Controlled Structuring of Hyaluronan Films by Phase Separation and Inversion.

This work explores application of phase separation phenomena for structuring of films made from hyaluronan. A time-sequenced dispensing of different solution mixtures was applied under rotation of hyaluronan-covered substrates to generate surface textures. This method is applicable in direct surface modification or cover layer deposition. Changes in the surface topography were characterized by atomic force microscopy, optical microscopy, and contact and non-contact profilometry. The mechanical properties of the surface-modified self-supporting films were compared using a universal testing machine. Experimental results show that diverse hyaluronan-based surface reliefs and self-supporting films with improved mechanical properties can be prepared using a newly designed multi-step phase separation process without the need for sacrificial removable templates or additives.

Synthesis and Exfoliation of Calcium Organophosphonates for Tailoring Rheological Properties of Sodium Alginate Solutions: A Path toward Polysaccharide-Based Bioink.

Layered nanoparticles with surface charge are explored as rheological modifiers for extrudable materials, utilizing their ability to induce electrostatic repulsion and create a house-of-cards structure. These nanoparticles provide mechanical support to the polymer matrix, resulting in increased viscosity and storage modulus. Moreover, their advantageous aspect ratio allows for shear-induced orientation and decreased viscosity during flow. In this work, we present a synthesis and liquid-based exfoliation procedure of phenylphosphonate-phosphate particles with enhanced ability to be intercalated by hydrophilic polymers. These layered nanoparticles are then tested as rheological modifiers of sodium alginate. The effective rheological modification is proved as the viscosity increases from 101 up to 103 Pa·s in steady state. Also, shear-thinning behavior is observed. The resulting nanocomposite hydrogels show potential as an extrudable bioink for 3D printing in tissue engineering and other biomedical applications, with good shape fidelity, nontoxicity, and satisfactory cell viability confirmed through encapsulation and printing of mouse fibroblasts.

Hierarchically Structured Surfaces Prepared by Phase Separation: Tissue Mimicking Culture Substrate.

The pseudo 3D hierarchical structure mimicking in vivo microenvironment was prepared by phase separation on tissue culture plastic. For surface treatment, time-sequenced dosing of the solvent mixture with various concentrations of polymer component was used. The experiments showed that hierarchically structured surfaces with macro, meso and micro pores can be prepared with multi-step phase separation processes. Changes in polystyrene surface topography were characterized by atomic force microscopy, scanning electron microscopy and contact profilometry. The cell proliferation and changes in cell morphology were tested on the prepared structured surfaces. Four types of cell lines were used for the determination of impact of the 3D architecture on the cell behavior, namely the mouse embryonic fibroblast, human lung carcinoma, primary human keratinocyte and mouse embryonic stem cells. The increase of proliferation of embryonic stem cells and mouse fibroblasts was the most remarkable. Moreover, the embryonic stem cells express different morphology when cultured on the structured surface. The acquired findings expand the current state of knowledge in the field of cell behavior on structured surfaces and bring new technological procedures leading to their preparation without the use of problematic temporary templates or additives.

Three-Dimensional Printing Process for Musical Instruments: Sound Reflection Properties of Polymeric Materials for Enhanced Acoustical Performance.

Acoustical properties of various materials were analyzed in order to determine their potential for the utilization in the three-dimensional printing process of stringed musical instruments. Polylactic acid (PLA), polyethylene terephthalate with glycol modification (PET-G), and acrylonitrile styrene acrylate (ASA) filaments were studied in terms of sound reflection using the transfer function method. In addition, the surface geometry parameters (Sa, Sq, Sz, and Sdr) were measured, and their relation to the acoustic performance of three-dimensional-printed samples was investigated. It was found that a higher layer height, and thus a faster printing process, does not necessarily mean poor acoustical properties. The proposed methodology also proved to be a relatively easy and rapid way to test the acoustic performance of various materials and the effect of three-dimensional printing parameters to test such a combination at the very beginning of the production process.

Magnetic Nanomaterials for Arterial Embolization and Hyperthermia of Parenchymal Organs Tumors: A Review.

Magnetic hyperthermia (MH), proposed by R. K. Gilchrist in the middle of the last century as local hyperthermia, has nowadays become a recognized method for minimally invasive treatment of oncological diseases in combination with chemotherapy (ChT) and radiotherapy (RT). One type of MH is arterial embolization hyperthermia (AEH), intended for the presurgical treatment of primary inoperable and metastasized solid tumors of parenchymal organs. This method is based on hyperthermia after transcatheter arterial embolization of the tumor's vascular system with a mixture of magnetic particles and embolic agents. An important advantage of AEH lies in the double effect of embolotherapy, which blocks blood flow in the tumor, and MH, which eradicates cancer cells. Consequently, only the tumor undergoes thermal destruction. This review introduces the progress in the development of polymeric magnetic materials for application in AEH.

Factors determining self-assembly of hyaluronan.

The conditions determining network-forming and aggregation properties of hyaluronan on the mica surface were studied. The hyaluronan was deposited on the surface from aqueous and saline solutions and attached by a bivalent cation. The morphology of the immobilized assemblies was characterized by atomic force microscopy. The experimental results show that the morphology and size of the aggregates as well as the density of the interconnecting fibrillar network, both made of hyaluronan, at the liquid-solid phase interface are determined not only by its molecular weight or concentration in solution, but also by the dissolution conditions and storage time. These findings extend the current state of knowledge about the conformational variability of this biologically important polymer. Understanding the conformational variability is of great importance, as it governs the physiological functions of hyaluronan, as well as its processability and formulations. That in turn determines its usability in different pharmacological and biomaterial applications.

Surface Modification of Metallic Inserts for Enhancing Adhesion at the Metal-Polymer Interface.

A combination of mechanical and chemical treatments was utilized to modify the surface textures of copper and duralumin inserts in order to enhance the adhesion at the metal-polymer interface and provide an adhesive joint with a high loadbearing capacity. Pretreatment of the surfaces with sandblasting was followed by etching with various chemical mixtures. The resulting surface textures were evaluated with a scanning electron microscope (SEM) and an optical confocal microscope. Surface geometry parameters (Sa, Sz, and Sdr) were measured and their relationships to the adhesion joint strength were studied. It was found that the virgin and purely mechanically treated inserts resulted in joints with poor loadbearing capacity, while a hundredfold (duralumin) and ninetyfold (copper) increase in the force to break was observed for some combinations of mechanical and chemical treatments. It was determined that the critical factor is overcoming a certain surface roughness threshold with the mechanical pretreatment to maximize the potential of the mechanical/chemical approach for the particular combination of material and etchant.

Electrospinning of Hyaluronan Using Polymer Coelectrospinning and Intermediate Solvent.

In the current study, we present methods of sodium hyaluronate, also denoted as hyaluronan (HA), nanofiber fabrication using a direct-current (DC) electric field. HA was spun in combination with poly(vinyl alcohol) (PVA) and polyethylene oxide (PEO) and as a pure polymer. Nonaggressive solvents were used due to the possible use of the fibers in life sciences. The influences of polymer concentration, average molecular weight (Mw), viscosity, and solution surface tension were analyzed. HA and PVA were fluorescent-labeled in order to examine the electrospun structures using fluorescence confocal microscopy. In this study, two intermediate solvent mixtures that facilitate HA electrospinning were found. In the case of polymer co-electrospinning, the effect of the surfactant content on the HA/PVA electrospinning process, and the effect of HA Mw on HA/PEO nanofiber morphology, were examined, respectively.

Hyaluronan hydrogels modified by glycinated Kraft lignin: Morphology, swelling, viscoelastic properties and biocompatibility.

Effects of the addition of water soluble glycinated Kraft lignin (WS/KL) on the mechanical stability and biocompatibility of hyaluronan (NaHy) hydrogels were evaluated in this work. Water soluble lignin was obtained by the modification of Kraft lignin via a Mannich reaction. It was found that WS/KL is highly compatible with hyaluronan due to its improved water solubility, which favours its use in designing new advanced composite hydrogels. The effects of the concentration of WS/KL on morphological, swelling and creep/recovery behaviours of hyaluronan hydrogels were investigated. It was detected that the creep resistance and creep recovery of NaHy hydrogels was improved by the incorporation of up to 3% (w/w) of WS/KL. In contrast, the swelling capacity of hydrogels was decreased. The cytotoxicity tests proved that glycinated KL lignin limits the viability of cells only slightly, and the final hyaluronan/lignin hydrogels were non-toxic materials.

Preparation of Textured Surfaces on Aluminum-Alloy Substrates.

The ways of producing porous-like textured surfaces with chemical etching on aluminum-alloy substrates were studied. The most appropriate etchants, their combination, temperature, and etching time period were explored. The influence of a specifically textured surface on adhesive joints' strength or superhydrophobic properties was evaluated. The samples were examined with scanning electron microscopy, profilometry, atomic force microscopy, goniometry, and tensile testing. It was found that, with the multistep etching process, the substrate can be effectively modified and textured to the same morphology, regardless of the initial surface roughness. By selecting proper etchants and their sequence one can prepare new types of highly adhesive or even superhydrophobic surfaces.

Variations of Polymer Porous Surface Structures via the Time-Sequenced Dosing of Mixed Solvents.

A new approach to polystyrene surface treatment via the time-sequenced dispensing of good and poor solvent mixtures on the rotating surface of treated substrate is presented in this study. It is demonstrated that the variation of the sequencing together with other variables (e.g., temperature and solvent concentration) affects the size and depth of pores evolving on the polystyrene surface. A model of the surface pore creation, associated with the viscoelastic phase separation, surface tension, and secondary flows caused by temperature variations and the rapid evaporation of the good solvent is proposed. Experimental results of profilometric, goniometric, and optical measurements show that this approach enables the simple and quick preparation of surfaces with various numbers, diameters, and depths of individual pores, which ultimately affects not only the wetting characteristics of the surfaces but also the fate of cells cultivated there. The presented method allows the easy preparation of a large number of structured substrates for effective cell cultivation and proliferation.

Viscoelastic and mechanical properties of hyaluronan films and hydrogels modified by carbodiimide.

This study investigated an effect of different ways of the preparation of insoluble hyaluronan material on its mechanical and viscoelastic properties. Hyaluronan (NaHy) of molecular weight Mw=500,000 g mol(-1) was modified with N-(3-dimethylaminopropyl-N'-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS), to be able absorb liquid without changing its mechanical properties. The modified, water insoluble NaHy materials were prepared in different geometry; as modified films and modified cylinders with exact dimensions. The occurrence of modification was confirmed by FT-IR (Fourier transform infrared spectroscopy) and (1)H NMR (proton nuclear magnetic resonance) spectroscopy and swelling test. The determined mechanical and viscoelastic properties of unmodified and modified hyaluronan revealed the high dependency of elasticity changes depending on the gel processing method. Moreover, NaHy gels in the cylindrical form with the sponge-like structure predominant them as a convenient geometry for application in a humid environment.

Maghemite based silicone composite for arterial embolization hyperthermia.

Maghemite nanoparticle based silicone composite for application in arterial embolization hyperthermia is developed. It possesses embolization ability, high heating efficiency in alternating magnetic fields and radiopaque property. The initial components of the composite are selected so that the material stays liquid for 20min, providing the opportunity for transcatheter transportation and filling of the tumour vascular system. After this induction period the viscosity increases rapidly and soft embolus is formed which is able to occlude the tumour blood vessels. The composite is thermally stable up to 225°C, displays rubber-elastic properties and has a thermal expansion coefficient higher than that of blood. Maghemite nanoparticles uniformly distributed in the composite provide its rapid heating (tens of °Cmin(-1)) due to Neel magnetization relaxation. Required X-ray contrast of composite is achieved by addition of potassium iodide.

The influence of quarternary salt on hyaluronan conformation and particle size in solution.

Interaction of hyaluronan (NaHy) with the quaternary salt, benzalkonium chloride (BAC), was studied. Based on the DLS experiments, viscometry and surface tension measurements executed on hyaluronan samples with two molecular weights of Mw=1.8 MDa and Mw=0.35 MDa, the hypothesis was proposed suggesting that at certain BAC concentrations, hyaluronan can form aggregates, which lead to increase of the polymer coil size measured as z-average diameter. Moreover, it was confirmed that within the whole range of BAC concentrations, repeated variations in size and conformations of polymer coils occur, being connected with the critical micellar concentration of BAC and with hydrophobic interactions of non-polar segments of BAC with hyaluronan hydrophobic domains. Tensiometry, DLS and viscometry data support the assumption that variations of thermodynamical "favourability" of BAC-BAC or NaHy-BAC interactions take place in hyaluronan solutions, based on the BAC concentration.