Quantification of Phthalate Esters in Carbonated Soft Drinks by Hollow Fiber-Microporous Membrane Liquid-Liquid Extraction and 96-Well Plate System Using Natural Deep Eutectic Solvents Based on Fatty Acids.

This study introduces a green approach to sample preparation by applying natural deep eutectic solvents (NADES) to determine phthalates in carbonated soft drinks using high-performance liquid chromatography with diode array detector (HPLC-DAD). The method employs hollow fiber-microporous membrane liquid-liquid microextraction combined with a 96-well plate system, utilizing fatty-acid-based DES in the pores of the membranes. This methodology substantially reduces the use of organic solvents, and its efficiency is comparable to or better than conventional methods. Fatty acids with chain lengths ranging from 6 to 12 carbons were investigated for the determination of dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), and benzyl butyl phthalate (BBP). The optimized approach used a NADES of decanoic and nonanoic acids (2:3 molar ratio), with 60 min of extraction and 30 min of desorption in acetonitrile:methanol (1:1 ratio). Limits of detection were reported as 8.2 µg/L for DMP, 7.6 µg/L for DEP and DBP, and 3.0 µg/L for BBP. Intraday precision ranged from 2.2% to 18.6% and inter-day precision from 8.8% to 18.8%. Relative recovery across 3 levels ranged from 83.1% to 113.5%. The methodology was evaluated by two tools with green metrics to indicate sustainability. Analytes are extracted, quantified, and confirmed as phthalates in two brands of carbonated soft drinks.

Petrographic and Petrophysical Characterization of Sandstones from Rio Bonito Formation, Paraná Basin (Southern Brazil).

This study focuses on the laboratory-scale petrophysical characterization of sandstones from the Rio Bonito Formation (Lower Permian), Paraná Basin, carried out from drill core samples from well PN-14-SC.02 obtained by CPRM-Brazilian Geological Service in the 1980s on the eastern edge of the Basin. This study includes integrating experimental data from routine petrophysics, sedimentary petrography, and nuclear magnetic resonance (NMR) obtained from 6 samples arranged in the normal direction of the stratification, present between 40 and 200 m deep. It was possible to conclude that the values of the permeability and porosity properties obtained from the NMR technique correlated in a very satisfactory way, with correlation coefficient R2 = 0.957 and Root Mean Squared Error (RMSE) = 0.208 about the porosity reference results offered by routine petrophysics, with lower values being less than a porosity unit (+/- 1 p.u.), in the range between 8 and 14%. The same was observed for the estimated permeability, R2 = 0.885 and RMSE = 0.152, by the Timur Coates method, with values in the range between 0.096 and 2.42 mD, which were well supported by the spectra information, as well as by petrographic analyses.

Antitumoral action of carvedilol-a repositioning study of the drug incorporated into mesoporous silica MCM-41.

We have studied repositioning of carvedilol (an antihypertensive drug) incorporated into MCM-41 mesoporous silica. The repositioning proposes a reduction in the slow pace of discovery of new drugs, as well as toxicological safety and a significant reduction in high research costs, making it an attractive strategy for researchers and large pharmaceutical companies. We obtained MCM-41 bytemplatesynthesis and functionalized it by post-synthesis grafting with aminopropyltriethoxysilane (APTES) only or with folic acid (FA), which gave MCM-41-APTES and MCM-41-APTES-FA, respectively. We characterized the materials by scanning and transmission electron microscopy, zeta potential (ZP) measurements, Fourier transform infrared absorption spectroscopy, x-ray diffractometry, nitrogen gas adsorption, and CHNS elemental analysis. We quantified the percentage of drug that was incorporated into the MCM-41 materials by thermogravimetric analysis and evaluated their cytotoxic activity in non-tumor human lung fibroblasts and the tumor human melanoma and human cervical adenocarcinoma cell lines by XTT salt reduction (2,3-bis-(2-methoxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-arboxanilide). The x-ray diffractograms of the MCM-41 materials displayed low-angle peaks in the 2θrange between 2° and 3°, and the materials presented type IV nitrogen adsorption isotherms and H2 hysteresis typical of the MCM-41hexagonal network. The infrared spectra, the charge changes revealed by ZP measurements, and the CHN ratios obtained from elemental analysis showed that MCM-41 was amino-functionalized, and that carvedilol was incorporated into it. MCM-41-APTES incorporated 23.80% carvedilol, whereas MCM-41 and MCM-41-APTES-FA incorporated 18.69% and 12.71% carvedilol, respectively. Incorporated carvedilol was less cytotoxic to tumor and non-tumor cells than the pure drug. Carvedilol repositioning proved favorable and encourages further studies aimed at reducing its cytotoxicity to non-tumor cells. Such studies may allow for larger carvedilol incorporation into drug carriers or motivate the search for a new drug nanocarrier to optimize the carvedilol antitumoral activity.

High removal of PS and PET microplastics from tap water by using Fe2O3 porous microparticles and photothermal irradiation with NIR light.

This work reports the synthesis of Fe2O3 (FeO) microparticles using the Pechini method and their use to remove microplastics from tap water. The analysis by electronic microscopy revealed that the FeO microparticles (FeMicroPs) have a porous structure and are formed by interconnected grains with sizes of 80-120 nm. In addition, the X-ray diffraction analysis pointed out that the FeMicroPs are composed of γ- Fe2O3 and α- Fe2O3 phases. To remove the PS and PET microplastics with sizes of 0.1-3 µm from the tap water, FeO was added to the contaminated water and the mixture of FeO + microplastics was irradiated with focused NIR light (980 nm). This provoked the melting of the microplastics on the FeO surface. Later, the FeMicroPs with adsorbed microplastics was recovered with magnets. This last procedure permitted a high removal of microplastics from the tap water, and the adsorption capacity was 1000 mg/g. In the next step, the microplastics adsorbed on the FeO were irradiated with NIR light to induce its thermal decomposition by photothermal irradiation, this in turn, produced the elimination of the microplastics from the FeO surface and allowed its reuse to remove more microplastics from the tap water. The elimination of the microplastics from the FeO surface was confirmed by the FTIR and Raman techniques, since the vibrational peaks associated with the microplastics disappeared from the FeO surface after the photothermal irradiation. Thus, the results of this investigation suggest that the photothermal irradiation with NIR light not only facilitates the removal of microplastics from the tap water, but also, it was useful to degrade the microplastics definitively without producing more contamination. This technique could be used to remove microplastics in water treatment plants.

Genipap Oil as a Natural Cross-Linker for Biodegradable and Low-Ecotoxicity Porous Absorbents via Reactive Extrusion.

Proteins derived from agroindustrial coproducts and a natural cross-linking agent (genipap oil containing genipin) were used to develop porous materials by reactive extrusion for replacing fossil-based absorbents. Incorporating genipap oil allowed the production of lightweight structures with high saline uptake (above 1000%) and competing retention capacity despite their porous nature. The mechanical response of the genipap-cross-linked materials was superior to that of the noncross-linked ones and comparable to those cross-linked using commercial genipin. The extruded products were hemocompatible and soil-biodegradable in less than 6 weeks. The compounds generated by the degradation process were not found to be toxic to the soil, showing a high bioassimilation capacity by promoting grass growth. The results demonstrate the potential of biopolymers and new green cross-linkers to produce fully renewable-based superabsorbents in hygiene products with low ecotoxicity. The study further promotes the production of these absorbents using low-cost proteins and continuous processing such as reactive extrusion.

Ionically-crosslinked carboxymethyl chitosan scaffolds by additive manufacturing for antimicrobial wound dressing applications.

Chitosan chemical functionalization is a powerful tool to provide novel materials for additive manufacturing strategies. The main aim of this study was the employment of computer-aided wet spinning (CAWS) for the first time to design and fabricate carboxymethyl chitosan (CMCS) scaffolds. For this purpose, the synthesis of a chitosan derivative with a high degree of O-substitution (1.07) and water soluble in a large pH range allowed the fabrication of scaffolds with a 3D interconnected porous structure. In particular, the developed scaffolds were composed of CMCS fibers with a small diameter (< 60 µm) and a hollow structure due to a fast non solvent-induced coagulation. Zn2+ ionotropic crosslinking endowed the CMCS scaffolds with stability in aqueous solutions, pH-sensitive water uptake capability, and antimicrobial activity against Escherichia coli and Staphylococcus aureus. In addition, post-printing functionalization through collagen grafting resulted in a decreased stiffness (1.6 ± 0.3 kPa) and a higher elongation at break (101 ± 9 %) of CMCS scaffolds, as well as in their improved ability to support in vitro fibroblast viability and wound healing process. The obtained results encourage therefore further investigation of the developed scaffolds as antimicrobial wound dressing hydrogels for skin regeneration.

Chitosan/collagen biomembrane loaded with 2,3-dihydrobenzofuran for the treatment of cutaneous Leishmaniasis.

In this work, chitosan/collagen-based membranes loaded with 2,3-dihydrobenzofuran (2,3-DHB) were developed through a simple solvent-casting procedure for use in the treatment of cutaneous Leishmaniasis. The obtained membranes were characterized by elemental analysis, FTIR, TG, DSC, and XRD. Porosity, swelling, mechanical properties, hydrophilicity, and antioxidant activity were analyzed. In addition, assessment to the biocompatibility, through fibroblasts/keratinocytes and in vitro wound healing essays were performed. The obtained results show that the new 2,3-DHB loaded chitosan/collagen membrane presented high porosity and swelling capacity as well as maximum strength, hydrophilicity, and antioxidant activity higher in relation to the control. The tests of antileishmanial activity and the AFM images demonstrate great efficacy of inhibition growth of the parasite, superior to those from the standard therapeutic agent that is currently used: Amphotericin B. The new membranes are biocompatible and stimulated the proliferation of keratinocytes. SEM images clearly demonstrate that fibroblasts were able to adhere, maintained their characteristic morphology. The healing test evidenced that the membranes have adequate environment for promoting cell proliferation and growth. As the conventional treatments often use drugs with high toxicity, the as-developed new membranes proved to be excellent candidate to treat cutaneous Leishmaniasis and can be clearly indicated for further advanced studies in vivo.

Hybrid organic monolithic column containing MIL-68(Al) for the separation of small molecules by capillary HPLC.

A hybrid organic monolithic column made of poly(lauryl methacrylate-co-1,6-hexanediol dimethacrylate) and the metal-organic framework MIL-68(Al) was prepared for the first time. The column was used in capillary liquid chromatography, both in isocratic and gradient elution modes. Separation performance towards small molecules of different chemical nature (polycyclic aromatic hydrocarbons, alkylbenzenes, phenols, etc.) was studied. Monte Carlo simulations were made to both select the proper precursors to obtain empty metal-organic framework micropores in the monolithic polymer and also, to analyze the potential free access of the studied analytes into the micropores (necessary to improve mass transfer and column efficiency). The hereby synthesized metal-organic framework microcrystals allowed obtaining homogeneous hybrid monolithic columns. Adding of MIL-68(Al) (1030 m2 g-1 BET specific surface area) increased the surface area from 3.9 m2 g-1 for the parent monolith to 18.2 m2 g-1 for the hybrid column containing 8 mg mL-1 of the microcrystals. Chromatographic performance of this new column was evaluated by studying retention factors, resolution, and plate counts at room temperature. Different compounds, not completely resolved in the parent monolith, were partially or completely separated after metal-organic framework addition. Using the monolithic column with only 2 mg mL-1 of MIL-68(Al), five alkylbenzenes were completely separated with very symmetrical peak shapes, resolution factors up to 3.60 and plate counts of 4300 plates m-1 for n-hexylbenzene. This value is higher than those obtained by other authors who used organic monolithic columns with embedded metal-organic frameworks to perform separations at room temperature. Additionally, nine polycyclic aromatic hydrocarbons were partially or completely resolved in gradient elution mode. The hybrid monolithic columns exhibited very good intra-day (%RSD=1.9), inter-day (%RSD=2.6), and column-to-column (%RSD=4.3) reproducibility values. Easy and fast column preparation, and versatility to efficiently separate several compounds of different chemical nature in isocratic and gradient mode, makes this new hybrid column a very good option for the analysis of small molecules in capillary (or nano) HPLC.

Analysis of human biological samples using porous graphitic carbon columns and liquid chromatography-mass spectrometry: a review.

Liquid chromatography-mass spectrometry (LC-MS) has emerged as a powerful analytical technique for analyzing complex biological samples. Among various chromatographic stationary phases, porous graphitic carbon (PGC) columns have attracted significant attention due to their unique properties-such as the ability to separate both polar and non-polar compounds and their stability through all pH ranges and to high temperatures-besides the compatibility with LC-MS. This review discusses the applicability of PGC for SPE and separation in LC-MS-based analyses of human biological samples, highlighting the diverse applications of PGC-LC-MS in analyzing endogenous metabolites, pharmaceuticals, and biomarkers, such as glycans, proteins, oligosaccharides, sugar phosphates, and nucleotides. Additionally, the fundamental principles underlying PGC column chemistry and its advantages, challenges, and advances in method development are explored. This comprehensive review aims to provide researchers and practitioners with a valuable resource for understanding the capabilities and limitations of PGC columns in LC-MS-based analysis of human biological samples, thereby facilitating advancements in analytical methodologies and biomedical research.

Design and simulation of scaffolds with lattice microstructures for bioprinting bone tissue.

BACKGROUND: Tissue engineering seeks to improve, maintain, or replace the biological functions of damaged organs or tissues with biological substitutes such as the development of scaffolds. In the case of bone tissue, they must have excellent mechanical properties like native bone. OBJECTIVE: In this work, three geometric models were designed for scaffolds with different structure lattices and porosity that could be biomechanically suitable and support cell growth for trabecular bone replacement applications in tissue engineering and regenerative medicine to the proximal femur area. METHODS: Geometries were designed using computer-aided design (CAD) software and evaluated using finite element analysis in compression tests. Three loads were considered according to the daily activity: 1177 N for slow walking, 2060 N for fast walking, and 245.25 N for a person in a bipedal position. All these loads for an adult weight of 75 kg. For each of them, three biomaterials were assigned: two polymers (poly-glycolic acid (PGA) and poly-lactic acid (PLA)) and one mineral (hydroxyapatite (HA)). 54 tests were performed: 27 for each of the tests. RESULTS: The results showed Young's modulus (E) between 1 and 4 GPa. CONCLUSION: If the resultant E is in the range of 0.1 to 5 GPa, the biomaterial is considered an appropriate alternative for the trabecular bone which is the main component of the proximal bone. However, for the models applied in this study, the best option is the poly-lactic acid which will allow absorbing the acting loads.

Theranostics Using MCM-41-Based Mesoporous Silica Nanoparticles: Integrating Magnetic Resonance Imaging and Novel Chemotherapy for Breast Cancer Treatment.

Advanced breast cancer remains a significant oncological challenge, requiring new approaches to improve clinical outcomes. This study investigated an innovative theranostic agent using the MCM-41-NH2-DTPA-Gd3⁺-MIH nanomaterial, which combined MRI imaging for detection and a novel chemotherapy agent (MIH 2.4Bl) for treatment. The nanomaterial was based on the mesoporous silica type, MCM-41, and was optimized for drug delivery via functionalization with amine groups and conjugation with DTPA and complexation with Gd3+. MRI sensitivity was enhanced by using gadolinium-based contrast agents, which are crucial in identifying early neoplastic lesions. MIH 2.4Bl, with its unique mesoionic structure, allows effective interactions with biomolecules that facilitate its intracellular antitumoral activity. Physicochemical characterization confirmed the nanomaterial synthesis and effective drug incorporation, with 15% of MIH 2.4Bl being adsorbed. Drug release assays indicated that approximately 50% was released within 8 h. MRI phantom studies demonstrated the superior imaging capability of the nanomaterial, with a relaxivity significantly higher than that of the commercial agent Magnevist. In vitro cellular cytotoxicity assays, the effectiveness of the nanomaterial in killing MDA-MB-231 breast cancer cells was demonstrated at an EC50 concentration of 12.6 mg/mL compared to an EC50 concentration of 68.9 mg/mL in normal human mammary epithelial cells (HMECs). In vivo, MRI evaluation in a 4T1 syngeneic mouse model confirmed its efficacy as a contrast agent. This study highlighted the theranostic capabilities of MCM-41-NH2-DTPA-Gd3⁺-MIH and its potential to enhance breast cancer management.

Microencapsulation of Hibiscus sabdariffa L. extract using porous starch and gum Arabic: Optimized process, characterization, stability, and simulated gastrointestinal conditions.

Hibiscus extract exhibits considerable antioxidant activity and a high anthocyanin content, which suggesting potential health benefits. However, these compounds are highly susceptible to environmental factors. The aim of this study was to establish the optimal conditions for the encapsulation of Hibiscus sabdariffa extract (HSE) using mixed porous maize starch-gum Arabic to enhance the stability of bioactive compounds under accelerated aging conditions. Response surface methodology (RSM) was used to optimize microencapsulation conditions through spray drying. The optimal conditions for microencapsulation of HSE by RSM were determined to be 126 °C at the inlet temperature (IT) and 8.5 % at the total solid content (TSC). Using these conditions, the amount of bioactive compounds in optimized microcapsules (OMs) was 2368 mg GAE/100 g, 694 mg QE/100 g, and 930 mg EC3G/100 g, of phenolic compounds, flavonoids, and anthocyanin, respectively. The release rate of anthocyanins during in vitro digestion was more effectively regulated in the OM sample, which retained up to 40 % of anthocyanins compared with 10 % in the HSE. The experimental values in this study exhibit high assertiveness, which renders the optimization model technologically and financially viable for the encapsulation of bioactive compounds with potential use in the food and pharmaceutical industries.

Optimized Electrophoretic Deposition of Chitosan/Mesoporous Glass Nanoparticles with Gentamicin on Titanium Implants: Enhancing Hemocompatibility and Antibacterial Activity.

Titanium-based implants have long been studied and used for applications in bone tissue engineering, thanks to their outstanding mechanical properties and appropriate biocompatibility. However, many implants struggle with osseointegration and attachment and can be vulnerable to the development of infections. In this work, we have developed a composite coating via electrophoretic deposition, which is both bioactive and antibacterial. Mesoporous bioactive glass particles with gentamicin were electrophoretically deposited onto a titanium substrate. In order to validate the hypothesis that the quantity of particles in the coatings is sufficiently high and uniform in each deposition process, an easy-to-use image processing algorithm was designed to minimize human dependence and ensure reproducible results. The addition of loaded mesoporous particles did not affect the good adhesion of the coating to the substrate although roughness was clearly enhanced. After 7 days of immersion, the composite coatings were almost dissolved and released, but phosphate-related compounds started to nucleate at the surface. With a simple and low-cost technique like electrophoretic deposition, and optimized stir and suspension times, we were able to synthesize a hemocompatible coating that significantly improves the antibacterial activity when compared to the bare substrate for both Gram-positive and Gram-negative bacteria.

Biocompatibility, bioactivity, porosity, and sealer/dentin interface of bioceramic ready-to-use sealers using a dentin-tube model.

This study evaluated the biocompatibility, bioactivity, porosity, and sealer/dentin interface of Sealer Plus BC (SP), Bio-C Sealer (BIOC), TotalFill BC Sealer (TF), and AH Plus (AHP). Dentin tubes filled with the sealers and empty tubes (control group) were implanted in the subcutaneous tissue of rats for different periods (n = 6 per group/period). Number of inflammatory cells (ICs), capsule thickness, von Kossa reaction, interleukin-6 (IL-6) and osteocalcin (OCN) were evaluated. Porosity and voids in the interface dentin/sealers were assessed by micro-computed tomography. The data were submitted to ANOVA/Tukey's tests (α = 0.05). Greater capsule thickness, ICs and IL-6 immunolabeling cells were observed in AHP. No significant difference in thickness of capsule, ICs, and IL-6- immunolabeling cells was detected between SP and TF, in all periods, and after 30 and 60 days between all groups. At 60 days all groups had reduction in capsule thickness, ICs and IL-6 immunolabeling cells. Von Kossa-positive and birefringent structures were observed in the capsules around the sealers. BIOC, SP, and TF exhibited OCN-immunolabeling cells. All sealers had porosity values below 5%, besides low and similar interface voids. BIOC, SP and TF are biocompatible, bioactive, and have low porosity and voids. The dentin-tube model used is an alternative for evaluating bioceramic materials.

Photo-crosslinkable hydrogel incorporated with bone matrix particles for advancements in dentin tissue engineering.

The objective of this study was to create injectable photo-crosslinkable biomaterials, using gelatin methacryloyl (GelMA) hydrogel, combined with a decellularized bone matrix (BMdc) and a deproteinized (BMdp) bovine bone matrix. These were intended to serve as bioactive scaffolds for dentin regeneration. The parameters for GelMA hydrogel fabrication were initially selected, followed by the incorporation of BMdc and BMdp at a 1% (w/v) ratio. Nano-hydroxyapatite (nHA) was also included as a control. A physicochemical characterization was conducted, with FTIR analysis indicating that the mineral phase was complexed with GelMA, and BMdc was chemically bonded to the amide groups of gelatin. The porous structure was preserved post-BMdc incorporation, with bone particles incorporated alongside the pores. Conversely, the mineral phase was situated inside the pore opening, affecting the degree of porosity. The mineral phase did not modify the degradability of GelMA, even under conditions of type I collagenase-mediated enzymatic challenge, allowing hydrogel injection and increased mechanical strength. Subsequently, human dental pulp cells (HDPCs) were seeded onto the hydrogels. The cells remained viable and proliferative, irrespective of the GelMA composition. All mineral phases resulted in a significant increase in alkaline phosphatase activity and mineralized matrix deposition. However, GelMA-BMdc exhibited higher cell expression values, significantly surpassing those of all other formulations. In conclusion, our results showed that GelMA-BMdc produced a porous and stable hydrogel, capable of enhancing odontoblastic differentiation and mineral deposition when in contact with HDPCs, thereby showing potential for dentin regeneration.

Utilization of Additive Manufacturing Techniques for the Development of a Novel Scaffolds with Magnetic Properties for Potential Application in Enhanced Bone Regeneration.

This study focuses on designing and evaluating scaffolds with essential properties for bone regeneration, such as biocompatibility, macroporous geometry, mechanical strength, and magnetic responsiveness. The scaffolds are made using 3D printing with acrylic resin and iron oxides synthesized through solution combustion. Utilizing triply periodic minimal surfaces (TPMS) geometry and mask stereolithography (MSLA) printing, the scaffolds achieve precise geometrical features. The mechanical properties are enhanced through resin curing, and magnetite particles from synthesized nanoparticles and alluvial magnetite are added for magnetic properties. The scaffolds show a balance between stiffness, porosity, and magnetic responsiveness, with maximum compression strength between 4.8 and 9.2 MPa and Young's modulus between 58 and 174 MPa. Magnetic properties such as magnetic coercivity, remanence, and saturation are measured, with the best results from scaffolds containing synthetic iron oxides at 1% weight. The viscosity of the mixtures used for printing is between 350 and 380 mPas, and contact angles between 90° and 110° are achieved. Biocompatibility tests indicate the potential for clinical trials, though further research is needed to understand the impact of magnetic properties on cellular interactions and optimize scaffold design for specific applications. This integrated approach offers a promising avenue for the development of advanced materials capable of promoting enhanced bone regeneration.

Effects of blood and root-dentin cleaning on the porosity and bond strength of a collagen bioceramic material.

To assess the effect of cleaning protocols on dentin contaminated with blood in reparative endodontic materials, bovine root samples were divided: no contamination (N); contamination (P); contamination and cleaning with saline (S), 2.5% NaOCl+saline (Na) or 2.5% NaOCl+17% EDTA+saline (NaE) and filled with: mineral trioxide aggregate (MTA), calcium-aluminate-cement (C), or C+collagen (Ccol) (n=13). The samples were evaluated for porosity, chemical composition, and bond strength. MTA porosity was lower than C (p=0.02) and higher than Ccol (p<0.001). P and NaE were similar (p=1.00), but higher than the other groups (p<0.001). MTA bond strength was similar to Ccol (p=0.777) and lower than C (p=0.028). P presented lower bond strength than the N (p<0.001); S and Na were similar to each other (p=0.969), but higher than P and lower than N (p<0.001). It was observed a predominance of mixed and cohesive failures. None of the samples showed Ca/P ratio values similar to human hydroxyapatite. This study showed that contamination with blood increased the materials porosity, but dentin cleaning with 2.5% NaOCl reduced this effect, and the collagen additive reduced the material porosity. Furthermore, blood contamination reduced the materials bond strength, and cleaning with saline or 2.5% NaOCl diminished this effect.

Additive manufacturing of bioactive and biodegradable poly (lactic acid)-tricalcium phosphate scaffolds modified with zinc oxide for guided bone tissue repair.

Bioactive and biodegradable scaffolds that mimic the natural extracellular matrix of bone serve as temporary structures to guide new bone tissue growth. In this study, 3D-printed scaffolds composed of poly (lactic acid) (PLA)-tricalcium phosphate (TCP) (90-10 wt.%) were modified with 1%, 5%, and 10 wt.% of ZnO to enhance bone tissue regeneration. A commercial chain extender named Joncryl was incorporated alongside ZnO to ensure the printability of the composites. Filaments were manufactured using a twin-screw extruder and subsequently used to print 3D scaffolds via fused filament fabrication (FFF). The scaffolds exhibited a homogeneous distribution of ZnO and TCP particles, a reproducible structure with 300 µm pores, and mechanical properties suitable for bone tissue engineering, with an elastic modulus around 100 MPa. The addition of ZnO resulted in enhanced surface roughness on the scaffolds, particularly for ZnO microparticles, achieving values up to 241 nm. This rougher topography was responsible for enhancing protein adsorption on the scaffolds, with an increase of up to 85% compared to the PLA-TCP matrix. Biological analyses demonstrated that the presence of ZnO promotes mesenchymal stem cell (MSC) proliferation and differentiation into osteoblasts. Alkaline phosphatase (ALP) activity, an important indicator of early osteogenic differentiation, increased up to 29%. The PLA-TCP composite containing 5% ZnO microparticles exhibited an optimized degradation rate and enhanced bioactivity, indicating its promising potential for bone repair applications.

Microstructural, Fluid Dynamic, and Mechanical Characterization of Zinc Oxide and Magnesium Chloride-Modified Hydrogel Scaffolds.

Scaffolds for the filling and regeneration of osteochondral defects are a current challenge in the biomaterials field, and solutions with greater functionality are still being sought. The novel approach of this work was to obtain scaffolds with biologically active additives possessing microstructural, permeability, and mechanical properties, mimicking the complexity of natural cartilage. Four types of scaffolds with a gelatin/alginate matrix modified with hydroxyapatite were obtained, and the relationship between the modifiers and substrate properties was evaluated. They differed in the type of second modifier used, which was hydrated MgCl2 in two proportions, ZnO, and nanohydroxyapatite. The samples were obtained by freeze-drying by using two-stage freezing. Based on microstructural observations combined with X-ray microanalysis, the microstructure of the samples and the elemental content were assessed. Permeability and mechanical tests were also performed. The scaffolds exhibited a network of interconnected pores and complex microarchitecture, with lower porosity at the surface (15 ± 7 to 29 ± 6%) and higher porosity at the center (67 ± 8 to 75 ± 8%). The additives had varying effects on the pore sizes and permeabilities of the samples. ZnO yielded the most permeable scaffolds (5.92 × 10-11 m2), whereas nanohydroxyapatite yielded the scaffold with the lowest permeability (1.18 × 10-11 m2), values within the range reported for trabecular bone. The magnesium content had no statistically significant effect on the permeability. The best mechanical parameters were obtained for ZnO samples and those containing hydrated MgCl2. The scaffold's properties meet the criteria for filling osteochondral defects. The developed scaffolds follow a biomimetic approach in terms of hierarchical microarchitecture and mechanical parameters as well as chemical composition. The obtained composite materials have the potential as biomimetic scaffolds for the regeneration of osteochondral defects.

Production and performance evaluation of chitosan/collagen/honey nanofibrous membranes for wound dressing applications.

Persistent bacterial infections are the leading risk factor that complicates the healing of chronic wounds. In this work, we formulate mixtures of polyvinyl alcohol (P), chitosan (CH), collagen (C), and honey (H) to produce nanofibrous membranes with healing properties. The honey effect at concentrations of 0 % (PCH and PCHC), 5 % (PCHC-5H), 10 % (PCHC-10H), and 15 % (PCHC-15H) on the physicochemical, antibacterial, and biological properties of the developed nanofibers was investigated. Morphological analysis by SEM demonstrated that PCH and PCHC nanofibers had a uniform and homogeneous distribution on their surfaces. However, the increase in honey content increased the fiber diameter (118.11-420.10) and drastically reduced the porosity of the membranes (15.79-92.62 nm). The addition of honey reduces the water vapor transmission rate (WVTR) and the adsorption properties of the membranes. Mechanical tests revealed that nanofibers were more flexible and elastic when honey was added, specifically the PCHC-15H nanofibers with the lowest modulus of elasticity (15 MPa) and the highest elongation at break (220 %). Also, honey significantly improved the antibacterial efficiency of the nanofibers, mainly PCHC-15H nanofibers, which presented the best bacterial reduction rates against Staphylococcus aureus (59.84 %), Pseudomonas aeruginosa (47.27 %), Escherichia coli (65.07 %), and Listeria monocytogenes (49.58 %). In vitro tests with cell cultures suggest that nanofibers were not cytotoxic and exhibited excellent biocompatibility with human fibroblasts (HFb) and keratinocytes (HaCaT), since all treatments showed higher or similar cell viability as opposed to the cell control. Based on the findings, PVA-chitosan-collagen-honey nanofibrous membranes have promise as an antibacterial dressing substitute.