Tailoring Hydrogel Sheet Properties through Co-Monomer Selection in AMPS Copolymer Macromers.

This study investigates hydrogels based on 2-Acrylamido-2-methyl-1-propanesulfonic acid sodium salt (AMPS) copolymers, incorporating N-hydroxyethyl acrylamide (HEA) and 3-sulfopropyl acrylate potassium salt (SPA). The addition of HEA and SPA is designed to fine-tune the hydrogels' water absorption and mechanical properties, ultimately enhancing their characteristics and expanding their potential for biomedical applications. A copolymer of AMPS, 2-carboxyethyl acrylate (CEA) combined with methacrylic acid (MAA) as poly(AMPS-stat-CEA-stat-MAA, PACM), was preliminarily synthesized. CEA and MAA were modified with allyl glycidyl ether (AGE) through ring-opening, yielding macromers with pendant allyl groups (PACM-AGE). Copolymers poly(AMPS-stat-HEA-stat-CEA-stat-MAA) (PAHCM) and poly(AMPS-stat-SPA-stat-CEA-stat-MAA) (PASCM) were also synthesized and modified with AGE to produce PAHCM-AGE and PASCM-AGE macromers. These copolymers and macromers were characterized by 1H NMR, FT-IR, and GPC, confirming successful synthesis and functionalization. The macromers were then photocrosslinked into hydrogels and evaluated for swelling, water content, and mechanical properties. The results revealed that the PASCM-AGE hydrogels exhibited superior swelling ratios and water retention, achieving equilibrium water content (~92%) within 30 min. While the mechanical properties of HEA and SPA containing hydrogels show significant differences compared to PACM-AGE hydrogel (tensile strength 2.5 MPa, elongation 47%), HEA containing PAHCM-AGE has a higher tensile strength (5.8 MPa) but lower elongation (19%). In contrast, SPA in the PASCM-AGE hydrogels led to both higher tensile strength (3.7 MPa) and greater elongation (92%), allowing for a broader range of hydrogel properties. An initial study on drug delivery behavior was conducted using PACM-AGE hydrogels loaded with photosensitizers, showing effective absorption, release, and antibacterial activity under light exposure. These AMPS-based macromers with HEA and SPA modifications demonstrate enhanced properties, making them promising for wound management and drug delivery applications.

Characterization and Performance Analysis of Hydrolyzed versus Non-Hydrolyzed Poly(NVF-co-HEA) Hydrogels for Cosmetic Applications.

This study explores the synthesis and modification of poly(N-vinylformamide-co-N-hydroxyethyl acrylamide) (poly(NVF-co-HEA)) hydrogels for cosmetic applications. Poly(NVF-co-HEA) hydrogels were produced followed by an acid hydrolysis reaction to produce poly(NVF-co-VAm-co-HEA) hydrogels, introducing poly(vinyl amine) (PVAm) into the structure. This modification considerably alters the hydrogels' properties, yielding materials with over 96% water content, predominantly in the form of non-freezing or free water, which is beneficial in the uptake and release of hydrophilic species. The primary amine groups from inclusion of VAm also improved the mechanical properties, as evidenced by an 8-fold increase in Young's modulus. The hydrogels also possessed pH-responsive behavior, which was particularly noticeable under acidic and basic conditions, where a large decrease in water content was observed (40% to 75% reduction). Characterizing the hydrogels' release capabilities involved using organic dyes of different functional groups and sizes to examine the pH impact on release. The results indicated that hydrolyzed hydrogels interacted more effectively with charged species, highlighting their suitability for pH-responsive delivery. The release of cosmetic active ingredients was also demonstrated through the controlled release of Liquid Azelaic™, specifically potassium azeloyl diglycinate (PAD). Our findings reveal that the hydrolyzed hydrogels exhibit superior burst release, especially under alkaline conditions, suggesting their suitability for cosmetic applications where controlled, pH-responsive delivery of active ingredients is desired. Overall, this investigation highlights the potential of hydrolyzed poly(NVF-co-HEA) hydrogels in cosmetic applications. Their ability to combine high water content with mechanical integrity, along with their pH-responsive release ability, allows for use in cosmetic formulations.

Hydroquinine Enhances the Efficacy of Contact Lens Solutions for Inhibiting Pseudomonas aeruginosa Adhesion and Biofilm Formation.

P. aeruginosa is one of the most common bacteria causing contact lens-related microbial keratitis (CLMK). Previous studies report that disinfecting solutions were ineffective in preventing biofilm formation. Solutions containing novel natural agents may be an excellent alternative for reducing the risk of CLMK. Here, we investigate the disinfecting properties of hydroquinine in combination with multipurpose solutions (MPSs) to prevent P. aeruginosa adhesion and biofilm formation. We examined the antibacterial, anti-adhesion, and anti-biofilm properties of hydroquinine-formulated MPSs compared to MPSs alone. Using RT-qPCR, hydroquinine directly affected the expression levels of adhesion-related genes, namely, cgrC, cheY, cheZ, fimU, and pilV, resulting in reduced adhesion and anti-biofilm formation. Using ISO 14729 stand-alone testing, hydroquinine met the criteria (>99.9% killing at disinfection time) against both P. aeruginosa reference and clinical strains. Using the crystal violet retention assay and FE-SEM, MPSs combined with hydroquinine were effective in inhibiting P. aeruginosa adhesion and destroying preexisting biofilms. This report is the first to highlight the potential utility of hydroquinine-containing formulations as a disinfecting solution for contact lenses, specifically for inhibiting adhesion and destroying biofilm. These findings may aid in the development of novel disinfectants aimed at combating P. aeruginosa, thereby potentially reducing the incidence of CLMK.

In Vitro Wound Healing Potential of a Fibroin Film Incorporating a Cannabidiol/2-Hydroxypropyl-ß-cyclodextrin Complex.

This study aimed to develop a film dressing prepared by incorporating a complex of cannabidiol and 2-hydroxypropyl-ß-cyclodextrin (CBD/HP-ß-CD) into a fibroin-based film and to investigate its wound healing capabilities. The fibroin from silkworm cocoons exhibited a total protein content of 96.34 ± 0.14% w/w and a molecular weight range of 25 to 245 kDa. Fourier-transform infrared spectroscopy (FTIR) revealed the presence of characteristic amide peaks (I, II, and III) in the isolated fibroin. The CBD/HP-ß-CD complex, prepared with a molar ratio of 1:2 (CBD to HP-ß-CD), had 81.5 ± 1.2% w/w CBD content, as determined by high-performance liquid chromatography (HPLC). X-ray diffraction (XRD) and FTIR analyses demonstrated successful encapsulation of CBD's hydrophobic aromatic rings by HP-ß-CD. Blending the fibroin solution with the CBD/HP-ß-CD complex produced a transparent, slightly yellowish film. Mechanical testing revealed a tensile strength of 48.67 ± 2.57 MPa and a % elongation at a break of 1.71 ± 0.21%. XRD and FTIR analyses showed distinctive crystalline and chemical structures of the film. In subsequent in vitro experiments with normal human dermal fibroblasts, the film demonstrated potential for wound healing. An increase in cell division (G2/M phase) was observed compared to the fibroin film without the CBD/HP-ß-CD complex. Additionally, fibroblasts treated with the film exhibited enhanced cell migration in a scratch assay and increased expression of vascular endothelial growth factor protein compared to the control group. Overall, these findings underscore the film's potential for enhancing wound healing outcomes.

Porous Poly(2-hydroxyethyl methacrylate) Hydrogel Scaffolds for Tissue Engineering: Influence of Crosslinking Systems and Silk Sericin Concentration on Scaffold Properties.

Tailored porous structures of poly(2-hydroxyethyl methacrylate) (PHEMA) and silk sericin (SS) were used to create porous hydrogel scaffolds using two distinct crosslinking systems. These structures were designed to closely mimic the porous nature of the native extracellular matrix. Conventional free radical polymerization of 2-hydroxyethyl methacrylate (HEMA) was performed in the presence of different concentrations of SS (1.25, 2.50, 5.00% w/v) with two crosslinking systems. A chemical crosslinking system with N'N-methylene bisacrylamide (MBAAm) and a physical crosslinking system with dimethylurea (DMU) were used: C-PHEMA/SS (crosslinked using MBAAm) and C-PHEMA/pC-SS (crosslinked using MBAAm and DMU). The focus of this study was on investigating the impact of these crosslinking methods on various properties of the scaffolds, including pore size, pore characteristics, polymerization time, morphology, molecular interaction, in vitro degradation, thermal properties, and in vitro cytotoxicity. The various crosslinked networks were found to appreciably influence the properties of the scaffolds, especially the pore sizes, in which smaller sizes and higher numbers of pores with high regularity were seen in C-PHEMA/1.25 pC-SS (17 ± 2 µm) than in C-PHEMA/1.25 SS (34 ± 3 µm). Semi-interpenetrating networks were created by crosslinking PHEMA-MBAAm-PHEMA while incorporating free protein molecules of SS within the networks. The additional crosslinking step involving DMU occurred through hydrogen bonding of the -C=O and -N-H groups with the SS, resulting in the simultaneous incorporation of DMU and SS within the PHEMA networks. As a consequence of this process, the scaffold C-PHEMA/pC-SS exhibited smaller pore sizes compared to scaffolds without DMU crosslinking. Moreover, the incorporation of higher loadings of SS led to even smaller pore sizes. Additionally, the gelation time of C-PHEMA/pC-SS was delayed due to the presence of DMU in the crosslinking system. Both porous hydrogel scaffolds, C-PHEMA/pC-SS and PHEMA, were found to be non-cytotoxic to the normal human skin dermal fibroblast cell line (NHDF cells). This promising result indicates that these hydrogel scaffolds have potential for use in tissue engineering applications.

Exploring the Potential of Roselle Calyx and Sappan Heartwood Extracts as Natural Colorants in Poly(butylene Succinate) for Biodegradable Packaging Films.

Recently, there has been a growing concern among consumers regarding the safety of packaging products, particularly due to the presence of potentially harmful substances like synthetic pigments and inorganic dyes. These substances, which are often used to attract consumer attention, can migrate and contaminate products over extended shelf storage periods. To address this issue, the focus of this research was the development of a biodegradable packaging film using poly(butylene succinate) (PBS) incorporated with natural colorants extracted from roselle (RS) and sappan heartwood (SP). RS and SP serve as non-toxic and alternative pigments when compared to synthetic colorants. The biodegradable packaging films were prepared using blown film extrusion, encompassing different weight percentages of RS and SP (0.1%, 0.2%, and 0.3%). The films exhibited distinct colors, with RS films appearing pink to purple and SP films exhibiting an orange hue. The water vapor transmission rate slightly decreased with an increasing content of RS and SP extracts, indicating improved barrier properties. Additionally, the films showed reduced light transmittance, as evidenced by the UV-Vis light barrier results. The degree of crystallinity in the films was enhanced, as confirmed by X-ray diffraction and differential scanning calorimetry techniques. Regarding mechanical properties, the PBS/RS and PBS/SP films exhibited slight increases in tensile strength and elongation compared to neat PBS films. Moreover, the blended films demonstrated higher stability after undergoing an aging test, further highlighting their potential for use in biodegradable packaging applications. The key advantages of these films lie in their non-toxicity, biodegradability, and overall environmental friendliness.

Hydroquinine Inhibits the Growth of Multidrug-Resistant Pseudomonas aeruginosa via the Suppression of the Arginine Deiminase Pathway Genes.

Hydroquinine has antimicrobial potential with demonstrated activity against several bacteria, including multidrug-resistant (MDR) P. aeruginosa reference strains. Despite this, there is limited evidence confirming the antibacterial activity of hydroquinine against clinical isolates and the underlying mechanism of action. Here, we aimed to investigate the antibacterial effect of hydroquinine in clinical P. aeruginosa strains using phenotypic antimicrobial susceptibility testing and synergistic testing. In addition, we examined the potential inhibitory mechanisms against MDR P. aeruginosa isolates using informatic-driven molecular docking analysis in combination with RT-qPCR. We uncovered that hydroquinine inhibits and kills clinical P. aeruginosa at 2.50 mg/mL (MIC) and 5.00 mg/mL (MBC), respectively. Hydroquinine also showed partial synergistic effects with ceftazidime against clinical MDR P. aeruginosa strains. Using SwissDock, we identified potential interactions between arginine deiminase (ADI)-pathway-related proteins and hydroquinine. Furthermore, using RT-qPCR, we found that hydroquinine directly affects the mRNA expression of arc operon. We demonstrated that the ADI-related genes, including the arginine/ornithine antiporter (arcD) and the three enzymes (arginine deiminase (arcA), ornithine transcarbamylase (arcB), and carbamate kinase (arcC)), were significantly downregulated at a half MIC of hydroquinine. This study is the first report that the ADI-related proteins are potential molecular targets for the inhibitory effect of hydroquinine against clinically isolated MDR P. aeruginosa strains.

Development of Natural Active Agent-Containing Porous Hydrogel Sheets with High Water Content for Wound Dressings.

This work was concerned with the fabrication of a porous hydrogel system suitable for medium to heavy-exudating wounds where traditional hydrogels cannot be used. The hydrogels were based on 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPs). In order to produce the porous structure, additional components were added (acid, blowing agent, foam stabilizer). Manuka honey (MH) was also incorporated at concentrations of 1 and 10% w/w. The hydrogel samples were characterized for morphology via scanning electron microscopy, mechanical rheology, swelling using a gravimetric method, surface absorption, and cell cytotoxicity. The results confirmed the formation of porous hydrogels (PH) with pore sizes ranging from ~50-110 µm. The swelling performance showed that the non-porous hydrogel (NPH) swelled to ~2000%, while PH weight increased ~5000%. Additionally, the use of a surface absorption technique showed that the PH absorbed 10 µL in <3000 ms, and NPH absorbed <1 µL over the same time. Incorporating MH the enhanced gel appearance and mechanical properties, including smaller pores and linear swelling. In summary, the PH produced in this study had excellent swelling performance with rapid absorption of surface liquid. Therefore, these materials have the potential to expand the applicability of hydrogels to a range of wound types, as they can both donate and absorb fluid.

Homo- and Copolymer Hydrogels Based on N-Vinylformamide: An Investigation of the Impact of Water Structure on Controlled Release.

This study investigated the performance of novel hydrogels based on poly (N-vinylformamide) (PNVF), copolymers of NVF with N-hydroxyethyl acrylamide (HEA) (P(NVF-co-HEA)), and 2-carboxyethyl acrylate (CEA) (P(NVF-co-CEA)), which were synthesized by photopolymerization using a UVLED light source. The hydrogels were analyzed for important properties such as equilibrium water content (%EWC), contact angle, freezing and non-freezing water, and diffusion-based in vitro release. The results showed that PNVF had an extremely high %EWC of 94.57%, while a decreasing NVF content in the copolymer hydrogels led to a decrease in water content with a linear relationship with HEA or CEA content. Water structuring in the hydrogels showed appreciably more variance, with ratios of free to bound water differing from 16.7:1 (NVF) to 1.3:1 (CEA), corresponding to PNVF having ~67 water molecules per repeat unit. The release studies of different dye molecules followed Higuchi's model, with the amount of dye released from the hydrogels depending on the amount of free water and the structural interactions between the polymer and the molecule being released. The results suggest that PNVF copolymer hydrogels have potential for controlled drug delivery by altering the polymer composition to govern the amount and ratio of free to bound water contained in the hydrogels.

In Situ Compatibilized Blends of PLA/PCL/CAB Melt-Blown Films with High Elongation: Investigation of Miscibility, Morphology, Crystallinity and Modelling.

Ternary-blended, melt-blown films of polylactide (PLA), polycaprolactone (PCL) and cellulose acetate butyrate (CAB) were prepared from preliminary miscibility data using a rapid screening method and optical ternary phase diagram (presented as clear, translucent, and opaque regions) as a guide for the composition selection. The compositions that provided optically clear regions were selected for melt blending. The ternary (PLA/PCL/CAB) blends were first melt-extruded and then melt-blown to form films and characterized for their tensile properties, tensile fractured-surface morphology, miscibility, crystallinity, molecular weight and chemical structure. The results showed that the tensile elongation at the break (%elongation) of the ternary-blended, melt-blown films (85/5/10, 75/10/15, 60/15/25 of PLA/PCL/CAB) was substantially higher (>350%) than pure PLA (ca. 20%). The range of compositions in which a significant increase in %elongation was observed at 55−85% w/w PLA, 5−20% w/w PCL and 10−25% w/w CAB. Films with high %elongation all showed good interfacial interactions between the dispersed phase (PCL and CAB) and matrix (PLA) in FE-SEM and showed improvements in miscibility (higher intermolecular interaction and mixing) and a decrease in the glass transition temperature, when compared to the low %elongation films. The decrease in Mw and Mn and the formation of the new NMR peaks (1H NMR at 3.68−3.73 ppm and 13C NMR at 58.54 ppm) were observed in only the high %elongation films. These are expected to be in situ compatibilizers that are generated during the melt processing, mostly by chain scission. In addition, mathematical modelling was used to study the optimal ratio and cost-effectiveness of blends with optimised mechanical properties. These ternary-blended, melt-blown films have the potential for use in both packaging and medical devices with excellent mechanical performance as well as inherent economic and environmental capabilities.

Surface-Modified Polypyrrole-Coated PLCL and PLGA Nerve Guide Conduits Fabricated by 3D Printing and Electrospinning.

The efficiency of nerve guide conduits (NGCs) in repairing peripheral nerve injury is not high enough yet to be a substitute for autografts and is still insufficient for clinical use. To improve this efficiency, 3D electrospun scaffolds (3D/E) of poly(l-lactide-co-ε-caprolactone) (PLCL) and poly(l-lactide-co-glycolide) (PLGA) were designed and fabricated by the combination of 3D printing and electrospinning techniques, resulting in an ideal porous architecture for NGCs. Polypyrrole (PPy) was deposited on PLCL and PLGA scaffolds to enhance biocompatibility for nerve recovery. The designed pore architecture of these "PLCL-3D/E" and "PLGA-3D/E" scaffolds exhibited a combination of nano- and microscale structures. The mean pore size of PLCL-3D/E and PLGA-3D/E scaffolds were 289 ± 79 and 287 ± 95 nm, respectively, which meets the required pore size for NGCs. Furthermore, the addition of PPy on the surfaces of both PLCL-3D/E (PLCL-3D/E/PPy) and PLGA-3D/E (PLGA-3D/E/PPy) led to an increase in their hydrophilicity, conductivity, and noncytotoxicity compared to noncoated PPy scaffolds. Both PLCL-3D/E/PPy and PLGA-3D/E/PPy showed conductivity maintained at 12.40 ± 0.12 and 10.50 ± 0.08 Scm-1 for up to 15 and 9 weeks, respectively, which are adequate for the electroconduction of neuron cells. Notably, the PLGA-3D/E/PPy scaffold showed superior cytocompatibility when compared with PLCL-3D/E/PPy, as evident via the viability assay, proliferation, and attachment of L929 and SC cells. Furthermore, analysis of cell health through membrane leakage and apoptotic indices showed that the 3D/E/PPy scaffolds displayed significant decreases in membrane leakage and reductions in necrotic tissue. Our finding suggests that these 3D/E/PPy scaffolds have a favorable design architecture and biocompatibility with potential for use in peripheral nerve regeneration applications.

The analytical and biomedical applications of carbon dots and their future theranostic potential: A review.

In recent years, carbon dots (C-dots) have gained appreciable interest owing to their unique optical properties, including tunable fluorescence, stability against photobleaching and photoblinking, and strong fluorescence. Simple and low-cost hydrothermal and electrochemical approaches have been widely used in the preparation of biocompatible and high-quality C-dots. Various C-dots have been used for the quantitation of small analytes, mostly based on analyte induced fluorescence quenching. Depending on the nature of precursors, synthetic conditions (such as reaction temperature and time), and surface conjugation, multi-function C-dots can be prepared and used in diagnostics and therapeutics. Their strong fluorescence and photostability, enables use in cell imaging. Their biological activity from the surface residues and capability of generating reactive oxygen species, have allowed many C-dots to become candidates as antibacterial and anticancer reagents. After suitable conjugation, biocompatible and fluorescent C-dots can be used for diagnostics and therapeutics, thus, showing their great potential in the area of theranostics.

Speciation of mercury in water and biological samples by eco-friendly ultrasound-assisted deep eutectic solvent based on liquid phase microextraction with electrothermal atomic absorption spectrometry.

A simple, fast, sensitive and eco-friendly ultrasound-assisted deep eutectic solvent liquid phase microextraction (UA-DES-LPME) was developed for preconcentration and speciation of Hg2+ and CH3Hg+ combined with ETAAS. Choline-phenol based DES (1:3, molar ratio) was used as an extractant for the determination of species of mercury, Hg2+ formed hydrophobic complexes with dithizone and complexes were then extracted using DES. For CH3Hg+ determination, CH3Hg+ can be extracted directly into DES phase because of its hydrophobic property. Under optimized conditions, the detection limits of Hg2+ and CH3Hg+ were 0.073 and 0.091 ng mL-1, respectively. %RSD (n = 7) were less than 4.1% and the enrichment factor (10 mL sample volume) were 34 and 18.3 for Hg2+ and CH3Hg+, respectively. The accuracy of the developed method was verified by analysis of SRM-1566b oyster tissue. The proposed method was applied to the speciation of mercury in several water and fresh water fish samples.

Determination of cadmium in herbs by SFODME with ETAAS detection.

A method for the determination of cadmium in herb samples based on solidified floating organic drop microextraction (SFODME) using 1-(2-Pyridylazo)-2-naphthol (PAN) as a chelating reagent and detection by electrothermal atomic absorption spectrometry (ETAAS) was developed in the present work. The effects of pH, extraction solvent, extraction time, stirring rate, and extraction temperature were investigated. Under the optimized conditions, the calibration graph was linear in the range of 0.017-3.0µgL-1, with a detection limit (LOD) of 0.0052µgL-1. The relative standard deviation (%RSD) for 6 replicate measurements of 1.0µgL-1 cadmium was ±2.67%. The method was applied to the analysis of 10 types of Thai herb samples. Percentage recoveries were in the range 94.5-110.2%. It was found that cadmium concentrations in all Thai herb samples were less than the maximum residue level.