Development of New Collagen/Clay Composite Biomaterials

The fabrication of collagen-based biomaterials for skin regeneration offers various challenges for tissue engineers. The purpose of this study was to obtain a novel series of composite biomaterials based on collagen and several types of clays. In order to investigate the influence of clay type on drug release behavior, the obtained collagen-based composite materials were further loaded with gentamicin. Physiochemical and biological analyses were performed to analyze the obtained nanocomposite materials after nanoclay embedding. Infrared spectra confirmed the inclusion of clay in the collagen polymeric matrix without any denaturation of triple helical conformation. All the composite samples revealed a slight change in the 2-theta values pointing toward a homogenous distribution of clay layers inside the collagen matrix with the obtaining of mainly intercalated collagen-clay structures, according X-ray diffraction analyses. The porosity of collagen/clay composite biomaterials varied depending on clay nanoparticles sort. Thermo-mechanical analyses indicated enhanced thermal and mechanical features for collagen composites as compared with neat type II collagen matrix. Biodegradation findings were supported by swelling studies, which indicated a more crosslinked structure due additional H bonding brought on by nanoclays. The biology tests demonstrated the influence of clay type on cellular viability but also on the antimicrobial behavior of composite scaffolds. All nanocomposite samples presented a delayed gentamicin release when compared with the collagen-gentamicin sample. The obtained results highlighted the importance of clay type selection as this affects the performances of the collagen-based composites as promising biomaterials for future applications in the biomedical field.

From Appendage to Crosslinker – Unusual Swelling Behavior in Spiropyran-Modified Hydrogels

Stimuli-responsive materials typically contain responsive molecular units that couple an external trigger to a defined macroscale response. Ongoing efforts to boost the versatility and complexity of these responses increasingly focus on multi-stimuli-responsive molecular units and crosslinkers, as these bear the potential to impart self-regulatory behaviors building on cooperative effects and feedback mechanisms. Herein, we study a stimuli-responsive platform consisting of polyacrylamide-based hydrogels with well-known multi-responsive spiropyrans covalently bound as pendant groups or ´non-innocent´ crosslinkers. Surprisingly, as compared to their appended counterparts, spiropyran crosslinkers cause up to two-fold larger hydrogel swelling in methylenebisacrylamide-crosslinked poly(acrylamide-co-acrylic acid) hydrogels, despite their increased relative crosslinking density. We seek the origin of this unexpected behavior by employing nanoindentation, swelling studies, and UV-vis spectroscopy to study changes in mechanical properties and in spiropyran isomer distribution as a function of solution pH, co-monomer chemistry, and swelling-induced polymer strain. We then estimate the osmotic counterion pressures as a function of spiropyran isomer distribution but find that such pressures alone are insufficient to explain the observed behavior. Charge complexation, cooperative effects between the hydrogel´s mechanics and chemistry, and aggregate formation may all be invoked to explain features of the observed ´non-innocence´ of spiropyran crosslinkers. Taken together, these insights will aid rational implementation of such responsive crosslinkers in materials design and extend the functionality of existing polymeric materials towards more complex and better tunable behaviors.

New Formulation and Characterization of Topical Films of Tioconazole and Evaluation of Their Antifungal Therapy

Purpose: New formulation of Scleroglucan (Sclg) films loaded with tioconazole, a medication typically applied for dermal treatments prepared. The feasibility of that treatment relies on the penetration of medications through the target layers of the skin in effective concentrations. Methods: Dynamic and mechanical characterization and swelling studies of the novel delivery system were analysed. An aqueous solution of Sclg (Cp=1% w/v) and glycerol (2% w/v) was prepared and kept at room temperature under magnetic stirring for 72 hrs. Tioconazole previously solubilised in Labrasol, was added to the polymer/glycerol solution. 4 ml of solution was poured in a plastic plate. The films were dried at 40°C for 1 hr and then allowed to dry at room temperature (about 25°C) for a week. Translucent films were obtained. The fungal strain used to test the film are CO23 sensitive to drugs, CO23 RFLC resistant to fluconazole, CO23 RFK resistant to micafungin, ATCC standard strain. Results: The water uptake of the films significantly increased up to 24 hrs. The optical microscope films images show that the presence of the drug did not significantly influence the appearance of the samples. The in vitro studies demonstrated the perceptible fungal activity of the new formulation against Candida albicans infections. Conclusion: The patches showed antimicrobial activity against all tested strains. An evident inhibition zone diameter, about 40 mm, for the strains sensitive to azoles (CO23 RFK and CO23) in comparison to strain resistant to fluconazole (CO23 RFLC) was observed. After 48 hours the inhibition zone diameters were reduced of about 6-7 mm in comparison to those observed after 24 hours of incubation.

Smart Hydrogels: Preparation, Characterization, and Determination of Transition Points of Crosslinked N-Isopropyl Acrylamide/Acrylamide/Carboxylic Acids Polymers

Smart hydrogels (SH) were prepared by thermal free radical polymerization of N-isopropyl acrylamide (NIPAAm), acrylamide (AAm) with acrylic acid (A) or maleic acid (M), and N, N′-methylene bisacrylamide. Spectroscopic and thermal characterizations of SHs were performed using FTIR, TGA, and DSC. To determine the effects of SHs on swelling characteristics, swelling studies were performed in different solvents, solutions, temperatures, pHs, and ionic strengths. In addition, cycle equilibrium swelling studies were carried out at different temperatures and pHs. The temperature and pH transition points of SHs are calculated using a sigmoidal equation. The pH transition points were calculated as 5.2 and 4.2 for SH-M and SH-A, respectively. The NIPAAm/AAm hydrogel exhibits a critical solution temperature (LCST) of 28.35 °C, while the SH-A and SH-M hydrogels exhibit the LCST of 34.215 °C and 28.798 °C, respectively, and the LCST of SH-A is close to the body. temperature. Commercial (CHSA) and blood human serum albumin (BHSA) were used to find the adsorption properties of biopolymers on SHs. SH-M was the most efficient SH, adsorbing 49% of CHSA while absorbing 16% of BHSA. In conclusion, the sigmoidal equation or Gaussian approach can be a useful tool for chemists, chemical engineers, polymer and plastics scientists to find the transition points of smart hydrogels.

The Effects of Monomer, Crosslinking Agent, and Filler Concentrations on the Viscoelastic and Swelling Properties of Poly(methacrylic acid) Hydrogels: A Comparison

The present work aims at comparatively studying the effects of the concentrations of a monomer (10–30 wt% based on the whole hydrogel composition), crosslinking agent (1–3 mol% based on the monomer), and reinforcing agent (montmorillonite-MMT, 1–3 wt.% based on the whole hydrogel composition) on the swelling and viscoelastic properties of the crosslinked hydrogels prepared from methacrylic acid (MAA) and N,N′-methylenebisacrylamide (BIS) in the presence of K2S2O8 in aqueous solution. The viscoelastic measurements, carried out on the as-prepared hydrogels, showed that the monomer concentration had the largest impact, its three-time enhancement causing a 30-fold increase in the storage modulus, as compared with only a fivefold increase in the case of the crosslinking agent and 1.5-fold increase for MMT in response to a similar threefold concentration increase. Swelling studies, performed at three pH values, revealed that the water absorption of the hydrogels decreased with increasing concentration of both the monomer and crosslinking agent, with the amplitude of the effect of concentration modification being similar at pH 5.4 and 7.4 in both cases, but very different at pH 1.2. Further, it was shown that the increased pH differently influenced the swelling degree in the case of the hydrogel series in which the concentrations of the monomer and crosslinking agent were varied. In contrast to the effect of the monomer and crosslinking agent concentrations, the increase in the MMT amount in the hydrogel resulted in an increased swelling degree at pH 5.4 and 7.4, while at pH 1.2, a slight decrease in the water absorption was noticed. The hydrogel crosslinking density determinations revealed that this parameter was most affected by the increase in the monomer concentration.

3D-Printed Gelatin Methacryloyl-Based Scaffolds with Potential Application in Tissue Engineering

The development of materials for 3D printing adapted for tissue engineering represents one of the main concerns nowadays. Our aim was to obtain suitable 3D-printed scaffolds based on methacrylated gelatin (GelMA). In this respect, three degrees of GelMA methacrylation, three different concentrations of GelMA (10%, 20%, and 30%), and also two concentrations of photoinitiator (I-2959) (0.5% and 1%) were explored to develop proper GelMA hydrogel ink formulations to be used in the 3D printing process. Afterward, all these GelMA hydrogel-based inks/3D-printed scaffolds were characterized structurally, mechanically, and morphologically. The presence of methacryloyl groups bounded to the surface of GelMA was confirmed by FTIR and 1H-NMR analyses. The methacrylation degree influenced the value of the isoelectric point that decreased with the GelMA methacrylation degree. A greater concentration of photoinitiator influenced the hydrophilicity of the polymer as proved using contact angle and swelling studies because of the new bonds resulting after the photocrosslinking stage. According to the mechanical tests, better mechanical properties were obtained in the presence of the 1% initiator. Circular dichroism analyses demonstrated that the secondary structure of gelatin remained unaffected during the methacrylation process, thus being suitable for biological applications.

FABRICATION OF NANO CLAY INTERCALATED POLYMERIC MICROBEADS FOR CONTROLLED RELEASE OF CURCUMIN

Objective: The objective of this study was to formulate and evaluate the Curcumin (CUR) encapsulated sodium alginate (SA)/badam gum (BG)/kaolin (KA) microbeads for controlled drug release studies. Methods: The fabricated microbeads were characterized by fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (X-RD), and scanning electron microscopy (SEM). Dynamic swelling studies and in vitro release kinetics were performed in simulated intestinal fluid (pH 7.4) and simulated gastric fluid (pH 1.2) at 37 °C. Results: FTIR confirms the formation of microbeads. DSC studies confirm the polymorphism of CUR in drug loaded microbeads which indicate the molecular level dispersion of the drug in the microbeads. SEM studies confirmed the microbeads are spherical in shape with wrinkled and rough surfaces. XRD studies reveal the molecular dispersion of CUR and the presence of KA in the developed microbeads. In vitro release studies and swelling studies depend on the pH of test media, which might be suitable for intestinal drug delivery. The % of drug release values fit into the Korsmeyer-Peppas equation and n values are obtained in the range of 0.577-0.664, which indicates that the developed microbeads follow the non-Fickian diffusion drug release mechanism. Conclusion: The results concluded that the CUR encapsulated microbeads are potentially good carriers for controlled drug release studies.