Self-Assembled Hydrogel Membranes with Structurally Tunable Mechanical and Biological Properties.

Using supramolecular self-assembled nanocomposite materials made from protein and polysaccharide components is becoming more popular because of their unique properties, such as biodegradability, hierarchical structures, and tunable multifunctionality. However, the fabrication of these materials in a reproducible way remains a challenge. This study presents a new evaporation-induced self-assembly method producing layered hydrogel membranes (LHMs) using tropocollagen grafted by partially deacetylated chitin nanocrystals (CO-g-ChNCs). ChNCs help stabilize tropocollagen's helical conformation and fibrillar structure by forming a hierarchical microstructure through chemical and physical interactions. The LHMs show improved mechanical properties, cytocompatibility, and the ability to control drug release using octenidine dihydrochloride (OCT) as a drug model. Because of the high synergetic performance between CO and ChNCs, the modulus, strength, and toughness increased significantly compared to native CO. The biocompatibility of LHM was tested using the normal human dermal fibroblast (NHDF) and the human osteosarcoma cell line (Saos-2). Cytocompatibility and cell adhesion improved with the introduction of ChNCs. The extracted ChNCs are used as a reinforcing nanofiller to enhance the performance properties of tropocollagen hydrogel membranes and provide new insights into the design of novel LHMs that could be used for various medical applications, such as control of drug release in the skin and bone tissue regeneration.

Carboxymethyl starch as a reducing and capping agent in the hydrothermal synthesis of selenium nanostructures for use with three-dimensional-printed hydrogel carriers.

The hydrothermal method is a cost-effective and eco-friendly route for preparing various nanomaterials. It can use a capping agent, such as a polysaccharide, to govern and define the nanoparticle morphology. Elemental selenium nanostructures (spheres and rods) were synthesized and stabilized using a tailor-made carboxymethyl starch (CMS, degree of substitution = 0.3) under hydrothermal conditions. CMS is particularly convenient because it acts simultaneously as the capping and reducing agent, as verified by several analytical techniques, while the reaction relies entirely on green solvents. Furthermore, the effect of sodium selenite concentration, reaction time and temperature on the nanoparticle size, morphology, microstructure and chemical composition was investigated to identify the ideal synthesis conditions. A pilot experiment demonstrated the feasibility of implementing the synthesized nanoparticles into vat photopolymerization three-dimensional-printed hydrogel carriers based on 2-hydroxyethyl methacrylate (HEMA). When submersed into the water, the subsequent particle release was confirmed by dynamic light scattering (DLS), promising great potential for use in bio-three-dimensional printing and other biomedical applications.

Deformation of Gels with Spherical Auxetic Inclusions.

Auxetic metamaterials possess unnatural properties, such as a negative Poisson's ratio, which offers interesting features when combined with traditional materials. This paper describes the deformation behavior of a gel consisting of spherical auxetic inclusions when embedded in a conventional matrix. The auxetic inclusions and conventional matrix were modeled as spherical objects with a controlled pore shape. The auxetic particle had a reentrant honeycomb, and the conventional phase contained honeycomb-shaped pores. The deformation behavior was simulated using various existing models based on continuum mechanics. For the continuum mechanics models-the simplest of which are the Mori-Tanaka theory and self-consistent field mechanics models-the auxetic particle was homogenized as a solid element with Young's modulus and Poisson's ratio and compared with the common composite gel filled with rigid spheres. The finite element analysis simulations using these models were performed for two cases: (1) a detailed model of one particle and its surroundings in which the structure included the design of both the reentrant and conventional honeycombs; and (2) a multiparticle face-centered cubic lattice where both the classic matrix and auxetic particle were homogenized. Our results suggest that auxetic inclusion-filled gels provide an unsurpassed balance of low density and enhanced stiffness.

Dynamic Responsive Formation of Nanostructured Fibers in a Hydrogel Network: A Molecular Dynamics Study.

In an effort to study natural fiber formation, such as, e.g., spider silk, we present a model, which is capable of forming biomimetic fibrillar nanostructure from a hydrogel micellar network. The latter consists of interacting atomic groups which form cores of micelles, and of flexible chains forming the shells of the micelles. Micelles are connected in a compact network by linearly stretched chains. The structural elements of the network can be transformed during deformation from micellar into fibrillary type and their evolution is found to depend significantly on strain rate. Our model suggests a set of conditions suitable for the formation of nanostructured fibrillar network. It demonstrates that a fibrillar structure is only formed upon sufficiently fast stretching while, in contrast, the micellar gel structure is preserved, if the material is pulled slowly. We illustrate this key aspect by a minimalistic model of only four chains as part of the whole network, which provides a detailed view on the mechanism of fibril formation. We conclude that such a simplified structure has similar functionality and is probably responsible for the formation of nano-structured molecular fibrils in natural materials.

Effect of Porosity Gradient on Mechanical Properties of Cellular Nano-Composites.

With their hierarchical architectures incorporating gradients in composition, porosity, and orientation, natural materials have evolved optimized balance of mechanical properties. Deciphered from the structure of bamboo, we prepared cellular solids with convex and/or concave porosity gradient and investigated their static mechanical and impact properties. Non-monotonous porosity dependences of tensile, crush, and impact strength were related to the shape of porosity gradient rather than to the properties of the wall material alone. Our results provide experimental evidence, that novel mechanically robust low density additively fabricated cellular nano-composites with convex porosity gradient satisfy the structural requirements of lightweight engineering parts. Moreover, novel functions, such as reduced flammability or electrical conductivity, can easily be introduced by selecting the type and spatial organization of nanoparticles and cellular structure of the cellular micro-particles (CMPs).

The development of a silicone vaginal ring with a prostaglandin analogue for potential use in the treatment of canine reproductive disorders.

In veterinary medicine, vaginal rings (VRs) are rarely used. However, there are diseases of female dogs' reproductive system which represent a suitable possibility for their usage. An example of such a disease is canine pyometra which can be treated by lipophilic prostaglandin drugs, unfortunately with harmful side effects after systemic administration. The aim of the study was to prove that the matrix VR based on silicone and channel-forming substance can be successfully used as a carrier for a three-day delivery of prostaglandin E2 (PGE2). Based on an in-vitro release study, an optimum channel-forming substance and its concentration were selected. The results were implemented during the construction of VR from the medical grade silicone DDU-4840 with PGE2 (5 mg). Glucose anhydrous in the 30% concentration was chosen as the most functional channel-forming substance due to synergism of osmotic activity and solubility. The DDU-VR containing PGE2 and 30% of glucose anhydrous exhibited excellent mechanical characteristics and ensured 29% drug release through water-filled channels in first-order kinetic manner. This is eight times higher than a sample without glucose where molecular diffusion through the silicone matrix was dominating the release mechanism. Moreover, drug-free VRs were tested for mechanical resistance and the design of removal thread.

Bulk polymer nanocomposites with preparation protocol governed nanostructure: the origin and properties of aggregates and polymer bound clusters.

Polymer nanocomposites (PNCs) hold great promise as future lightweight functional materials processable by additive manufacturing technologies. However, their rapid deployment is hindered by their performance depending strongly on the nanoparticle (NP) spatial organization. Therefore, the ability to control nanoparticle dispersion in the process of PNC preparation is a crucial prerequisite for utilizing their potential in functional composites. We report on the bulk processing technique of tailored NP spatial organization in a model glass forming polymer matrix controlled by structural and kinetic variables of the preparation protocol. Namely, we studied the impact of solvent on the NP arrangement, which was already known as a tuning parameter of the solid-state structure. We emphasized the qualitative differences between "poorly dispersed" NP arrays, which, by combination of rheological assessment and structural analysis (TEM, USAXS), we identified as chain bound clusters and aggregates of either thermodynamic or kinetical origin. They are characterized by substantially distinct formation kinetics and mismatched properties compared to each other and individually dispersed NPs. We quantitatively linked all the currently observed types of NP dispersion with their rheological properties during the solution blending step and the amount of polymer adsorption and depletion attraction. We propose the ratio of NP-polymer and NP-solvent enthalpy of adsorption as a parameter capable of the quantitative prediction of NP arrangement in systems similar to our current model PNC. Finally, we bring forth the comparison of glass transition temperatures to further demonstrate the importance of NP spatial organization in PNCs.

The Effect of Network Solvation on the Viscoelastic Response of Polymer Hydrogels.

The majority of investigations consider the deformation response of hydrogels, fully controlled by the deformation behavior of their polymer network, neglecting the contribution caused by the presence of water. Here, we use molecular dynamics simulation in an attempt to include the effect of physically bound water via polymer chain solvation on the viscoelastic response of hydrogels. Our model allows us to control the solvation of chains as an independent variable. The solvation of the chain is independent of other factors, mainly the effect (pH) which interferes significantly in experiments. The solvation of hydrophilic chains was controlled by setting a partial charge on the chains and quantified by the Bjerrum length (BL). The BL was calculated from the partial electric charge of the solvent and macromolecular network. When the BL is short, the repulsive Van der Waals interactions are predominant in the vicinity of macromolecules and solvation is not observed. For a long BL, the water molecules in the solvation zone of network are in the same range as attractive intermolecular forces and the solvation occurs. The model also allows the consideration of molecules of water attached to two chains simultaneously, forming a temporary bridging. By elucidating the relations between solvation of the network and structural changes during the network deformation, one may predict the viscoelastic properties of hydrogels knowing the molecular structure of its polymer chains.

Novel electrospun gelatin/oxycellulose nanofibers as a suitable platform for lung disease modeling.

Novel hydrolytically stable gelatin nanofibers modified with sodium or calcium salt of oxycellulose were prepared by electrospinning method. The unique inhibitory effect of these nanofibers against Escherichia coli bacteria was examined by luminometric method. Biocompatibility of these gelatin/oxycellulose nanofibers with eukaryotic cells was tested using human lung adenocarcinoma cell line NCI-H441. Cells firmly adhered to nanofiber surface, as determined by scanning electron microscopy, and no signs of cell dying were detected by fluorescent live/dead assay. We propose that the newly developed gelatin/oxycellulose nanofibers could be used as promising scaffold for lung disease modeling and anti-cancer drug testing.

Nanotechnology and mesenchymal stem cells with chondrocytes in prevention of partial growth plate arrest in pigs.

INTRODUCTION: This study describes the results achieved using a combination of allogeneic mesenchymal stem cells (MSCs) with chondrocytes (CHC) and a new scaffold consisting of type-I collagen and chitosan nanofibers in the prevention of partial growth plate arrest after iatrogenic injury in pigs. MATERIAL AND METHODS: The miniature pig was selected as an experimental model to compare the results in the left femoral bones (MSCs and CHC in scaffold transplantation into the iatrogenic partial distal growth plate defect) and right femoral bones (scaffold alone transplantation). The experimental group consisted of 10 animals. Bone marrow from os ilium as the source of MSCs was used. A porous cylinder consisting of 0.5% by weight type-I collagen and 30% by weight chitosan, was the optimal choice. The length of the bone and angular deformity of distal femur after the healing period was measured and the quality and structure of the newly formed cartilage was histologically examined. RESULTS: Transplantation of the composite scaffold in combination with MSCs and chondrocytes led to the prevention of growth disorder and angular deformity in the distal epiphysis of the left femur. Compared to the right (control) femur, tissue similar to hyaline cartilage with signs of columnar organization typical of the growth plate occurred in most cases. CONCLUSIONS: The promising results of this study reveal the new and effective means for the prevention of bone bridge formation after growth plate injury.

Bond strength of five dental adhesives using a fracture mechanics approach.

OBJECTIVES: The adhesion tests utilized in dentistry are unable to separate the effects of adhesive composition, substrate properties, joint geometry and type of loading on the measured bond strength. This makes it difficult for the clinician to identify the most suitable adhesive for a given procedure and for the adhesive manufacturer to optimize its composition. Thus, an adhesion test protocol based on the fracture mechanics has been proposed to generate data for which separation of the effect of composition from that of the joint geometry on the shear (τ(a)) and tensile (σ(a)) bond strengths was possible for five commercial dental adhesives. METHODS: Planar 40×5×5 mm(3) sections of bovine femur were used as model adherends. The adhesive thickness (h) was varied from 15 to 500 µm. Commercial adhesives with fracture toughness (K(IC)) ranging from 0.3 to 1.6 MPa m(1/2) were used. Double lap joint (DLJ) and modified compact tension (MCT) specimens were conditioned for 24 h in 37 °C distilled water, then dried in a vacuum oven at 37 °C for 24 h prior to testing. The thickness dependence of σ(a) and τ(a) was measured at constant strain rate and analyzed using the interface corner stress intensity factor model. RESULTS: Both τ(a) and σ(a) increased with increasing adhesive thickness, exhibiting a maximum bond strength at the optimum thickness (h(opt)). For h