Development of pH-Responsive, Thermosensitive, Antibacterial, and Anticancer CS/PVA/Graphene Blended Hydrogels for Controlled Drug Delivery.

Drug delivery techniques based on polymers have been investigated for their potential to improve drug solubility, reduce systemic side effects, and controlled and targeted administration at infection site. In this study, we developed a co-polymeric hydrogel composed of graphene sheets (GNS), polyvinyl alcohol (PVA), and chitosan (CS) that is loaded with methotrexate (MTX) for in vitro liver cancer treatment. Fourier transform infrared spectroscopy (FTIR) and atomic force microscopy (AFM) was employed to check the structural properties and surface morphology. Moreover, tests were conducted on the cytotoxicity, hemolytic activity, release kinetics, swelling behaviour and degradation of hydrogels. A controlled release of drug from hydrogel in PBS at pH 7.4 was examined using release kinetics. Maximal drug release in six hours was 97.34%. The prepared hydrogels did not encourage the HepG2 growth and were non-hemolytic. The current study highlights the potential of GNS-based hydrogel loaded with MTX as an encouraging therapy for hepatocellular carcinoma. HepG2 cell viability of MTX-loaded CS-PVA-GNS hydrogel was (IC50 5.87 µg/200 mL) in comparison to free MTX (IC50 5.03 µg/200 mL). These outcomes recommend that hydrogels with GNS ensure improved drug delivery in cancer microenvironment while lessening adverse consequences on healthy cells.

Tuning phase separation in DPPDTT/PMMA blend to achieve molecular self-assembly in the conducting polymer for organic field effect transistors.

The semiconductor/insulator blends for organic field-effect transistors are a potential solution to improve the charge transport in the active layer by inducing phase separation in the blends. However, the technique is less investigated for long-chain conducting polymers such as Poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno [3,2-b]thiophene)] (DPPDTT), and lateral phase separation is generally reported due to the instability during solvent evaporation, which results in degraded device performance. Herein, we report how to tailor the dominant mechanism of phase separation in such blends and the molecular assembly of the polymer. For DPPDTT/PMMA blends, we found that for higher DPPDTT concentrations (more than 75%) where the vertical phase separation mechanism is dominant, PMMA assisted in the self-assembly of DPPDTT to form nanowires and micro-transport channels on top of PMMA. The formation of nanowires yielded 13 times higher mobility as compared to pristine devices. For blend ratios with DPPDTT ≤ 50%, both the competing mechanisms, vertical and lateral phase separation, are taking place. It resulted in somewhat lower charge carrier mobilities. Hence, our results show that by systematic tuning of the blend ratio, PMMA can act as an excellent binding material in long-chain polymers such as DPPDTT and produce vertically stratified and aligned structures to ensure high mobility devices.

Synthesis and Characterization of Cobalt-Doped Ferrites for Biomedical Applications.

Novel materials for biomedical applications are in critical need of time. In the present work, the antibacterial properties of Co1-x Ni x Mg x Fe2O4 nanoparticles (NPs) are assessed by the disc diffusion method for the common pathogen, that is, Gram-negative (Escherichia coli and Pseudomonas aeruginosa) and Gram-positive (Staphylococcus aureus) bacteria. Overnight grown bacterial cultures were individually lawn-cultured on nutrient agar plates. All samples of NP concentrations (2 mg/mL) were prepared in sterile water and dispensed by sonication. Sterile filter paper discs (1.0 mm) were saturated by the (doped CoFe2O4) NP solution and incubated at 37 ± 0.1 °C for 24 h. The NPs with a fine size of 30-70 nm of Co1-x Ni x Mg x Fe2O4 were achieved using the sol-gel method by doping CoFe2O4 initially with Ni and codoping with Mg, and their properties were studied by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and Fourier transform infrared techniques. According to the results, Co0.5Ni0.25Mg0.25Fe2O4 NPs exhibited potent antibacterial activities against s. aureus having an inhibition zone of 6.5 mm and P. aeruginosa having an inhibition zone of 6 mm as that were examined. The result shows that the bacteriostatic properties of NPs are used for numerous applications such as hyperthermia, antibacterial treatments, and targeted drug delivery.

Role of Solvent Used in Development of Graphene Oxide Coating on AZ31B Magnesium Alloy: Corrosion Behavior and Biocompatibility Analysis.

Clinical applications of bio-absorbable magnesium (Mg) and its alloys can be enhanced by increasing their corrosion resistance, using surface modification and functionality. In this study, we synthesized graphene oxide (GO) through improved Hummers' method and deposited it on biodegradable AZ31B Mg alloy for further characterization. Different suspensions of GO were prepared in various solvents, like deionized water, ethanol, and acetone by ultra-sonication. Electrophoretic deposition (EPD) was used to develop GO coatings on AZ31B Mg using different GO suspensions. Effect of various solvents on corrosion behavior, as well as in vitro biocompatibility, was studied. The optimized EPD parameters were 3 volts and 90 s for coating. Different characterization techniques were used to study GO and prepared coatings. Atomic force microscopy found that the average thickness of GO was ~1 nm. Electrochemical behavior of coatings was studied through electrochemical impedance spectroscopy (EIS) and Tafel analysis in Ringer's lactate solution. Tafel analysis revealed that GO coatings deposited by GO water suspension increased corrosion protection efficiency of AZ31B Mg alloy by ~94%. After 72 h incubation in MC3T3-E1 osteoblast cells extract, in vitro analysis was performed to determine the cell viability and biocompatibility of the GO- coated and bare Mg samples. GO coatings deposited by GO water suspension demonstrated ~2× cell viability, as well as nontoxicity and better biocompatibility compared to the bare and other GO-coated Mg samples.

Smart and pH-sensitive rGO/Arabinoxylan/chitosan composite for wound dressing: In-vitro drug delivery, antibacterial activity, and biological activities.

Carbohydrate polymers are biological macromolecules that have sparked a lot of interest in wound healing due to their outstanding antibacterial properties and sustained drug release. Arabinoxylan (ARX), Chitosan (CS), and reduced graphene oxide (rGO) sheets were combined and crosslinked using tetraethyl orthosilicate (TEOS) as a crosslinker to fabricate composite hydrogels and assess their potential in wound dressing for skin wound healing. Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM), transmission electron microscopy (TEM), and biological assays were used to evaluate the composite hydrogels. FTIR validated the effective fabrication of the composite hydrogels. The rough morphologies of the composite hydrogels were revealed by SEM and AFM (as evident from the Ra values). ATC-4 was discovered to have the roughest surface. TEM revealed strong homogeneous anchoring of the rGO to the polymer matrix. However, with higher amount of rGO agglomeration was detected. The % swelling at various pHs (1-13) revealed that the hydrogels were pH-sensitive. The controlled release profile for the antibacterial drug (Silver sulfadiazine) evaluated at various pH values (4.5, 6.8, and 7.4) in PBS solution and 37 °C using the Franz diffusion method revealed maximal drug release at pH 7.4 and 37 °C. The antibacterial efficacy of the composite hydrogels against pathogens that cause serious skin diseases varied. The MC3T3-E1 cell adhered, proliferated, and differentiated well on the composite hydrogels. MC3T3-E1 cell also illustrated excellent viability (91%) and proper cylindrical morphologies on the composite hydrogels. Hence, the composite hydrogels based on ARX, CS, and rGO are promising biomaterials for treating and caring for skin wounds.

Development of Antibacterial, Degradable and pH-Responsive Chitosan/Guar Gum/Polyvinyl Alcohol Blended Hydrogels for Wound Dressing.

The present research is based on the fabrication preparation of CS/PVA/GG blended hydrogel with nontoxic tetra orthosilicate (TEOS) for sustained paracetamol release. Different TEOS percentages were used because of their nontoxic behavior to study newly designed hydrogels' crosslinking and physicochemical properties. These hydrogels were characterized using Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and wetting to determine the functional, surface morphology, hydrophilic, or hydrophobic properties. The swelling analysis in different media, degradation in PBS, and drug release kinetics were conducted to observe their response against corresponding media. The FTIR analysis confirmed the components added and crosslinking between them, and surface morphology confirmed different surface and wetting behavior due to different crosslinking. In various solvents, including water, buffer, and electrolyte solutions, the swelling behaviour of hydrogel was investigated and observed that TEOS amount caused less hydrogel swelling. In acidic pH, hydrogels swell the most, while they swell the least at pH 7 or higher. These hydrogels are pH-sensitive and appropriate for controlled drug release. These hydrogels demonstrated that, as the ionic concentration was increased, swelling decreased due to decreased osmotic pressure in various electrolyte solutions. The antimicrobial analysis revealed that these hydrogels are highly antibacterial against Gram-positive (Staphylococcus aureus and Bacillus cereus) and Gram negative (Pseudomonas aeruginosa and Escherichia coli) bacterial strains. The drug release mechanism was 98% in phosphate buffer saline (PBS) media at pH 7.4 in 140 min. To analyze drug release behaviour, the drug release kinetics was assessed against different mathematical models (such as zero and first order, Higuchi, Baker-Lonsdale, Hixson, and Peppas). It was found that hydrogel (CPG2) follows the Peppas model with the highest value of regression (R2 = 0.98509). Hence, from the results, these hydrogels could be a potential biomaterial for wound dressing in biomedical applications.

Chitosan/Poly Vinyl Alcohol/Graphene Oxide Based pH-Responsive Composite Hydrogel Films: Drug Release, Anti-Microbial and Cell Viability Studies.

The composite hydrogels were produced using the solution casting method due to the non-toxic and biocompatible nature of chitosan (CS)/polyvinyl alcohol (PVA). The best composition was chosen and crosslinked with tetraethyl orthosilicate (TEOS), after which different amounts of graphene oxide (GO) were added to develop composite hydrogels. Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM) and contact angle was used to analyze the hydrogels. The samples were also evaluated for swelling abilities in various mediums. The drug release profile was studied in phosphate-buffered saline (PBS) at a pH of 7.4. To predict the mechanism of drug release, the data were fitted into kinetic models. Finally, antibacterial activity and cell viability data were obtained. FTIR studies revealed the successful synthesis of CS/PVA hydrogels and GO/CS/PVA in hydrogel composite. SEM showed no phase separation of the polymers, whereas AFM showed a decrease in surface roughness with an increase in GO content. 100 µL of crosslinker was the critical concentration at which the sample displayed excellent swelling and preserved its structure. Both the crosslinked and composite hydrogel showed good swelling. The most acceptable mechanism of drug release is diffusion-controlled, and it obeys Fick's law of diffusion for drug released. The best fitting of the zero-order, Hixson-Crowell and Higuchi models supported our assumption. The GO/CS/PVA hydrogel composite showed better antibacterial and cell viability behaviors. They can be better biomaterials in biomedical applications.

Development of Biopolymeric Hybrid Scaffold-Based on AAc/GO/nHAp/TiO2 Nanocomposite for Bone Tissue Engineering: In-Vitro Analysis.

Bone tissue engineering is an advanced field for treatment of fractured bones to restore/regulate biological functions. Biopolymeric/bioceramic-based hybrid nanocomposite scaffolds are potential biomaterials for bone tissue because of biodegradable and biocompatible characteristics. We report synthesis of nanocomposite based on acrylic acid (AAc)/guar gum (GG), nano-hydroxyapatite (HAp NPs), titanium nanoparticles (TiO2 NPs), and optimum graphene oxide (GO) amount via free radical polymerization method. Porous scaffolds were fabricated through freeze-drying technique and coated with silver sulphadiazine. Different techniques were used to investigate functional group, crystal structural properties, morphology/elemental properties, porosity, and mechanical properties of fabricated scaffolds. Results show that increasing amount of TiO2 in combination with optimized GO has improved physicochemical and microstructural properties, mechanical properties (compressive strength (2.96 to 13.31 MPa) and Young's modulus (39.56 to 300.81 MPa)), and porous properties (pore size (256.11 to 107.42 µm) and porosity (79.97 to 44.32%)). After 150 min, silver sulfadiazine release was found to be ~94.1%. In vitro assay of scaffolds also exhibited promising results against mouse pre-osteoblast (MC3T3-E1) cell lines. Hence, these fabricated scaffolds would be potential biomaterials for bone tissue engineering in biomedical engineering.

Correction: Development and in vitro evaluation of κ-carrageenan based polymeric hybrid nanocomposite scaffolds for bone tissue engineering.

[This corrects the article DOI: 10.1039/D0RA07446B.].

Grain Fe and Zn contents linked SSR markers based genetic diversity in rice.

Rice is critical for sustainable food and nutritional security; however, nominal micronutrient quantities in grains aggravate malnutrition in rice-eating poor populations. In this study, we evaluated genetic diversity in grain iron (Fe) and zinc (Zn) contents using trait-linked simple sequence repeat (SSR) markers in the representative subset of a large collection of local and exotic rice germplasm. Results demonstrated that aromatic fine grain accessions contained relatively higher Fe and Zn contents in brown rice (BR) than coarse grain accessions and a strong positive correlation between both mineral elements. Genotyping with 24 trait-linked SSR markers identified 21 polymorphic markers, among which 17 demonstrated higher gene diversity and polymorphism information content (PIC) values, strongly indicating that markers used in current research were moderate to highly informative for evaluating the genetic diversity. Population structure, principal coordinate and phylogenetic analyses classified studied rice accessions into two fine grain specific and one fine and coarse grain admixture subpopulations. Single marker analysis recognized four ZnBR and single FeBR significant marker-trait associations (MTAs) contributing 15.41-39.72% in total observed phenotypic variance. Furthermore, high grain Fe and Zn contents linked marker alleles from significant MTAs were also identified. Collectively, these results indicate a wide genetic diversity exist in grain Fe and Zn contents of studied rice accessions and reveal perspective for marker-assisted biofortification breeding.

Novel functional antimicrobial and biocompatible arabinoxylan/guar gum hydrogel for skin wound dressing applications.

It is a challenging task to develop active biomacromolecular wound dressing materials that are biocompatible and possesses antibacterial properties against the bacterial strains that cause severe skin disease. This work is focused on the preparation of a biocompatible and degradable hydrogel for wound dressing application using arabinoxylan (ARX) and guar gum (GG) natural polymers. Fourier transform infrared spectroscopy (FT-IR) confirmed that both ARX and GG interacted well with each other, and their interactions further increased with the addition of crosslinker tetraethyl orthosilicate. Scanning electron microscope (SEM) micrographs showed uniform porous morphologies of the hydrogels. The porous morphologies and uniform interconnected pores are attributed to the increased crosslinking of the hydrogel. Elastic modulus, tensile strength, and fracture strain of the hydrogels significantly improved (from ATG-1 to ATG-4) with crosslinking. Degradability tests showed that hydrogels lost maximum weight in 7 days. All the samples showed variation in swelling with pH. Maximum swelling was observed at pH 7. The hydrogel samples showed good antibacterial activity against Pseudomonas aeruginosa (Gram-negative) and Staphylococcus aureus (Gram-positive) in PBS, good drug release profile (92% drug release), and nontoxic cellular behavior. The cells not only retained their cylindrical morphologies onto the hydrogel but were also performing their normal activities. It is, therefore, believed that as-developed hydrogel could be a potential material for wound dressing application.

Development and in vitro evaluation of κ-carrageenan based polymeric hybrid nanocomposite scaffolds for bone tissue engineering.

The excellent biocompatible and osteogenesis characteristics of porous scaffolds play a vital role in bone regeneration. In this study, we have synthesized polymeric hybrid nanocomposites via free-radical polymerization from carrageenan/acrylic-acid/graphene/hydroxyapatite. Porous hybrid nanocomposite scaffolds were fabricated through a freeze-drying method to mimic the structural and chemical composition of natural bone. Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and water contact-angle studies were carried-out for functional groups, surface morphology and hydrophilicity of the materials, followed by biodegradation and swelling analysis. The cell viability, cell culture and proliferation were evaluated against mouse pre-osteoblast (MC3T3-E1) cell lines using neutral red dye assay. The cell adherence and proliferation studies were determined by SEM. Physical characterization including optimum porosity and pore size (49.75% and 0.41 × 103 µm2), mechanical properties (compression strength 8.87 MPa and elastic modulus 442.63 MPa), swelling (70.20% at 27 °C and 77.21% at 37 °C) and biodegradation (23.8%) were performed. The results indicated CG-g-AAc-3 with a high optical density and better cell viability. Hence, CG-g-AAc-3 was found to be more efficient for bone regeneration with potential applications in fractured bone regeneration.

Functionalized graphene oxide coating on Ti6Al4V alloy for improved biocompatibility and corrosion resistance.

The present study focused on the development of magnesium-functionalized graphene oxide (FGO) coating on titanium alloy (Ti6Al4V) by electrophoretic deposition. Graphene oxide (GO) was synthesized by modified Hummers' method and functionalized with magnesium ions. X-ray diffraction, infrared spectroscopy (IR) and Raman spectroscopy were employed to confirm the synthesis of GO and GO-coatings on Ti6Al4V. Functionalization of GO with Mg ions was confirmed by energy dispersive X-ray spectroscopy. The surface morphology of coated samples was examined through scanning electron microscopy. Reduction of FGO coating (labelled as rFGO) by heating at 200 °C was confirmed by IR. The rFGO coated Ti6Al4V was found to be hydrophilic in nature as determined by contact angle measurement which showed reduction in the contact angle of Ti6Al4V from 95.4° to 42.1°. The percent cell viability over the coated sample was appreciably improved compared to as-received Ti6Al4V sample owing to hydrophilicity of the former. The positive shift in open circuit potential and increase in polarization resistance was observed after coating Ti6Al4V samples with FGO. The significant decrease in the corrosion current density and negative polarization loop in the reverse scan of samples also confirmed the improved corrosion resistance of rFGO-coated Ti6Al4V over uncoated Ti6Al4V in the PBS solution. Furthermore, the impedance spectroscopy revealed that the preferential adsorption of ionic species (indicated by large Rads) at the surface improved the barrier characteristics of rFGO coated samples and exhibited an order of magnitude higher Rct compared to as-received samples.

Graphite nanoplatelets produced by oxidation and thermal exfoliation of graphite and electrical conductivities of their epoxy composites.

Graphite nanoplatelets were produced by sonication of thermally reduced graphite oxide produced from three precursor graphites. The thicknesses of the resulting graphite nanoplatlets were measured by X-ray diffraction and transmission electron microscopy. The type and size of the precursor graphite plays an important role in the final graphite nanoplatelet quality. The thinnest graphite nanoplatelets (average thickness of 4-7 nm) were obtained from Sri Lankan powdered graphite (average particle size of 0.1-0.2 mm). Thicker graphite nanoplatelets (average thickness of 30-60 nm), were obtained from a Canadian graphite (with an average flake size of 0.5-2 mm). Graphite nanoplatelets obtained by acid intercalation of Sri Lankan graphite were much thicker (an average thickness of 150 nm). Graphite nanoplatelet/epoxy composites containing 4 wt.% graphite nanoplatelets derived from Canadian or Sri Lankan natural graphite have electrical conductivities significantly above the percolation conductivity threshold. In contrast, corresponding composites, produced with (4 wt.%) commercial graphite nanoplatelets, either as-received or re-exfoliated, were electrically insulating. This behaviour is attributed to the highly wrinkled morphology, folded edges and abundant surface functional groups of the commercial graphite nanoplatelets. Thermal reduction of graphite oxide produced from natural flake graphite is therefore a promising route for producing graphite nanoplatelets fillers for electrically-conducting polymer composites.