA fibers with high macromolecular alignment, as demonstrated by SEM, and in the ß polymorph, as detected by X-ray diffraction (XRD) without the requirement of post-processing. For that, PLA fibers were prepared by using an electrospinning coupled to a drum collector. This set up and the optimization of the parameters (voltage flow-rate, and drum collector speed) induced molecular stretching giving rise to uniaxially oriented and highly aligned fibers.

Enzymatic Synthesis of Polyesters and Their Bioapplications: Recent Advances and Perspectives.

This article reviews the most important advances in the enzymatic synthesis of polyesters. In first place, the different processes of polyester enzymatic synthesis, i.e., polycondensation, ring opening, and chemoenzymatic polymerizations, and the key parameters affecting these reactions, such as enzyme, concentration, solvent, or temperature, are analyzed. Then, the latest articles on the preparation of polyesters either by direct synthesis or via modification are commented. Finally, the main bioapplications of enzymatically obtained polyesters, i.e., antimicrobial, drug delivery, or tissue engineering, are described. It is intended to point out the great advantages that enzymatic polymerization present to obtain polymers and the disadvantages found to develop applied materials.

Incorporation of Poly(Itaconic Acid) with Quaternized Thiazole Groups on Gelatin-Based Films for Antimicrobial-Active Food Packaging.

Poly(itaconic acid) (PIA) was synthesized via conventional radical polymerization. Then, functionalization of PIA was carried out by an esterification reaction with the heterocyclic groups of 1,3-thiazole and posterior quaternization by N-alkylation reaction with iodomethane. The modifications were confirmed by Fourier transform infrared (FTIR) and proton nuclear magnetic resonance (1H-NMR), as well as ζ-potential measurements. Their antimicrobial activity was tested against different Gram-negative and Gram-positive bacteria. After characterization, the resulting polymers were incorporated into gelatin with oxidized starch and glycerol as film adjuvants, and dopamine as crosslinking agent, to develop antimicrobial-active films. The addition of quaternized polymers not only improved the mechanical properties of gelatin formulations, but also decreased the solution absorption capacity during the swelling process. However, the incorporation of synthesized polymers increased the deformation at break values and the water vapor permeability of films. The antioxidant capacity of films was confirmed by radical scavenging ability and, additionally, those films exhibited antimicrobial activity. Therefore, these films can be considered as good candidates for active packaging, ensuring a constant concentration of the active compound on the surface of the food, increasing products' shelf-life and reducing the environmental impact generated by plastics of petrochemical origin.

Chemical Hydrogels Bearing Thiazolium Groups with a Broad Spectrum of Antimicrobial Behavior.

Several hydrogels based on 2-hydroxyethyl methacrylate and a methacrylic monomer containing a thiazole group in its lateral chain have been prepared by thermal polymerization at 60 °C in water solution varying the chemical composition of the gels. The posterior quaternization of the thiazole groups with methyl iodine has rendered positively charged hydrogels with potential antimicrobial activity. This modification has been structurally characterized by infrared spectroscopy, whereas the thermal stability of all hydrogels has been studied by thermal degradation in inert atmosphere. The swelling behavior in distilled water and the rheology of the different hydrogels have been analyzed as a function of 2-(4-methylthiazol-5-yl)ethyl methacrylate (MTA) monomer content as well as its methylation. Finally, the active character of hydrogels against Gram-positive and Gram-negative bacteria and fungi has been evaluated, revealing excellent antimicrobial activity against all tested microorganisms. The methylated hydrogels could be used as potential materials for wound healing or contact lens applications.

Hybrid Biocomposites Based on Poly(Lactic Acid) and Silica Aerogel for Food Packaging Applications.

Bionanocomposites based on poly (lactic acid) (PLA) and silica aerogel (SiA) were developed by means of melt extrusion process. PLA-SiA composite films were plasticized with 15 wt.% of acetyl (tributyl citrate) (ATBC) to facilitate the PLA processability as well as to attain flexible polymeric formulations for films for food packaging purposes. Meanwhile, SiA was added in four different proportions (0.5, 1, 3 and 5 wt.%) to evaluate the ability of SiA to improve the thermal, mechanical, and barrier performance of the bionanocomposites. The mechanical performance, thermal stability as well as the barrier properties against different gases (carbon dioxide, nitrogen, and oxygen) of the bionanocomposites were evaluated. It was observed that the addition of 3 wt.% of SiA to the plasticized PLA-ATBC matrix showed simultaneously an improvement on the thermal stability as well as the mechanical and barrier performance of films. Finally, PLA-SiA film formulations were disintegrated in compost at the lab-scale level. The combination of ATBC and SiA sped up the disintegration of PLA matrix. Thus, the bionanocomposites produced here show great potential as sustainable polymeric formulations with interest in the food packaging sector.

Physical methods for controlling bacterial colonization on polymer surfaces.

The adhesion and formation of microbial biofilm on material surfaces is a relevant problem in many areas including in medicine and biomaterials engineering. Biofilms are the primary cause of persistent infections associated with biomedical devices and clinical settings due to their tolerance and resistance to antimicrobial treatment. Reducing initial bacterial attachment to surfaces could decrease the formation of biofilms and, consequently, the posterior dispersion stage in which bacteria present within biofilms expand to other regions, spreading the infection. In this context, the use of surface topography to minimize microbial infections and biofilm formation represents an emerging area of research as it tackles this problem without the need to use antibiotics or other chemical agents. Herein, we review recent progress in surface topography-based antimicrobial approaches and provide an overview of the influence of micro- and nano-topography on bacterial surface attachment. We focus primarily on structured polymeric surfaces. The versatility and properties of polymer materials, along with their propensity to standardization at different length scales, make them an excellent option for fabrication of numerous medical devices. This work also provides a brief overview of recent advances in patterning polymers using lithography, direct-write patterning techniques, and instability-induced patterning. The impact of micro-, nano- and hierarchical surface structuration on the antimicrobial response of polymeric surfaces is addressed to offer new insights for the preparation of antimicrobial materials.

Antibacterial Character of Cationic Polymers Attached to Carbon-Based Nanomaterials.

The preparation of hybrid polymeric systems based on carbon derivatives with a cationic polymer is described. The polymer used is a copolymer of a quaternizable methacrylic monomer with another dopamine-based monomer capable of anchoring to carbon compounds. Graphene oxide and graphene as well as hybrid polymeric systems were widely characterized by infrared, Raman and photoemission X-ray spectroscopies, electron scanning microscopy, zeta potential and thermal degradation. These allowed confirming the attachment of copolymer onto carbonaceous materials. Besides, the antimicrobial activity of hybrid polymeric systems was tested against Gram positive Staphylococcus aureus and Staphylococcus epidermidis and Gram negative Escherichia coli and Pseudomonas aeruginosa bacteria. The results showed the antibacterial character of these hybrid systems.

Modified Starch as a Filter Controller in Water-Based Drilling Fluids.

Herein, the effectiveness of an itaconic acid (IA) graft copolymer on native corn starch (NCS) as a filter control agent in fresh water-based drilling fluids (WBDFs) was evaluated. The copolymer (S-g-IA_APS) was synthesized by conventional radical dispersion polymerization using the redox initiation system (NH4)2S2O8/NaHSO3. The modification of the starches was verified by volumetry, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Then, three WBDFs were formulated in which only the added polymer (NCS, S-g-IA_APS, and a commercial starch (CPS)) was varied to control the fluid losses. The physico-chemical, rheological, and filtering properties of the formulated systems were evaluated in terms of density (ρ), pH, plastic viscosity (µp), apparent viscosity (µa), yield point (Yp), gel strength (Rg), and filtrated volume (VAPI). In order to evaluate the resistance to temperature and contaminants of the WBDFs, they were subjected to high pressure and high temperature filtering (VHPHT). The filter control agents were also subjected to aging and contamination with cement and salt. The S-g-IA_APS addition improved the filtering behavior at a high pressure and temperature by 38%.