Methylcellulose–Cellulose Nanocrystal Composites for Optomechanically Tunable Hydrogels and Fibers

Chemical modification of cellulose offers routes for structurally and functionally diverse biopolymer derivatives for numerous industrial applications. Among cellulose derivatives, cellulose ethers have found extensive use, such as emulsifiers, in food industries and biotechnology. Methylcellulose, one of the simplest cellulose derivatives, has been utilized for biomedical, construction materials and cell culture applications. Its improved water solubility, thermoresponsive gelation, and the ability to act as a matrix for various dopants also offer routes for cellulose-based functional materials. There has been a renewed interest in understanding the structural, mechanical, and optical properties of methylcellulose and its composites. This review focuses on the recent development in optically and mechanically tunable hydrogels derived from methylcellulose and methylcellulose–cellulose nanocrystal composites. We further discuss the application of the gels for preparing highly ductile and strong fibers. Finally, the emerging application of methylcellulose-based fibers as optical fibers and their application potentials are discussed.     

Incorporation of Copper-Doped Mesoporous Bioactive Glass Nanospheres in Experimental Dental Composites: Chemical and Mechanical Characterization

Experimental dental resin composites incorporating copper-doped mesoporous bioactive glass nanospheres (Cu-MBGN) were designed to impart antibacterial and remineralizing properties. The study evaluated the influence of Cu-MBGN on the mechanical properties and photopolymerization of resin composites. Cu-MBGN were synthesized using a microemulsion-assisted sol–gel method. Increasing amounts of Cu-MBGN (0, 1, 5, and 10 wt %) were added to the organic polymer matrix with inert glass micro- and nanofillers while maintaining a constant resin/filler ratio. Six tests were performed: X-ray diffraction, scanning electron microscopy, flexural strength (FS), flexural modulus (FM), Vickers microhardness (MH), and degree of conversion (DC). FS and MH of Cu-MBGN composites with silica fillers showed no deterioration with aging, with statistically similar results at 1 and 28 days. FM was not influenced by the addition of Cu-MBGN but was reduced for all tested materials after 28 days. The specimens with 1 and 5% Cu-MBGN had the highest FS, FM, MH, and DC values at 28 days, while controls with 45S5 bioactive glass had the lowest FM, FS, and MH. DC was high for all materials (83.7–93.0%). Cu-MBGN composites with silica have a potential for clinical implementation due to high DC and good mechanical properties with adequate resistance to aging.     

Biopolymer Composites with Sensors for Environmental and Medical Applications

One of the biggest economic and environmental sustainability problems is the over-reliance on petroleum chemicals in polymer production. This paper presents an overview of the current state of knowledge on biopolymers combined with biosensors in terms of properties, compounding methods and applications, with a focus on medical and environmental aspects. Therefore, this article is devoted to environmentally friendly polymer materials. The paper presents an overview of the current state of knowledge on biopolymers combined with biosensors in terms of properties, compounding methods and applications, with a special focus on medical and environmental aspects. The paper presents the current state of knowledge, as well as prospects. The article shows that biopolymers made from renewable raw materials are of great interest in various fields of science and industry. These materials not only replace existing polymers in many applications, but also provide new combinations of properties for new applications. Composite materials based on biopolymers are considered superior to traditional non-biodegradable materials due to their ability to degrade when exposed to environmental factors. The paper highlights the combination of polymers with nanomaterials which allows the preparation of chemical sensors, thus enabling their use in environmental or medical applications due to their biocompatibility and sensitivity. This review focuses on analyzing the state of research in the field of biopolymer-sensor composites.     

Development of New Hybrid Casein-Loaded PHEMA-PEGDA Hydrogels with Enhanced Mineralisation Potential

Casein is a micellar protein rich in glutamic and aspartic acids as well as in phosphoserine. Considering its native affinity for calcium and the connection of sub-micelles through calcium phosphate nanoclusters, this protein holds promise for stimulating biomimetic mineralisation phenomena and direct binding with the mineral phase of hard tissues. In this work we prepared new hybrids based on casein embedded in a poly(2-hydroxyethyl methacrylate)-polyethyleneglycol diacrylate (PHEMA-PEGDA) hydrogel. The resulting materials were investigated structurally by Fourier transform infrared (FT-IR). Casein modified the water affinity and the rheological properties of the hybrids. The microstructure was explored by scanning electron microscopy (SEM) and the distribution of the protein was established by combined SEM micrographs and elemental mapping considering the casein-specific elements (P, N and S) not contained by the synthetic hydrogel matrix. The effect of casein on the mineralisation potential and stability of the mineral phase was investigated by FT-IR and SEM when alternating incubation in Ca/P solutions is performed. Increasing casein content in the hybrids leads to improved mineralisation, with localised formation of nanoapatite phase on the protein areas in the richest sample in protein. This behaviour was proved microstructurally by SEM and through overlapping elemental distribution of Ca and P from the newly formed mineral and P, S and N from the protein. This study indicates that nanoapatite-casein-PHEMA-PEGDA nanocomposites may be developed for potential use in bone repair and regeneration.     

Preparation and Swelling Behaviors of High-Strength Hemicellulose-g-Polydopamine Composite Hydrogels

Hemicellulose-based composite hydrogels were successfully prepared by adding polydopamine (PDA) microspheres as reinforcing agents. The effects of PDA microsphere size, dosage, and nitrogen content in hydrogel on the mechanical and rheological properties was studied. The compressive strength of hydrogel was increased from 0.11 to 0.30 MPa. The storage modulus G’ was increased from 7.9 to 22.0 KPa. The gaps in the hemicellulose network are filled with PDA microspheres. There is also chemical cross-linking between them. These gaps increased the density of the hydrogel network structure. It also has good water retention and pH sensitivity. The maximum cumulative release rate of methylene blue was 62.82%. The results showed that the release behavior of hydrogel was pH-responsive, which was beneficial to realizing targeted and controlling drug release.     

Correlations on the Structure and Properties of Collagen Hydrogels Produced by E-Beam Crosslinking

In this study, a collagen hydrogel using collagen exclusively produced in Romania, was obtained by electron beam (e-beam) crosslinking. The purpose of our study is to obtain new experimental data on the crosslinking of collagen and to predict as faithfully as possible, its behavior at high irradiation doses and energies. To pursue this, the correlations between macromolecular structure and properties of collagen hydrogels were determined by rheological analysis, Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), and Differential Scanning Calorimetry (DSC), respectively. The gel fraction, swelling degree, and network parameters of the collagen hydrogels were also investigated at different irradiation doses. Through experimental exploration, we concluded that irradiation with e-beam up to 25 kGy induces crosslinking processes in collagen structure without producing advanced degradation processes. E-beam technology is a great method to develop new materials for medical applications without adding other chemical reagents harmful to human health. The future aim is to develop new wound dressings for rapid healing based on collagen, through irradiation technologies.     

Chitin-Methacrylate: Preparation,Characterization and Hydrogel Formation

Chitin-methacrylate (CM) was prepared by the reaction of methacrylic acid on chitin in 5% LiCl/DMAc in the presence of N,N’-dicyclocarbodiimide and dimethylaminopyridine. The resultant chitin-methacrylate product was isolated in 61% yield and was found to be readily water-soluble. The derivative was found to be a mixture of methacrylate and methacrylic-dimethylaminopyridine complex substituents at the C-6 position in approximately equal amounts. In order to evaluate the activity of the methacrylate double bond, a chitin-methacrylate water solution was photo-crosslinked in the presence of Irgacure 2959 photo-initiator to generate CM-hydrogel. The CM-hydrogel was evaluated for its biodegradability characteristics by enzymatic degradation with lysozyme solutions of varying concentrations. Completely water-soluble products were obtained within 48 h. In vitro cytotoxicity assays of the CM-hydrogel and its extract against three cell lines, NCTC clone 929, IMR-90 and MG-63, indicated the hydrogel was non-cytotoxic with cells able to adhere and proliferate well on the hydrogel.     

Functionalization of Cellulose-Based Hydrogels with Bi-Functional Fusion Proteins Containing Carbohydrate-Binding Modules

Materials with novel and enhanced functionalities can be obtained by modifying cellulose with a range of biomolecules. This functionalization can deliver tailored cellulose-based materials with enhanced physical and chemical properties and control of biological interactions that match specific applications. One of the foundations for the success of such biomaterials is to efficiently control the capacity to combine relevant biomolecules into cellulose materials in such a way that the desired functionality is attained. In this context, our main goal was to develop bi-functional biomolecular constructs for the precise modification of cellulose hydrogels with bioactive molecules of interest. The main idea was to use biomolecular engineering techniques to generate and purify different recombinant fusions of carbohydrate binding modules (CBMs) with significant biological entities. Specifically, CBM-based fusions were designed to enable the bridging of proteins or oligonucleotides with cellulose hydrogels. The work focused on constructs that combine a family 3 CBM derived from the cellulosomal-scaffolding protein A from Clostridium thermocellum (CBM3) with the following: (i) an N-terminal green fluorescent protein (GFP) domain (GFP-CBM3); (ii) a double Z domain that recognizes IgG antibodies; and (iii) a C-terminal cysteine (CBM3C). The ability of the CBM fusions to bind and/or anchor their counterparts onto the surface of cellulose hydrogels was evaluated with pull-down assays. Capture of GFP-CBM3 by cellulose was first demonstrated qualitatively by fluorescence microscopy. The binding of the fusion proteins, the capture of antibodies (by ZZ-CBM3), and the grafting of an oligonucleotide (to CBM3C) were successfully demonstrated. The bioactive cellulose platform described here enables the precise anchoring of different biomolecules onto cellulose hydrogels and could contribute significatively to the development of advanced medical diagnostic sensors or specialized biomaterials, among others.     

The Preparation and Characterization of Chitosan-Based Hydrogels Cross-Linked by Glyoxal

In this study, hydrogels based on chitosan cross-linked by glyoxal have been investigated for potential medical applications. Hydrogels were loaded with tannic acid at different concentrations. The thermal stability and the polyphenol-releasing rate were determined. For a preliminary assessment of the clinical usefulness of the hydrogels, they were examined for blood compatibility and in the culture of human dental pulp cells (hDPC). The results showed that after immersion in a polyphenol solution, chitosan/glyoxal hydrogels remain nonhemolytic for erythrocytes, and we also did not observe the cytotoxic effect of hydrogels immersed in tannic acid (TA) solutions with different concentration. Tannic acid was successfully released from hydrogels, and its addition improved material thermal stability. Thus, the current findings open the possibility to consider such hydrogels in clinics.     

Preclinical Evaluation of Poly(HEMA-co-acrylamide) Hydrogels Encapsulating Glucose Oxidase and Palladium Benzoporphyrin as Fully Implantable Glucose Sensors

Background:

Continuous glucose monitors (CGMs) require percutaneous wire probes to monitor glucose. Sensors based on luminescent hydrogels are being explored as fully implantable alternatives to traditional CGMs. Our previous work investigated hydrogel matrices functionalized with enzymes and oxygen-quenched phosphors, demonstrating sensitivity to glucose, range of response, and biofouling strongly depend on the matrix material. Here, we further investigate the effect of matrix composition on overall performance in vitro and in vivo.

Methods:

Sensors based on three hydrogels, a poly(2-hydroxyethyl methacrylate) (pHEMA) homopolymer and 2 poly(2-hydroxyethyl methacrylate-co-acrylamide) (pHEMA-co-AAm) copolymers, were compared. These were used to entrap glucose oxidase (GOx), catalase, and an oxygen-sensitive benzoporphyrin phosphor. All sensor formulations were evaluated for glucose response and stability at physiological temperatures. Selected sensors were then evaluated as implanted sensors in a porcine model challenged with glucose and insulin. The animal protocol used in this study was approved by an IACUC committee at Texas A&M University.

Results:

PHEMA-co-AAm copolymer hydrogels (75:25 HEMA:AAm) yielded the most even GOx and dye dispersion throughout the hydrogel matrix and best preserved GOx apparent activity. In response to in vitro glucose challenges, this formulation exhibited a dynamic range of 12-167 mg/dL, a sensitivity of 1.44 ± 0.46 µs/(mg/dL), and tracked closely with reference capillary blood glucose values in vivo.

Conclusions:

The hydrogel-based sensors exhibited excellent sensitivity and sufficiently rapid response to the glucose levels achieved in vivo, proving feasibility of these materials for use in real-time glucose tracking. Extending the dynamic range and assessing long-term effects in vivo are ongoing efforts.     

Polymer Composites with Self-Regulating Temperature Behavior: Properties and Characterization

A novel conductive composite material with homogeneous binary polymer matrix of HDPE (HD) and LLDPE (LLD), mixed with conductive filler consisting of carbon black (CB) and graphite (Gr), was tested against a HDPE composite with a similar conductive filler. Even the concentration of the conductive filler was deliberately lower for (CB + Gr)/(LLD + HD), and the properties of this composite are comparable or better to those of (CB + Gr)/HD. The kinetic parameters of the ρ-T curves and from the DSC curves indicate that the resistivity peak is obtained when the polymer matrix is fully melted. When subjected to repeated thermal cycles, the composite (CB + Gr)/(LLD + HD) presented a better electrical behavior than composite CB + Gr)/HD, with an increase in resistivity (ρ_max) values with the number of cycles, as well as less intense NTC (Negative Temperature Coefficient) effects, both for the crosslinked and thermoplastic samples. Radiation crosslinking led to increased ρ_max values, as well as to inhibition of NTC effects in both cases, thus having a clear beneficial effect. Limitation effects of surface temperature and current intensity through the sample were observed at different voltages, enabling the use of these materials as self-regulating heating elements at various temperatures below the melting temperature. The procedure based on physical mixing of the components appears more efficient in imparting lower resistivity in solid state and high PTC (Positive Temperature Coefficient) effects to the composites. This effect is probably due to the concentration of the conductive particles at the surface of the polymer domains, which would facilitate the formation of the conductive paths. Further work is still necessary to optimize both the procedure of composite preparation and the properties of such materials.     

Bioactive Properties of Composites Based on Silicate Glasses and Different Silver and Gold Structures

Using an ideal biomaterial to treat injured bones can accelerate the healing process and simultaneously exhibit antibacterial properties; thus protecting the patient from bacterial infections. Therefore, the aim of this work was to synthesize composites containing silicate-based bioactive glasses and different types of noble metal structures (i.e., AgI pyramids, AgIAu composites, Au nanocages, Au nanocages with added AgI). Bioactive glass was used as an osteoconductive bone substitute and Ag was used for its antibacterial character, while Au was included to accelerate the formation of new bone. To investigate the synergistic effects in these composites, two syntheses were carried out in two ways: AgIAu composites were added in either one step or AgI pyramids and Au nanocages were added separately. All composites showed good in vitro bioactivity. Transformation of AgI in bioactive glasses into Ag nanoparticles and other silver species resulted in good antibacterial behavior. It was observed that the Ag nanoparticles remained in the Au nanocages, which was also beneficial in terms of antibacterial properties. The presence of Au nanoparticles contributed to the composites achieving high cell viability. The most outstanding result was obtained by the consecutive addition of noble metals into the bioactive glasses, resulting in both a high antibacterial effect and good cell viability.     

Preparation and Characterization of Injectable Brushite Filled-Poly (Methyl Methacrylate) Bone Cement

Powder-liquid poly (methyl methacrylate) (PMMA) bone cements are widely utilized for augmentation of bone fractures and fixation of orthopedic implants. These cements typically have an abundance of beneficial qualities, however their lack of bioactivity allows for continued development. To enhance osseointegration and bioactivity, calcium phosphate cements prepared with hydroxyapatite, brushite or tricalcium phosphates have been introduced with rather unsuccessful results due to increased cement viscosity, poor handling and reduced mechanical performance. This has limited the use of such cements in applications requiring delivery through small cannulas and in load bearing. The goal of this study is to design an alternative cement system that can better accommodate calcium-phosphate additives while preserving cement rheological properties and performance. In the present work, a number of brushite-filled two-solution bone cements were prepared and characterized by studying their complex viscosity-versus-test frequency, extrusion stress, clumping tendency during injection through a syringe, extent of fill of a machined void in cortical bone analog specimens, and compressive strength. The addition of brushite into the two-solution cement formulations investigated did not affect the pseudoplastic behavior and handling properties of the materials as demonstrated by rheological experiments. Extrusion stress was observed to vary with brushite concentration with values lower or in the range of control PMMA-based cements. The materials were observed to completely fill pre-formed voids in bone analog specimens. Cement compressive strength was observed to decrease with increasing concentration of fillers; however, the materials exhibited high enough strength for consideration in load bearing applications. The results indicated that partially substituting the PMMA phase of the two-solution cement with brushite at a 40% by mass concentration provided the best combination of the properties investigated. This alternative material may find applications in systems requiring highly injectable and viscous cements such as in the treatment of spinal fractures and bone defects.     

Synthesis and Characterization of Wood Rigid Polyurethane Composites

Incorporating biodegradable reinforcement, such as wood particles, into rigid polyurethane foams (RPUFs) is among the alternatives to reduce their environmental impact. This study aims to assess the effect of different wood particles as reinforcement in RPUFs. Reinforced rigid polyurethane foams are synthesized with milled wood particles of various forms and sizes and commercial polyol and isocyanate. The effect of fiber treatments and mechanical stirring on foams’ properties is also studied. Additional tests on polyisocyanurate foams (PIR) were undertaken to assess the effect of reinforcement on their properties. Mechanical properties are measured to investigate the impact of wood particle reinforcement on the foam. Confocal microscopy and Fourier-transform infrared spectroscopy (FTIR) showed the interaction between the wood fibers and the matrix. Despite the adhesion observed for some fibers, most of the cell walls of RPUFs were punctured by the rigid wood fibers, which explained the decrease in the compressive strength of the composites for manually mixed foams. Mechanical stirring proved to be an efficient method to enhance the reinforcement power of untreated fibers. RPUF foams’ properties showed similar changes when untreated wood flour was introduced to the formula, increasing compressive strength significantly.     

An Electroconductive,Thermosensitive, and Injectable Chitosan/Pluronic/Gold-Decorated Cellulose Nanofiber Hydrogel as an Efficient Carrier for Regeneration of Cardiac Tissue

Myocardial infarction is a major cause of death worldwide and remains a social and healthcare burden. Injectable hydrogels with the ability to locally deliver drugs or cells to the damaged area can revolutionize the treatment of heart diseases. Herein, we formulate a thermo-responsive and injectable hydrogel based on conjugated chitosan/poloxamers for cardiac repair. To tailor the mechanical properties and electrical signal transmission, gold nanoparticles (AuNPs) with an average diameter of 50 nm were physically bonded to oxidized bacterial nanocellulose fibers (OBC) and added to the thermosensitive hydrogel at the ratio of 1% w/v. The prepared hydrogels have a porous structure with open pore channels in the range of 50–200 µm. Shear rate sweep measurements demonstrate a reversible phase transition from sol to gel with increasing temperature and a gelation time of 5 min. The hydrogels show a shear-thinning behavior with a shear modulus ranging from 1 to 12 kPa dependent on gold concentration. Electrical conductivity studies reveal that the conductance of the polymer matrix is 6 × 10⁻² S/m at 75 mM Au. In vitro cytocompatibility assays by H9C2 cells show high biocompatibility (cell viability of >90% after 72 h incubation) with good cell adhesion. In conclusion, the developed nanocomposite hydrogel has great potential for use as an injectable biomaterial for cardiac tissue regeneration.     

Synthesis and Physicochemical Evaluation of Bees’ Chitosan-Based Hydrogels Modified with Yellow Tea Extract

The novelty of the research involves designing the measurement methodology aimed at determining the structure–property relationships in the chitosan-based hydrogels containing yellow tea extract. Performed investigations allowed us to determine the swelling properties of hydrogels in selected time intervals, evaluate the mutual interactions between the hydrogels and simulated physiological liquids via pH measurements and directly assess the impact of such interactions on the chemical structure of hydrogels using Fourier transform infrared (FT-IR) spectroscopy and their wettability by the measurements of the flatness of the drop on the surface of the tested samples via the static drop method. Next, the surface morphology of hydrogels was characterized by the Scanning Electron Miscorcopy (SEM) and their elasticity under the tension applied was also verified. It was proved that incubation in simulated physiological liquids resulted in a decrease in contact angles of hydrogels, even by 60%. This also caused their certain degradation which was reflected in lower intensities of bands on FT-IR spectra. Further, 23% v/v yellow tea extract in hydrogel matrices caused the decrease of their tensile strength. An increase in the amount of the crosslinker resulted in a decrease in the sorption capacity of hydrogels wherein their modification caused greater swelling ability. In general, the investigations performed provided much information on the tested materials which may be meaningful considering their application, e.g., as dressing materials.     

In Vitro and Pre-Clinical Evaluation of Locally Isolated Phages,vB_Pae_SMP1 and vB_Pae_SMP5, Formulated as Hydrogels against Carbapenem-Resistant Pseudomonas aeruginosa

The inadequate therapeutic opportunities associated with carbapenem-resistant Pseudomonas aeruginosa (CRPA) clinical isolates impose a search for innovative strategies. Therefore, our study aimed to characterize and evaluate two locally isolated phages formulated in a hydrogel, both in vitro and in vivo, against CRPA clinical isolates. The two phages were characterized by genomic, microscopic, phenotypic characterization, genomic analysis, in vitro and in vivo analysis in a Pseudomonas aeruginosa-infected skin thermal injury rat model. The two siphoviruses belong to class Caudovirectes and were named vB_Pae_SMP1 and vB_Pae_SMP5. Each phage had an icosahedral head of 60 ± 5 nm and a flexible, non-contractile tail of 170 ± 5 nm long, while vB_Pae_SMP5 had an additional base plate containing a 35 nm fiber observed at the end of the tail. The hydrogel was prepared by mixing 5% w/v carboxymethylcellulose (CMC) into the CRPA propagated phage lysate containing phage titer 10⁸ PFU/mL, pH of 7.7, and a spreadability coefficient of 25. The groups were treated with either Phage vB_Pae_SMP1, vB_Pae_SMP5, or a two-phage cocktail hydrogel cellular subepidermal granulation tissues with abundant records of fibroblastic activity and mixed inflammatory cell infiltrates and showed 17.2%, 25.8%, and 22.2% records of dermal mature collagen fibers, respectively. In conclusion, phage vB_Pae_SMP1 or vB_Pae_SMP5, or the two-phage cocktails formulated as hydrogels, were able to manage the infection of CRPA in burn wounds, and promoted healing at the injury site, as evidenced by the histopathological examination, as well as a decrease in animal mortality rate. Therefore, these phage formulae can be considered promising for clinical investigation in humans for the management of CRPA-associated skin infections.     

Characterization of Bioactive Colored Materials Produced from Bacterial Cellulose and Bacterial Pigments

A Bacterial Cellulose (BC) film was developed and characterized as a potential functional bioactive material. BC films, obtained from a microbial consortium of bacteria and yeast species, were functionalized with the bacterial pigment prodigiosin, produced by Serratia plymuthica, and flexirubin-type pigment, from Chryseobacterium shigense, which exhibit a wide range of biological properties. BC was successfully functionalized at 15% over the weight of the fiber at 40 °C during 60 min, and a color strength of 1.00 ± 0.01 was obtained for BC_prodigiosin and 0.38 ± 0.02 for BC_flexirubin-type pigment. Moreover, the BC films showed moderate hydrophilic character following alkaline treatment, which was maintained after both pigments were incorporated. The porosity and mechanical performance of the functionalized BC samples also remained unaffected. Furthermore, the BC samples functionalized with prodigiosin presented antibacterial activity and were able to inhibit the growth of pathogenic bacteria Staphylococcus aureus and Pseudomonas aeruginosa, with inhibition rates of 97.89 ± 0.60% and 85.12 ± 0.17%, respectively, while BC samples functionalized with flexirubin-type pigment exhibited the highest antioxidant activity, at 38.96 ± 0.49%. This research provides an eco-friendly approach to grant BC film-based material with color and advantageous bioactive properties, which can find application in several fields, especially for medical purposes.