Enhancing the bioactivity of melt electrowritten PLLA scaffold by convenient, green, and effective hydrophilic surface modification.

As an emerging additive manufacturing (AM) technique, melt electrospinning writing (MEW) is used to fabricate three-dimensional (3D) submicron filament-based scaffolds with adjustable pore size and customized structure for bone regeneration. Poly(L-lactic acid) (PLLA) scaffold with excellent biodegradability and biocompatibility is first successfully manufactured using our self-assembled MEW device. However, the ultralow cell affinity and poor bioactivity severely hamper their practical applications in bone tissue engineering. These issues are caused by the severe inherent biologically inert, hydrophobicity as well as the smooth surface of the MEW PLLA filaments. In this study, a green and robust alkaline method is applied to modify the scaffold surface and to improve the bioactivity of the MEW PLLA scaffold. Without deterioration in mechanical property but robust surface hydrophilicity, the optimal MEW PLLA scaffold shows promoted surface roughness, enhanced filament tensile modulus (~ 2 folds of the as-prepared sample), and boosted crystallizability (ultrahigh WAXD intensity). Moreover, after being cultured with KUSA-A1 cells, the 0.5 M NaOH, 2 h treated MEW PLLA scaffold exhibits higher osteoinductive ability and increased immature bone tissue amounts (3 times of controlled scaffold). Thus, the flexible surface functionalization by the specific alkaline treatment was found to be an effective method for the preparation of bioactivated MEW PLLA scaffolds with promoted bone regeneration.

Fabrication and Properties of Electrospun Collagen Tubular Scaffold Crosslinked by Physical and Chemical Treatments.

Tissue engineered scaffold was regarded as a promising approach instead of the autograft. In this study, small diameter electrospun collagen tubular scaffold with random continuous smooth nanofibers was successfully fabricated. However, the dissolution of collagen in concentrated aqueous (conc. aq.) acetic acid caused to the serious denaturation of collagen. A novel method ammonia treatment here was adopted which recovered the collagen triple helix structure according to the analysis of IR spectra. Further dehydrothermal (DHT) and glutaraldehyde (GTA) treatments were applied to introduce the crosslinks to improve the properties of collagen tube. The nanofibrous structure of collagen tube in a wet state was preserved by the crosslinking treatments. Swelling ratio and weight loss decreased by at least two times compared to those of the untreated collagen tube. Moreover, tensile strength was significantly enhanced by DHT treatment (about 0.0076 cN/dTex) and by GTA treatment (about 0.075 cN/dTex). In addition, the surface of crosslinked collagen tube kept the hydrophilic property. These results suggest that DHT and GTA treatments can be utilized to improve the properties of electrospun collagen tube which could become a suitable candidate for tissue engineered scaffold.

Effect of the Application of a Dehydrothermal Treatment on the Structure and the Mechanical Properties of Collagen Film.

Dehydrothermal (DHT) treatment was used to improve the properties of collagen casings because of its non-cytotoxicity. Understanding the effects of DHT treatment on the structure and mechanical properties of collagen films is beneficial to developing satisfying collagen casings. Herein, DHT treatment with various temperatures (85-145 °C) and timescales (1-7 days) were investigated. It was clarified that the chemical crosslinking covalent bond between collagen molecules was formed after the DHT treatment. Crosslinking density increased with increasing DHT treatment temperatures, contributing to the increase of tensile strength up to over three times of that of the untreated collagen film. The increased crosslinking density was also found when increasing the DHT treatment time, and the maximum was obtained in 3 days. Further DHT treatment time did not change the crosslinking density. The damage in the triple helix structure and the self-assembly of collagen molecules were observed from IR and SAXS. The extent of denaturation increased with increasing DHT treatment temperature and time, although the effect of the DHT treatment time on the denaturation was more moderate. When the DHT treatment temperature was as high as 145 °C or the DHT treatment time exceeded 5 days, serious denaturation occurs, leading to the deterioration of mechanical properties.

The structure and properties of natural sheep casing and artificial films prepared from natural collagen with various crosslinking treatments.

The structure and properties of natural sheep casing and collagen films with various crosslinking treatments have been investigated in detail to develop satisfied artificial casings prepared from collagen. The sheep casing consists of large number of thick collagen fibers oriented at ±45° from longitudinal direction with high-density interwoven network structure. The structural feature of sheep casing gave the special mouthfeel of 'cracking bite' of sausages. Whereas, layered structure filled with fine collagen fibrils and large gaps in collagen film results in poor mechanical properties and higher swelling ratio in water. Furthermore, a degree of denaturation of collagen during extraction process also lead to poor mechanical properties. After glutaraldehyde (GTA) and dehydrothermal (DHT) treatments, the formation of crosslinking improved mechanical properties of collagen films significantly and the tensile strength and tensile modulus increased more than three times compared with those of untreated collagen film in wet before and after boiling. The swelling ratio of treated collagen films also decreased dramatically. No obvious effects on denaturation of collagen film after GTA treatment, but the degree of denaturation of DHT treated collagen film increased slightly.

Regeneration of cellulose dissolved in ionic liquid using laser-heated melt-electrospinning.

A "green" and highly efficient route was proposed to fabricate ultrafine cellulose fibers. The processing steps include cellulose dissolution, gel preparation, melt-electrospinning and fiber coagulation. High DP cellulose can be easily dissolved in 1-butyl-3-methylimidazolium chloride (BmimCl) when the blend was stirred at 110 °C for 2 h. The maximum solubility can reach up to 16.7 wt%. A homogeneous ternary cellulose/BmimCl/ethanol or cellulose/BmimCl/water gel was made by the methods of crystallization and casting for the purpose of fixing the shape of the cellulose/BmimCl solution. After laser-heating and electrospinning, multiple jets were ejected from the gel tip and then frozen on a super cold target. Pure cellulose fibers without beads and blocks were achieved after coagulation. The results of WAXD and FTIR indicated that the regenerated cellulose fibers were amorphous and chemically stable. More importantly, this approach can be applied to other polysaccharides for the preparation of ultrafine fibers.

A spiropyran-based X-ray sensitive fiber.

This study attempted to visualize reversible X-ray radiation by using a poly-(l-lactic acid) (PLLA) composite fiber with an average diameter of 150 µm. The fiber contains photostimulable phosphor (PSP) BaFCl:Eu(2+) particles that are subsequently dyed with the photochromic spiropyran dye (1,3,3-trimethylindolino-6'-nitrobenzopyrylospiran) (6-nitro BIPS).

Surface structure of chitosan and hybrid chitosan-amylose films-restoration of the antibacterial properties of chitosan in the amylose film.

The surface structure of films prepared by casting aqueous solutions of mixtures of water soluble chitosan (WSC) and amylose as well as a fully deacetylated chitosan was studied. Zeta potential measurements indicated that the surface of WSC and fully deacetylated chitosan films is positively charged but very weakly, whereas, a film of amylose blended with WSC exhibited an obvious positive charge. X-ray photoelectron spectra of these films suggest that less amino groups are exposed on the surface of WSC and fully deacetylated chitosan films, whereas, more amino groups are exposed on the surface of a WSC film blended with amylose. A sheet structure in which free amino groups are less exposed on the surface of the film of WSC or fully deacetylated chitosan is proposed. This accounts for the loss of antibacterial activity of chitosan on the WSC film surface. When blended with amylose, the morphology of the film may be disrupted, resulting in strong antibacterial properties.