Complexation‐Induced Biomimetic Long Range Fibrous Orientation in a Rigid‐Flexible Block Copolymer Thermogel

Abstract

The orientation of the organofibrous structure plays an important role not only in the biomineralization process but also in the extracellular matrix (ECM) of articular cartilage by providing cells with biomechanical cues. Here, it is reported that a long range nanofibrous orientation can be realized by a self‐assembling ionic complex between (+)‐charged amphiphilic peptide block copolymers with a rigid‐flexible block structure (polyalanine‐PLX‐polyalanine; PA‐PLX‐PA) and (‐)‐charged hyaluronic acid (HA). A biomimetic 3D culture system encapsulating chondrocytes is formed by a temperature‐sensitive sol‐to‐gel transition of the PA‐PLX‐PA/HA complex aqueous solution, which provides a compatible microenvironment for the cells. The cell proliferation and biomarker expression for articular cartilage are significantly improved in the PA‐PLX‐PA/HA complex system relative to the PA‐PLX‐PA or the commercially available Matrigel systems. In particular, noticeable cell clustering is observed in the PA‐PLX‐PA/HA complex system with the long range nanofibrous structure. This research suggests a new method for developing a nanofibrous structure using an amphiphilic peptide block copolymer and demonstrates its potential uses as a unique biomimetic cell‐culture matrix.

Poly(Ethylene Glycol)-Poly(l-Alanine)/Hyaluronic Acid Complex as a 3D Platform for Understanding Cancer Cell Migration in the Tumor Microenvironment

“…This trend is caused by a change in the secondary structure of P, a poly(L-alanine) polymer, through secondary structural change due to the attraction between P and HA. These results support that PHA has unique physical and chemical properties due to the interaction of P and HA [9].…”

“…The black arrow in the 2D-NMR of PHA indicates the methyl/methine (-CH 3 /-CH-) coupling resulting from the complexation between the ammonium group of terminal alanine of P and the carboxylate groups of HA. These results support the chemical shift and appearance of a new peak in 1 H-NMR spectra, and 2D-NMR indicates that the P interacted with HA by ionic complexation [9]. The poly(L-alanine), including α-helix, β-sheet, and random coil conformations, have their characteristic chiroptical properties in CD spectra [24,25].…”

2D and 3D Hybrid Systems for Enhancement of Chondrogenic Differentiation of Tonsil‐Derived Mesenchymal Stem Cells

“…The hydroxyl and carboxylate resemble the functional groups of glycosaminoglycan and hyaluronic acid which are components of the extracellular matrix of the native cartilage. Hyaluronic acid is reported to improve chondrocyte proliferation during the 3D culture . In our current study, the chondrogenic media enriched with TGF β3 was particularly effective in cell aggregation as well as chondrogenic differentiation.…”

A new light triggered approach to develop a micro porous tough hydrogel

“…S4 †). Hydrogels of PEG-PA (storage modulus $500 Pa) 1 and PLX-PA and PA-PLX-PA/HA (storage modulus 400-1600 Pa) 49 have been reported for 3D cell culture as well. However, these materials form hydrogel at higher concentrations and the pore sizes are also smaller.…”