Tetracycline removal by polyelectrolyte copolymers in conjunction with ultrafiltration membranes through liquid-phase polymer-based retention.

In this study, we used a liquid-phase polymer-based retention technique assisted by polyelectrolyte copolymers containing quaternary ammonium and sulfonate groups that are capable of removing the antibiotic tetracycline (TC) through electrostatic interactions. The polymers were synthesized using zwitterionic, anionic, and cationic monomers with the aim of obtaining copolymers with different charge balances at the ratios of 1:1, 2:1, and 1:2 (negative: positive). The parameters investigated for each copolymer included the pH, ionic strength, concentration of polymer, maximum retention capacity, and sorption-elution process at pH 11.0 and 3.0. The copolymers with a charge ratio of 1:2 achieved the highest retention (80.0%) at alkaline pH, while the copolymers with charge ratios of 2:1 and 1:1 exhibited the maximum retention (72.0%) at acidic pH. Based on these results, the pH and charge of the polyelectrolyte copolymers play important roles in the TC removal processes. Additionally, the maximum retention capacity (MRC) recorded was 731.2, 176.8, and 214.8 mg TC/g of copolymer in the first charge for the three copolymer polyelectrolytes, and the second charge of the MRC process did not improve compared with the first load.

Polyelectrolytes for Environmental, Agricultural, and Medical Applications.

In recent decades, polyelectrolytes (PELs) have attracted significant interest owing to a surge in research dedicated to the development of new technologies and applications at the biological level. Polyelectrolytes are macromolecules of which a substantial portion of the constituent units contains ionizable or ionic groups. These macromolecules demonstrate varied behaviors across different pH ranges, ionic strengths, and concentrations, making them fascinating subjects within the scientific community. The aim of this review is to present a comprehensive survey of the progress in the application studies of polyelectrolytes and their derivatives in various fields that are vital for the advancement, conservation, and technological progress of the planet, including agriculture, environmental science, and medicine. Through this bibliographic review, we seek to highlight the significance of these materials and their extensive range of applications in modern times.

Formulations based on pullulan and a derivative as coating material for the food sector.

Carboxymethylated derivatives of pullulan (PU) were synthesized and evaluated as coating for the postharvest preservation of blueberries. Carboxymethylpullulan was obtained by etherification reaction with the substitution degrees of 0.52, 0.34, and 0.26 for CMP1, CMP2, and CMP3 respectively. Infrared spectroscopy and nuclear magnetic resonance results showed characteristic signals of the carbonyl group belonging to the carboxymethyl group. Thermal analysis showed that CMP1, CMP2, and CMP3 derivatives presented thermal stability values of 209.91 C, 214.73 C, and 225.52 °C, respectively, and were lower with respect to PU with Td of 238.84 °C. Furthermore, an increase in the glass transition temperature due to carboxymethylation was determined. The chemical modification decreased the contact angle with respect to PU (71.34°) with values for CMP1, CMP2, and CMP3 of 39.89°, 53.72° and 60.61°, respectively. The carboxymethylation also increased the water vapor permeability and mechanical properties of the films. In addition, it was found that the CMP molecules affected the optical properties. The application of CMP-based coatings reduced the mass loss and ripening rate of blueberries compared to native pullulan, therefore, packaging from CMP molecules could be used as a coating capable of delaying ripening and extending the shelf life of fruits.

Surface-enhanced Raman sensor with molecularly imprinted nanoparticles as highly sensitive recognition material for cancer marker amino acids.

Surface-enhanced Raman scattering (SERS) is a powerful technique primarily due to its high sensitivity and signal-enhancing properties, which enable the identification of unique vibrational fingerprints. These fingerprints can be used for the diagnosis and monitoring of diseases such as cancer. It is crucial to selectively identify cancer biomarkers for early diagnosis. A correlation has been established between the reduction in the concentration of specific amino acids and the stage of the disease, particularly tryptophan (TPP) and tyrosine (TRS) in individuals diagnosed with prostate cancer. In this work, we present a strategy to analyze TPP and TRS amino acids using molecularly imprinted polymer nanoparticles (nanoMIPs), which selectively detect target molecules in a SERS sensor. NanoMIPs are synthesized using the solid-phase molecular imprinting method with TPP and TRS as templates. These are then immobilized on a SERS substrate with gold nanoparticles to measure samples prepared from tryptophan and tyrosine in phosphate-buffered saline. The detection and quantification limits of the designed sensor are 7.13 µM and 23.75 µM for TPP, and 22.11 µM and 73.72 µM for TRS, respectively. Our study lays the groundwork for future investigations utilizing nanoMIPs in SERS assessments of TPP and TRS as potential biomarkers for prostate cancer detection.

Bio-Based Polymeric Membranes: Development and Environmental Applications.

Nowadays, membrane technology is an efficient process for separating compounds with minimal structural abrasion; however, the manufacture of membranes still has several drawbacks to being profitable and competitive commercially under an environmentally friendly approach. In this sense, this review focuses on bio-based polymeric membranes as an alternative to solve the environmental concern caused by the use of polymeric materials of fossil origin. The fabrication of bio-based polymeric membranes is explained through a general description of elements such as the selection of bio-based polymers, the preparation methods, the usefulness of additives, the search for green solvents, and the characterization of the membranes. The advantages and disadvantages of bio-based polymeric membranes are discussed, and the application of bio-based membranes to recover organic and inorganic contaminants is also discussed.

Study of the Efficiency of a Polycation Using the Diafiltration Technique in the Removal of the Antibiotic Oxytetracycline Used in Aquaculture.

The presence of antibiotics in aquatic systems in recent years has become a global environmental and public health concern due to the appearance of strains resistant to these antibiotics. Oxytetracycline (OXT) is a high-impact antibiotic used for both human and veterinary consumption, and it is the second most used antibiotic in aquaculture in Chile. Based on the above, this problem is addressed using a linear polymer whose structure is composed of aromatic rings and quaternary ammonium groups, which will help enhance the removal capacity of this antibiotic. To obtain the polycation, a radical polymerization synthesis was carried out using (4-vinylbenzyl)-trimethylammonium chloride as the monomer. The polycation was characterized via Fourier Transform Infrared spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR). The removal studies were conducted under different experimental conditions such as pH levels (3.0, 5.0, 7.0, 8.0, and 11.0), ionic strength (0.0-0.50 mg L-1 of NaCl), polymer dose (0.25-25.5 mg), variation of the antibiotic concentration (1-100 mg L-1), and evaluation of the maximum retention capacity, as well as load and discharge studies. The antibiotic retention removal was higher than 80.0%. The antibiotic removal performance is greatly affected by the effect of pH, ionic strength, molar ratio, and/or OXT concentration, as these parameters directly affect the electrostatic interactions between the polymer and the antibiotics. The diafiltration technique was shown to be highly efficient for the removal of OXT, with maximum removal capacities of 1273, 966, and 778 mg OXT g-1 polycation. In conclusion, it can be said that coupling water-soluble polymers to the diafiltration technique is an excellent low-cost way to address the problem of antibiotics in aquatic systems.

Comparative Study of the Removal Efficiency of Nalidixic Acid by Poly[(4-vinylbenzyl)trimethylammonium Chloride] and N-Alkylated Chitosan through the Ultrafiltration Technique and Its Approximation through Theoretical Calculations.

Emerging antibiotic contaminants in water is a global problem because bacterial strains resistant to these antibiotics arise, risking human health. This study describes the use of poly[(4-vinylbenzyl) trimethylammonium chloride] and N-alkylated chitosan, two cationic polymers with different natures and structures to remove nalidixic acid. Both contain ammonium salt as a functional group. One of them is a synthetic polymer, and the other is a modified artificial polymer. The removal of the antibiotic was investigated under various experimental conditions (pH, ionic strength, and antibiotic concentration) using the technique of liquid-phase polymer-based retention (LPR). In addition, a stochastic algorithm provided by Fukui's functions is used. It was shown that alkylated N-chitosan presents 65.0% removal at pH 7, while poly[(4-vinylbenzyl)trimethylammonium chloride] removes 75.0% at pH 9. The interaction mechanisms that predominate the removal processes are electrostatic interactions, π-π interactions, and hydrogen bonding. The polymers reached maximum retention capacities of 1605 mg g-1 for poly[(4-vinylbenzyl) trimethylammonium chloride] and 561 mg g-1 of antibiotic per gram for alkylated poly(N-chitosan). In conclusion, the presence of aromatic groups improves the capacity and polymer-antibiotic interactions.

Towards recycling of waste carbon fiber: Strength, morphology and structural features of recovered carbon fibers.

Carbon fiber is one of the most widely used materials in high demand applications due to its high specific properties, however, its post-recycling properties limit its use to low performance applications. In this research, the carbon fiber recovering is examined using two methods: two-step pyrolysis and microwave-assisted thermolysis. The results indicate that the fibers recovered by pyrolysis show reduced surface and structural damage, maintaining the original mechanical properties of the fiber with losses below 5%. The fibers recovered by microwaves undergo significant surface changes that reduce their tensile strength by up to 60% and changes in their graphitic structure, increasing their degree of crystallinity by Raman index ID/IG from 1.98 to 2.86 and their amorphous degree by ID"/IG ratio from 0.411 to 1.599. Recovering fibers from microwave technique is 70% faster compared to two step pyrolysis, and provides recycled fibers with superior surface activation with the presence of polar functional groups -OH, -CO, and -CH that react with the epoxy matrix. The thermal, morphological, structural and mechanical characterizations of the recovered fibers detailed in this work provide valuable findings to evaluate their direct reuse in new composite materials.

Study of the Antibacterial Capacity of a Biomaterial of Zeolites Saturated with Copper Ions (Cu2+) and Supported with Copper Oxide (CuO) Nanoparticles.

In this work, copper (II) ions were saturated and copper oxide nanoparticles (CuO NPs) were supported in natural zeolite from Chile; this was achieved by making the adsorbent material come into contact with a copper ion precursor solution and using mechanical agitation, respectively. The kinetic and physicochemical process of the adsorption of copper ions in the zeolite was studied, as well as the effect of the addition of CuO NPs on the antibacterial properties. The results showed that the saturation of copper (II) ions in the zeolite is an efficient process, obtaining a 27 g L-1 concentration of copper ions in a time of 30 min. The TEM images showed that a good dispersion of the CuO NPs was obtained via mechanical stirring. The material effectively inhibited the growth of Gram-negative and Gram-positive bacteria that have shown resistance to methicillin and carbapenem. Furthermore, the zeolite saturated with copper at the same concentration had a better bactericidal effect than the zeolite supported with CuO NPs. The results suggested that the ease of processing and low cost of copper (II) ion-saturated zeolitic material could potentially be used for dental biomedical applications, either directly or as a bactericidal additive for 3D printing filaments.

Effect of low aspect ratio one-dimensional nanoparticles on properties of photocrosslinked alginate nanocomposite hydrogels.

One-dimensional nanoparticles such as fibers, wires, represent an exciting type of filler for obtaining nanocomposite hydrogels due to their high aspect ratio. Unlike continuous fibers, in composites with short fibers, stress transfer occurs not only at the cylindrical surface of the fiber but also at the fiber ends. This work aimed to study the influence of the length of low aspect ratio one-dimensional nanoparticles on the rheological, swelling and thermal properties of nanocomposite hydrogels. We synthesized nanocomposite hydrogels via photopolymerization of methacrylated alginate macromonomers and aluminum oxide nanoparticles, nanowires and nanofibers as fillers. The main difference between the nanoparticles lies in their length. Longer nanoparticles (nanofibers) provided a glassier structure and a more significant reinforcement to the hydrogel, for example, at the concentration of 0.5 wt% the complex modulus increased approximately 2-fold and 8-fold for nanowires and nanofibers, respectively. Similarly, the incorporation of nanofibers produced hydrogels with a lower swelling capacity (2.5-fold decrease), which was attributed to a more connected network structure due to the higher aspect ratio of the nanofibers. Finally, both nanoparticle types produced an increase in the activation energy of thermal degradation.

Electrospun Poly(acrylic acid-co-4-styrene sulfonate) as Potential Drug-Eluting Scaffolds for Targeted Chemotherapeutic Delivery Systems on Gastric (AGS) and Breast (MDA-Mb-231) Cancer Cell Lines.

Potential drug-eluting scaffolds of electrospun poly(acrylic acid-co-styrene sulfonate) P(AA-co-SS) in clonogenic assays using tumorigenic gastric and ovarian cancer cells were tested in vitro. Electrospun polymer nanofiber (EPnF) meshes of PAA and PSSNa homo- and P(AA-co-SS) copolymer composed of 30:70, 50:50, 70:30 acrylic acid (AA) and sodium 4-styrene sulfonate (SSNa) units were performed by electrospinning (ES). The synthesis, structural and morphological characterization of all EPnF meshes were analyzed by optical and electron microscopy (SEM-EDS), infrared spectroscopy (FTIR), contact angle, and X-ray diffraction (XRD) measurements. This study shows that different ratio of AA and SSNa of monomers in P(AA-co-SS) EPnF play a crucial role in clonogenic in vitro assays. We found that 50:50 P(AA-co-SS) EPnF mesh loaded with antineoplastic drugs can be an excellent suppressor of growth-independent anchored capacities in vitro assays and a good subcutaneous drug delivery system for chemotherapeutic medication in vivo model for surgical resection procedures in cancer research.

N-Alkylated chitosan coupled to the liquid-phase polymer-based retention (LPR) technique to remove arsenic (V) from aqueous systems.

Water-soluble polymer based on alkylated chitosan with a quaternary ammonium group (Ch-QAG) was prepared, characterized, and applied to remove arsenate ions from aqueous solution by LPR technique. The arsenic removal was performed by the washing method (WM) and enrichment method (EM). Through the WM, studies of the pH and variation in the concentrations of interferents and arsenate ions were carried out. The effect of the removal of arsenate ions in simulated water was determined from the Camarones River in northern Chile. Ch-QAG showed high affinity for binding arsenate species (99% of removal) at pH 11.0 at a molar ratio of 20:1 polymer: As(V). High selectivity was also observed in the presence of interfering ions such as Cl-, SO42-, and PO43-, resulting in a removal rate over 80% at percentages over 95% for a concentration of 100 mg L-1 of As (V). The maximum retention capacity obtained was 112, 105, and 98 mg g-1 for three load cycles. The retention percentage for simulated water was 46.3% at a concentration of 1300 µ g L-1. In conclusion, the results presented in this study show that using Ch-QAG with ultrafiltration membranes is a great alternative to remove As (V) at high removal rates.

Tuning the softness of poly(2-hydroxyethyl methacrylate) nanocomposite hydrogels through the addition of PEG coated nanoparticles.

HYPOTHESIS: In nanocomposites, several factors govern the enhancement of properties when a nanofiller is added into a polymer matrix. Previously, our group have demonstrated that stabilizing nanoparticles improves the dispersion of nanoparticles in a hydrogel, but their effect on viscoelastic properties remain unclear. We hypothesized that coating the nanoparticles will block matrix-nanoparticle interactions, which would then affect the transfer of stress when the hydrogel is subjected to stress. EXPERIMENT: To this end, we investigated the effects that nanofillers coated with polyethylene glycol (PEG) of variable molar mass have on the properties of physical hydrogels made from poly(2-hydroxyethyl methacrylate). PEG with molar masses of 6, 20, and 35 kDa were used at different concentrations and the viscoelastic properties of the resulting hydrogels were studied and compared with control hydrogels with and without nanofillers. FINDINGS: The coated nanofiller resulted in enhanced dispersion stabilization as the molar mass and concentration of the PEG increased. However, there were noticeable changes in viscoelastic properties. In general, the nanocomposite hydrogels exhibited reduced shear modulus, greater creep, and more accentuated shear thinning behaviour. These effects were attributed to hindered matrix-nanoparticle interactions because of the PEG coating, an increased slippage of the PHEMA chains as well as a plasticizing effect.

Polyelectrolyte nanocomposite hydrogels filled with cationic and anionic clays.

Polyelectrolyte nanocomposite hydrogels (NHGs) were synthesized. NHGs were formed from a polymer matrix composed of a cationic, anionic, and alkylated chitosan polymer modified with vinyl groups (ChAV) to achieve greater crosslinking. Cationic and anionic clays montmorillonite and hydrotalcite, respectively, were used as nanofillers to introduce electrostatic interaction with the matrix. NHGs were obtained via in situ polymerization. The ChAV and NHGs were then characterized. Based on X-ray diffraction and transmission electron microscopy results, the morphology of the nanocomposite was generally intercalated with some nanocomposites showing exfoliation. Rheological studies revealed improvements in shear modulus of NHGs with respect to hydrogel without clay. Lower relaxation times were noted as the clay content increased and it was attributed to the interactions between the clay sheets and the polymer. In conclusion the rheological properties of the material are improved with the addition of clay and the interactions present with the polymer matrix.

Antibiotics removal using a chitosan-based polyelectrolyte in conjunction with ultrafiltration membranes.

The emergence of antibiotics as pollutants in the environment is one of the worldwide concerns because the bacterial strains generate a threat to the aquatic ecosystem and human health. In this study, an alkylated chitosan polyelectrolyte (ChA-PE) was used in conjunction with ultrafiltration membranes to remove three commonly used antibiotics, including amoxicillin (AMX), tetracycline (TET), and ciprofloxacin (CIP), in aqueous systems. The removal study considered diverse experimental variables through two methods: washing (pH, ionic strength, polymer ratio, and antibiotic concentration) and enrichment (maximum retention capacity). The retention percentage reached 80% at a pH of 11.0 at different polymer/antibiotic molar ratios. The ChA-PE presented irreversibly bound antibiotic interaction values of 0.51, 0.74, and 0.92 for CIP, AMX, and TET, respectively, at a pH of 11, showing that the polymer presents stronger permanent interactions with AMX and TET. On the other hand, the ChA-PE presented maximum retention capacity values of 185.6, 420.2, and 632.8 mg g-1 for CIP, AMX, and TET, respectively, in accordance with the association efficiency percentage values of 73.54, 87.08, and 93.83% for CIP, AMX, and TET, respectively.