The Multi-Challenges of the Multi-Ion-Imprinted Polymer Synthesis.

Multi-ion-imprinted polymers (MIIPs) are materials with a wide range of applications mainly focused on environmental recovery, mining, technology, sensors, etc. MIIPs can incorporate ions such as heavy metals, transition metals, rare earth elements, radionuclides, and other types of ions. The chemical structures of MIIPs can be designed for different purposes and with certain morphologies, such as gels, crystals, or powders, and the surface area and porosity are also considered. All these properties provide the material with several desirable characteristics, like high selectivity, high specificity, adequate efficiency, good stability, the possibility of reusability, and strategy technology adaptation. In this review, we show the multitude of challenges of multi-ion imprinted polymer chemical synthesis based on the different and interesting methods reported previously.

Effect of graphene on the key electrical, optical, and magnetic properties of polymethylmethacrylate: a study based on molecular modeling.

CONTEXT: In this work, a new polymeric structure was designed consisting of a nanometric sheet of graphene (G) and a polymethylmethacrylate (PMMA) repeat unit, which was designated as PMMA-G. Three degrees of polymerization of PMMA-G were considered: monomer (PMMA-G1), dimer (PMMA-G2), and trimer (PMMA-G3). The effect of incorporating a nanometric sheet of graphene into the molecular structure of PMMA on the modification of some of its main optical, magnetic, and electrical properties was investigated. Currently, the study presented here is of great relevance since various areas of technology require new materials with specific properties for the development of new devices. The results of our study reveal that the dielectric constant of PMMA is reduced when graphene is incorporated. However, a percentage increase of 14.48% in the refractive index of PMMA when graphene is inserted to form the nanocomposite is observed. It is found that the absolute value of molar magnetic susceptibility of PMMA increases considerably when reinforced with graphene. Finally, when reinforcing PMMA with graphene to obtain the PMMA-G nanocomposite, the electrical resistivity increases by almost an order of magnitude. METHODS: We used computational tools under Materials Studio (MS) software. We built a PMMA molecule with three degrees of polymerization, graphene sheet, and polymethylmethacrylate-graphene composite (PMMA-G) was built also with three degrees of polymerization using a concentration of 50% graphene over the PMMA polymer. For each structure, we used computational code DMol3 of MS, which is based on the Density Functional Theory, and the geometry optimization process was carried out to obtain the most stable structures. Finally, using the connectivity indices method together with topological properties of the molecular structures, implemented in Synthia computational code of MS software, we calculated the dielectric constant, magnetic susceptibility, refractive index, and electrical resistivity, for pure PMMA and PMMA-G structures for their three degrees of polymerization. The results were analyzed, and the changes in these properties were discussed in terms of the effect of an electric and magnetic field on the molecular structures of PMMA-G with respect to PMMA.

A bibliometric review on applications of lignocellulosic fibers in polymeric and hybrid composites: Trends and perspectives.

Over the past 10 years, materials science and engineering have shown increasing interest in incorporating lignocellulosic fibers into polymer and hybrid composites (LCF-CPH). This bibliometric analysis, covering the period 2012 to 2022, examines the current state of research on the application of these fibers in composites, with the aim of identifying significant contributions, new trends, and possible future directions. The analysis included a comprehensive database search using specific criteria, which revealed a significant increase in research activity on a variety of lignocellulosic fibers, such as flax, jute, hemp and sisal. This growth is particularly evident in the packaging, automotive, aerospace and construction industries. Hybrid composites based on these fibers have gained prominence due to their enhanced properties, which include improvements in mechanical, thermal and environmental characteristics. The findings of this research have significant implications for governments, corporations, and academic institutions. Researchers gain a deeper understanding of emerging trends, industry gains valuable insights into the advantages of adopting lignocellulosic fibers, and policymakers gain essential information to support the development of sustainable composites. In the field of advanced composites and sustainable materials, this work lays a solid foundation for future research and industrial applications.

Magnetic particle spray mass spectrometry for the determination of beta-blockers in plasma samples.

Magnetic particle spray mass spectrometry (MPS-MS), an innovative ambient ionization technique proposed by our research group, was employed to determine beta-blockers in human plasma samples. A dispersive solid phase extraction of atenolol, metoprolol, labetalol, propranolol, nadolol, and pindolol was carried out using magnetic molecularly imprinted polymer (M-MIP) particles that were attached to the tip of a metal probe, which was placed in the mass spectrometer inlet. A solvent (1% formic acid in methanol) was dispensed on the particles, and the Taylor cone was formed around them (in high voltage). The analytes were desorbed/ionized and determined by a triple quadrupole mass spectrometer. M-MIP was synthesized with oxprenolol as a pseudo-template, demonstrating good selectivity to beta-blockers compared with no-analog molecules, with an adsorption process occurring in monolayers, according to isotherm studies. Kinetic experiments indicated chemisorption as the predominant M-MIP/analyte interaction. The analytical curves were linear (R2 > 0.98), and the limit of quantification was 3 µg L-1 for all the analytes. Limits of detection ranged from 0.64 to 2.41 µg L-1. Precisions (relative standard deviation) and accuracies (relative error) ranged from 3.95 to 21.20% and -17.05 to 18.93%, respectively. MPS-MS proved to be a simple, sensitive, and advantageous technique compared with conventional approaches. The analyses were fast, requiring no chromatographic separation and without ionic suppression. The method is aligned with green chemistry principles, requiring minimal sample, solvent, and sorbent amounts. MPS-MS successfully integrates sample preparation and ambient ionization mass spectrometry and holds great potential for application with other sorbents, samples, and analytes.

Feasibility of new polymeric matrices in the production of ferrous sulphate dosimeters.

External beam radiotherapy is a treatment modality that employs high doses for curative or palliative purposes. Safety in such treatments, particularly with high-precision equipment, necessitates strict adherence to quality control protocols to ensure the efficacy of oncological treatments. In this context, chemical dosimeters, particularly the Fricke gel, have emerged as valuable tools for quantitatively analysing absorbed radiation doses. These dosimeters can be applied both as tissue-equivalent phantoms and as radiation detectors in radiotherapy centers. The objective of this study was to evaluate the feasibility of new gelling matrices, comprising common materials such as CMC, GGU, and PVA, for producing ferrous sulphate dosimeters aimed at the relative quantification of radiation dose. A rheological study was conducted for different Fricke gel dosimetric formulations. Initially, the performance of these dosimeters, produced at various gel concentrations, was evaluated in terms of their consistency at room temperature. This was achieved through the straightforward process of humidification the gels with glycerine. These matrices consist of both natural and synthetic polymers that are readily accessible, easy to handle, and can be easily incorporated into the acidic ferrous sulphate solution. Parameters such as the influence of gelling matrix concentration, linearity, and stability were assessed and correlated with those previously investigated for Fricke gel produced with bloom 300 pig skin gelatine (GEL). Ferrous sulphate dosimeters fabricated with sodium carboxymethylcellulose (CMC), guar gum (GGU), and polyvinyl alcohol (PVA) exhibited a coefficient of variation of less than 1% relative to the dose response evaluated in this study. By using readily available and easily manageable materials, it is possible to replicate dosimeters with a favourable dosimetric response for high-dose measurements.

Does cannula's size alter rheological properties of hyaluronic acid filler?

This study evaluated the rheological properties of various hyaluronic acid (HA) gels after passing through different-sized cannulas (22-G and 25-G). Five commercial brands of highly crosslinked HA fillers were analyzed: (A) Rennova® Ultra Deep, (B) Restylane® Lyft, (C) Hialurox® - Ultra Lift, (D) Belotero® Volume, and (E) E.P.T.Q S500. Rheological characterization was conducted using an automated controlled stress rheometer. The rheological properties of the fillers were assessed both before and after passing through the cannulas. Each filler brand and cannula size was tested three times by a researcher who was blinded to the commercial brands. For data analysis, frequencies of 0.1, 0.5, and 2 Hz were employed. The rheological properties (storage modulus [G'] and loss modulus [G"]) of the high-crosslink HA fillers did not change after being passed through cannulas of different sizes (22-G and 25-G) (p > 0.109) compared to baseline measurements (no cannula). Furthermore, all fillers displayed desirable solid-like, volumizing behavior at low frequencies and strain amplitudes (<10 %). Under physiologically relevant conditions for skin and facial applications, the cannula size did not alter the rheological properties of high crosslink HA fillers.

Recent Applications of Amphiphilic Copolymers in Drug Release Systems for Skin Treatment.

Amphiphilic copolymers (ACs) are versatile systems with self-assembling and aggregating properties, enabling the formation of nanomaterials (NMs) such as micelles, vesicles, nanocapsules, and nanogels. These materials have been extensively explored for the delivery of various drugs and active compounds, enhancing the solubility and permeation of poorly water-soluble drugs into skin tissue. This improvement facilitates the treatment of skin diseases, including chronic conditions like cancer, as well as infections caused by bacteria, fungi, and viruses. This review summarizes recent applications of ACs in skin treatment, with a particular focus on their use in anti-cancer drug therapy. It covers the synthesis, classification, and characterization of ACs using various experimental techniques. Additionally, it discusses recent research on different drug delivery pathways using ACs, including encapsulation efficiency, release behavior, characteristics, applications, and responses to various chemical and physical stimuli (both in vivo and in vitro). Furthermore, this review provides a comprehensive analysis of the effects of ACs NMs on several skin diseases, highlighting their potential as alternative treatments.

Polymer-Assisted Graphite Exfoliation: Advancing Nanostructure Preparation and Multifunctional Composites.

Exfoliated graphite (ExG) embedded in a polymeric matrix represents an accessible, cost-effective, and sustainable method for generating nanosized graphite-based polymer composites with multifunctional properties. This review article analyzes diverse methods currently used to exfoliate graphite into graphite nanoplatelets, few-layer graphene, and polymer-assisted graphene. It also explores engineered methods for small-scale pilot production of polymer nanocomposites. It highlights the chemistry involved during the graphite intercalation and exfoliation process, particularly emphasizing the interfacial interactions related to steric repulsion forces, van der Waals forces, hydrogen bonds, π-π stacking, and covalent bonds. These interactions promote the dispersion and stabilization of the graphite derivative structures in polymeric matrices. Finally, it compares the enhanced properties of nanocomposites, such as increased thermal and electrical conductivity and electromagnetic interference (EMI) shielding applications, with those of neat polymer materials.

Technologies for Mechanical Recycling of Carbon Fiber-Reinforced Polymers (CFRP) Composites: End Mill, High-Energy Ball Milling, and Ultrasonication.

Carbon fiber reinforced polymer (CFRP) composites have very high specific properties, which is why they are used in the aerospace, wind power, and sports sectors. However, the high consumption of CFRP compounds leads to a high volume of waste, and it is necessary to formulate mechanical recycling strategies for these materials at the end of their useful life. The recycling differences between cutting-end mills and high-energy ball milling (HEBM) were evaluated. HEBM recycling allowed us to obtain small recycled particles, but separating their components, carbon fiber, epoxy resin, and CFRP particles, was impossible. In the case of mill recycling, these were obtained directly from cutting a CFRP composite laminate. The recycled materials resulted in a combination of long fibers and micrometric particles-a sieving step allowed for more homogeneous residues. Although long, individual carbon fibers can pass through the sieve. Ultrasonication did not significantly affect HEBM recyclates because of the high energy they are subjected to during the grinding process, but it was influential on end mill recyclates. The ultrasonication amplitude notably impacted the separation of the epoxy resin from the carbon fiber. The end mill and HEBM waste production process promote the presence of trapped air and electrostatics, which allows recyclates to float in water and be hydrophobic.

Diet composition and plastic ingestion in Poecilia reticulata from urban streams.

Fish are excellent bioindicators and can reveal the presence of plastic in the environment. Diagnosing the composition and abundance of polymers in the fish diet makes it possible to evaluate their point sources and possible trophic transfers. We aimed to use the gastrointestinal contents of Poecilia reticulata in subtropical urban streams to detect the occurrence, shape, color, size, and chemical composition of polymers. For this, the diet of 240 individuals was analyzed using the volumetric method, and the microplastics (MPs; < 5 mm) recorded were characterized using Raman spectroscopy. Individuals predominantly consumed organic detritus and aquatic macroinvertebrates, with higher proportions of Diptera. A total of 111 plastic particles (< 0.5 to 12 mm) were recorded, and a subset of 14.4% was subjected to a micro-Raman spectrometer (830 nm excitation). The occurrence of polyethylene terephthalate (PET) and polypropylene (PP) with phthalocyanine dye was recorded. Some fragments could not be identified by Raman, but they contained indigo blue dye. Poecilia reticulata had a predominantly detritivorous diet with a record of plastic consumption, reflecting environmental pollution. Our results demonstrate that individuals of P. reticulata have ingested MPs in urban streams. This reinforces the need for future studies on the relationship between the presence of MPs in fish and the level of pollution in streams, comparisons with species of different feeding habits, and the potentially harmful effects on the entire biota.

Electrospun nonwoven fabric of poly(ε-caprolactone)/n-phosphonium chitosan for antiviral applications: Fabrication, characterization, and potential efficacy.

This work reports the virucidal properties of nonwoven fibers developed via electrospinning with polycaprolactone (PCL) and chitosan quaternized with phosphonium salt (NPCS), emphasizing the influence of NPCS concentration on the structure of fibers and their performance against the MHV-3 coronavirus. The addition of NPCS enhances solutions conductivity and viscosity, leading to fibers containing a finer porous structure with a more hydrophilic and smoother surface, thereby making them a potent barrier against respiratory particles, which is a key factor for protective face masks. In terms of degradation, NPCS paced-up the process, suggesting potential environmental benefits. PCL/NPCS (90/10) fibers exhibit a 99 % coronavirus inhibition within a five-minute exposure without cellular toxicity, while also meeting breathability standards for medical masks. These findings suggest the use of NPCS as a promising strategy to design materials with remarkable virucidal performance and physical characteristics that reinforce their use in the field of biomaterials engineering.

Effect of combining aminomethacrylate and fluoride against erosive and abrasive challenges on enamel and dentin.

This study evaluated the effect of solutions containing aminomethacrylate copolymer (AA) and sodium fluoride (F; 225 ppm F-) or fluoride plus stannous chloride (FSn; 225 ppm F-, 800 ppm Sn2+) against enamel and dentin erosion/abrasion. Solutions F, FSn, AA, F+AA, FSn+AA, and deionized water as negative control were tested. Bovine enamel and dentin specimens (n = 13/solution/substrate) underwent a set of erosion-abrasion cycles (0.3% citric acid [5 min, 4×/day], human saliva [1 h, 4×/day], brushing [15 s, 2×/day], and treatments [2 min, 2×/day]) for each of five days. Initial enamel erosion was evaluated using Knoop microhardness after the first and second acid challenge on day 1, and surface loss with profilometry after day 5. KOH-soluble fluoride was assessed. Data were analyzed with ANOVA/Tukey tests. The combination of fluoride and AA resulted in higher protection against enamel erosion, whereas this was not the case for the combination of AA and FSn. All treatments protected against enamel and dentin loss. The lowest surface loss values were observed with F+AA and FSn+AA. The polymer did not significantly influence the KOH-soluble fluoride formation on enamel/dentin specimens. The aminomethacrylate copolymer effectively enhanced the efficacy of sodium fluoride against initial erosion and improved the control of enamel and dentin wear of F and FSn solutions.

Role of Underlying Substrates on the Interfacial Thermal Transport in Supported Graphene Nanochannels: Implications of Thermal Translucency.

We study the role of underlying substrates on interfacial heat transfer within supported graphene nanochannels. Due to graphene's translucency, the underlying substrate, apart from its known hydrodynamic impact on fluid flow, also influences heat transport. We introduce the term "thermal translucency" to describe this phenomenon in the context of interfacial heat transfer. Our findings reveal that the Kapitza resistance, RK, is dependent on the specific underlying substrate. The specific underlying substrate alters the water-graphene interface potential landscape due to graphene's translucency, leading to a breakdown in the inverse relationship between interfacial water density peaks and RK values, typically observed at water-graphene and water-graphite interfaces. Remarkably, higher interfacial water density peaks correlate with more ordered energy patterns, not necessarily tied to more hydrophilic substrates as the literature commonly suggests for lower RK values. The insights provided have implications for controlling and tuning thermal transport and heat storage in nanofluidic devices.

The production and materials of mouthguards: Conventional vs additive manufacturing - A systematic review.

This investigation presents a critical analysis of mouthguard production, focusing on the evaluation of conventional vs additive manufacturing methods, the materials involved, and aspects such as their failure and prevention. It also summarizes the current trends, perspectives, and the main limitations. It is shown that some of the shortcomings can be solved by implementing additive manufacturing technologies, which are systematically reviewed in this research. Due to the specific materials used to produce mouthguards, there are certain additive manufacturing technologies that dominate and a wide variety of raw materials. The costs vary depending on the technology.

Sensors Based on Molecularly Imprinted Polymers in the Field of Cancer Biomarker Detection: A Review.

Biomarkers play a pivotal role in the screening, diagnosis, prevention, and post-treatment follow-up of various malignant tumors. In certain instances, identifying these markers necessitates prior treatment due to the complex nature of the tumor microenvironment. Consequently, advancing techniques that exhibit selectivity, specificity, and enable streamlined analysis hold significant importance. Molecularly imprinted polymers (MIPs) are considered synthetic antibodies because they possess the property of molecular recognition with high selectivity and sensitivity. In recent years, there has been a notable surge in the investigation of these materials, primarily driven by their remarkable adaptability in terms of tailoring them for specific target molecules and integrating them into diverse analytical technologies. This review presents a comprehensive analysis of molecular imprinting techniques, highlighting their application in developing sensors and analytical methods for cancer detection, diagnosis, and monitoring. Therefore, MIPs offer great potential in oncology and show promise for improving the accuracy of cancer screening and diagnosis procedures.

Immobilization of the ß-galactosidase enzyme by encapsulation in polymeric matrices for application in the dairy industry.

Lactose intolerance affects approximately 65% of the global adult population, leading to the demand for lactose-free products. The enzyme ß-galactosidase (ßG) is commonly used in the industry to produce such products, but its recovery after lactose hydrolysis is challenging. In this scenario, the study aims to encapsulate ßG within capsules, varying in dimensions and wall materials, to ensure their suitability for efficient industrial recovery. The enzyme ßG was encapsulated through ionic gelation using alginate and its blends with pectin, maltodextrin, starch, or whey protein as wall materials. The capsules produced underwent evaluation for encapsulation efficiency, release profiles, activity of the ßG enzyme, and the decline in enzyme activity when reused over multiple cycles. Alginate at 5% wt/vol concentrations, alone or combined with polymers such as maltodextrin, starch, or whey protein, achieved encapsulation efficiencies of approximately 98%, 98%, 80%, and 88%, respectively. The corresponding enzyme recovery rates were 34%, 19%, 31%, and 48%. Capsules made with an alginate-pectin blend exhibited no significant hydrolysis and maintained an encapsulation efficiency of 79%. Encapsulation with alginate alone demonstrated on poor retention of enzyme activity, showing a loss of 74% after just 4 cycles of reuse. Conversely, when alginate was mixed with starch or whey protein concentrate, the loss of enzyme activity was less than 40% after 4 reuses. These results highlight the benefits of combining encapsulation materials to improve enzyme recovery and reuse, offering potential economic advantages for the dairy industry.

Microplastics associated with stranded macroalgae on an impacted estuarine beach, Rio de Janeiro, Brazil.

Microplastics (MPs) are contaminants widely distributed in marine ecosystems. Only few studies approached MP interactions with marine plants, which are considered potential traps for MPs. Here, we determined MPs' densities and types associated with stranded macroalgae on a eutrophic beach in Guanabara Bay. Our results showed that red algae exhibited higher MP densities (1.48 MPs g-1), possibly due to their more branched thalli, than green algae (0.27 MPs g-1). The predominant MP types were blue and white fragments <3 mm in size and polymers were classified as polyethylene and polyvinyl chloride in fragments, and polypropylene in fibers. The higher densities of MPs in algae seemed to be influenced by the inner bay waters. The densities of MPs associated with algae from Guanabara Bay surpassed those reported in other studies. High MPs densities increase the chances that organisms associated with algae entangle or ingest MPs, impacting their health and survival.

Molecular dynamics simulations in pre-polymerization mixtures for peptide recognition.

CONTEXT: Molecularly imprinted polymers (MIPs) have promising applications as synthetic antibodies for protein and peptide recognition. A critical aspect of MIP design is the selection of functional monomers and their adequate proportions to achieve materials with high recognition capacity toward their targets. To contribute to this goal, we calibrated a molecular dynamics protocol to reproduce the experimental trends in peptide recognition of 13 pre-polymerization mixtures reported in the literature for the peptide toxin melittin. METHODS: Three simulation conditions were tested for each mixture by changing the box size and the number of monomers and cross-linkers surrounding the template in a solvent-explicit environment. Fully atomistic MD simulations of 350 ns were conducted with the AMBER20 software, with ff19SB parameters for the peptide, gaff2 parameters for the monomers and cross-linkers, and the OPC water model. Template-monomer interaction energies under the LIE approach showed significant differences between high-affinity and low-affinity mixtures. Simulation systems containing 100 monomers plus cross-linkers in a cubic box of 90 Å3 successfully ranked the mixtures according to their experimental performance. Systems with higher monomer densities resulted in non-specific intermolecular contacts that could not account for the experimental trends in melittin recognition. The mixture with the best recognition capacity showed preferential binding to the 13-26-α-helix, suggesting a relevant role for this segment in melittin imprinting and recognition. Our findings provide insightful information to assist the computational design of molecularly imprinted materials with a validated protocol that can be easily extended to other templates.

Comportamiento orgánico en la utilización de barreras con polímeros impresos 3D para la regeneración ósea guiada en implantología / Organic behavior in the utilization of barriers with 3D printed polymers for guided bone regeneration in implantology

Este estudio aborda la viabilidad y los retos inherentes al uso de barreras de polímeros impresos en 3D para la regeneración ósea guiada (en adelante, ROG) en procedimientos de implantología dental. A través del análisis exhaustivo de investigaciones y aplicaciones clínicas actuales, se evalúa detalladamente la biocompatibilidad, la funcionalidad estructural y las respuestas biológicas inducidas por estas barreras innovadoras en entornos terapéuticos. Este enfoque permite una comprensión más profunda de las interacciones osteointegrativas y las perspectivas de adaptabilidad tisular asociadas con materiales poliméricos avanzados (AU)

This scholarly investigation delineates the efficacy and inherent challenges of utilizing 3D printed polymer barriers for guided bone regeneration (GBR) in dental implantology procedures. An extensive review of current research and clinical implementations provides a critical assessment of biocompatibility, structural functionality, and the biological responses elicited by these innovative barriers within therapeutic contexts. The study delves into the osteointegrative interactions and tissue adaptability prospects facilitated by advanced polymeric materials, offering significant insights into their clinical utility.(AU)

PLGA-LEC/F127 hybrid nanoparticles loaded with curcumin and their modulatory effect on monocytes.

Aim: To investigate the effect of surfactant type on curcumin-loaded (CUR) PLGA nanoparticles (NPs) to modulate monocyte functions. Materials & methods: The nanoprecipitation method was used, and PLGA NPs were designed using Pluronic F127 (F127) and/or lecithin (LEC) as surfactants. Results: The Z-average of the NPs was <200 nm, they had a spherical shape, Derjaguin-Muller-Toporov modulus >0.128 MPa, they were stable during storage at 4°C, ζ-potential ∼-40 mV, polydispersity index <0.26 and % EE of CUR >94%. PLGA-LEC/F127 NPs showed favorable physicochemical and nanomechanical properties. These NPs were bound and internalized mainly by monocytes, suppressed monocyte-induced reactive oxygen species production, and decreased the ability of monocytes to modulate T-cell proliferation. Conclusion: These results demonstrate the potential of these NPs for targeted therapy.

This study explores how different surfactants affect curcumin-loaded PLGA nanoparticles, a biodegradable polymer. The nanoparticles were designed using Pluronic F127 and/or lecithin as surfactants. They are less than 200 nm and spherical. They are stable when stored at 4 °C, with a surface charge of about -40 mV, and can encapsulate more than 94% of curcumin.The results of this study are promising, showing that PLGA nanoparticles using a mixture of lecithin and Pluronic F127 as surfactants have favorable properties toward monocyte adhesion. They are primarily taken up by monocytes, a type of white blood cell, and demonstrate a remarkable ability to reduce the production of reactive oxygen species, which can cause cell damage, as well as the ability of monocytes to stimulate the proliferation of T cells. This underscores the potential of these nanoparticles in targeted therapy, particularly in diseases where monocytes play a pivotal role, such as chronic inflammatory conditions.