Abstract

Supramolecular hydrogels based on N-protected phenylalanine (Fmoc–Phe–OH) were used to encapsulate non-ionic surfactant vesicles (niosomes).

Highlights

  • The synthesis of the amphiphilic lipid-1 (ESI, Fig. S1†) and the subsequent preparation of the cationic niosomal formulation were successfully accomplished following the experimental procedures described in our previous studies.[30,31]

  • Nioplexes-containing Fmoc– Phe–OH–based hydrogels-(2–4) crosslinked with increasing concentration of k-carrageenan were prepared in PBS buffer (ESI, Fig. S2B†)

  • These differences were observed for hydrogel-1 when compared to the corresponding native material. These results suggest that the presence of k-carrageenan and cationic niosomes within the supramolecular gel network could induce certain deformations in the systems under speci c stress conditions, increasing the hydrogel rigidity and the corresponding shear stress resistance.[46]

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Summary

Introduction

Since Wichterle and Lim reported for the rst time the synthesis of crosslinked poly(hydroxyethylmethacrylate) (pHEMA) for biological use,[1] synthetic and natural polymer-based hydrogels have gained substantial importance over the years in a good number of biomedical, pharmaceutical and biotechnological applications such as tissue engineering, drug delivery systems or cell culture scaffolds.[2,3,4,5] The research in this area has contributed to the development of novel smart polymer gel networks having speci c responses to external stimuli such as pH, light, temperature or chemical additives,[6,7,8] which could facilitate the controlled liberation of embedded therapeutic drugs.[9]In contrast to polymer or chemical gels[10] that are based on covalent bonds, physical or supramolecular gels[11] are typically made of low molecular weight (LMW) compounds self-assembled through non-covalent interactions (e.g., hydrogen-bonding, p–p stacking, van der Waals, dipole–dipole, charge-transfer and coordination interactions). The solid-like appearance and rheological properties of the gels result from the immobilization of the liquid (major component) into the interstices of a solid matrix (minor component) mainly through capillary forces.[12] The formation of the 3D-network with numerous junction zones results from the entanglement of 1D-suprapolymeric strands of gelator molecules usually of nm diameters and mm lengths.[13] The synthetic versatility of many LMW gelators together with their biocompatible properties have allowed their use in a number of biomedical applications including cell adhesion, cell growth, tissue engineering and controlled drug delivery.[14,15,16,17] Among the plethora of LMW compounds that are able to form supramolecular hydrogel networks, aminoacid derivatives and peptide conjugates[18,19,20,21,22,23] constitute one of the most studied groups Within this context, the use of phenylalanine (Phe) derivatives as hydrogelator was reported for the rst time in 2006.24,25 In 2011, Roy and Banerjee[26] reported the ability of N-terminally

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