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Supramolecular Hydrogels for Protein Delivery in Tissue Engineering

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Supramolecular Hydrogels for Protein Delivery in Tissue Engineering molecules Review Supramolecular Hydrogels for Protein Delivery in Tissue Engineering Yaqi Lyu and Helena S. Azevedo * School of Engineering and Materials Science, Institute of Bioengineering, Queen Mary University of London, Mile End Road, London E1 4NS, UK; [email protected] * Correspondence: [email protected]; Tel.: +44-20-7882-5502 Abstract: Therapeutic proteins, such as growth factors (GFs), have been used in tissue engineering (TE) approaches for their ability to provide signals to cells and orchestrate the formation of functional tissue. However, to be effective and minimize off-target effects, GFs should be delivered at the target site with temporal control. In addition, protein drugs are typically sensitive water soluble macro- molecules with delicate structure. As such, hydrogels, containing large amounts of water, provide a compatible environment for the direct incorporation of proteins within the hydrogel network, while their release rate can be tuned by engineering the network chemistry and density. Being formed by transient crosslinks, afforded by non-covalent interactions, supramolecular hydrogels offer important advantages for protein delivery applications. This review describes various types of supramolecular hydrogels using a repertoire of diverse building blocks, their use for protein delivery and their further application in TE contexts. By reviewing the recent literature on this topic, the merits of supramolecular hydrogels are highlighted as well as their limitations, with high expectations for new advances they will provide for TE in the near future. Keywords: supramolecular interactions; hydrogels; injectable; stimuli-responsive; controlled release; proteins drugs; tissue engineering Citation: Lyu, Y.; Azevedo, H.S. Supramolecular Hydrogels for Protein Delivery in Tissue Engineering. Molecules 2021, 26, 873. 1. Introduction https://doi.org/10.3390/ Tissue engineering (TE) has emerged as a result of bioengineering breakthroughs molecules26040873 in the early 1990s [1] aiming to repair malfunction tissues in the body caused by genetic mutations, congenital abnormalities, aging, disease or injury. TE approaches are focused Academic Editor: Silvia Marchesan on the combined use of (1) cells, as building workers to repair and produce new tissue, (2) Received: 29 December 2020 scaffolds, to support and guide cells and (3) biomolecules, which are able to regulate the Accepted: 3 February 2021 Published: 7 February 2021 fate of cells. Typically, those biomolecules are bioactive proteins, like growth factors (GFs), that regulate cell proliferation, differentiation, migration and other cell behaviors during Publisher’s Note: MDPI stays neutral tissue development [2,3]. The use of bioactive proteins has been widely exploited in TE, with regard to jurisdictional claims in not only because of their direct effects on cells but also due to the rapid development of published maps and institutional affil- biotechnology, in particular the production of recombinant proteins. Direct administration iations. of bioactive proteins in the body is known to be poorly controlled and can lead to undesired effects. Besides, the half-life of protein drugs in serum is very short, often within hours, requiring repeated dosing to maintain sufficient concentrations to produce therapeutic effects. To improve the availability of bioactive proteins, elegant delivery systems have been designed for their controlled and sustained release. Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. Hydrogels have become popular materials in biomedical applications due to their This article is an open access article generally accepted biocompatibility and wide range of properties, from soft to stiff, to distributed under the terms and stimuli-responsive and cell-instructive. Hydrogels own a three-dimensional structure rich conditions of the Creative Commons in water and held by a network of hydrophilic polymers. This architecture resembles the Attribution (CC BY) license (https:// native extracellular matrix (ECM) in tissues. As such, hydrogels have been also highly creativecommons.org/licenses/by/ considered for TE applications where they can hold cells [4] and provide mechanical sup- 4.0/). port [5]. In addition, the properties of hydrogels offer various possibilities for the controlled Molecules 2021, 26, 873. https://doi.org/10.3390/molecules26040873 https://www.mdpi.com/journal/molecules Molecules 2021, 26, x FOR PEER REVIEW 2 of 31 Molecules 2021, 26, 873 2 of 31 considered for TE applications where they can hold cells [4] and provide mechanical sup- port [5]. In addition, the properties of hydrogels offer various possibilities for the con- trolleddelivery delivery of of proteins: proteins: (1) 1) The The massive massive water water content content enables enables the the easy easy encapsulation encapsulation of water- of water-solublesoluble molecules molecules such such as proteins;as proteins; (2) 2) The The cross-linked cross-linked network network and and composition composition of the of thehydrogels hydrogels can can be be tailored, tailored, allowing allowing control control over over the the mesh mesh size size and and thus thus the the possibility possi- to bility governto govern the the release release of entrapped of entrapped proteins, proteins, based based on theiron their size size and and affinity affinity to the to hydrogelthe hydrogelcomponents; components; (3) The 3) hydratedThe hydrated network netw providesork provides protection protection to entrapped to entrapped proteins pro- against teins proteolyticagainst proteolytic degradation degradation and prolongs and prol theirongs bioactivity. their bioactivity. Based on Based the crosslinking on the cross- method, linkinghydrogels method, canhydrogels be classified can be intoclassified two maininto two types: main chemically types: chemically (through (through covalent co- bonds) valentand bonds) physically and physically (or supramolecular) (or supramolecular) crosslinked crosslinked hydrogels. hydrogels. Supramolecular Supramolecular hydrogels are hydrogelsformed are via formed non covalent via non interactionscovalent interact suchions as hydrogen such as hydrogen bonding, bonding, hydrophobic hydropho- effects, host– bic effects,guest host–guest recognitions, recognitions, electrostatic electrostatic interactions, interactions, metal-ligand metal-ligand interactions, interactions,π-π interactions π- π interactionsand van derand Waals van der forces Waals (Figure forces1). (Figure 1). Figure 1. Application of supramolecular chemistry to create physically crosslinked hydrogels. (a) hy- Figuredrophobic 1. Application effects; of ( bsupramolecular) hydrogen bonding; chemistry (c) electrostatic to create physically interactions; crosslinked (d) host-guest hydrogels. interactions; (a) (e) hydrophobic effects; (b) hydrogen bonding; (c) electrostatic interactions; (d) host-guest interactions; metal ligand interactions; (f) π-π stacking. (e) metal ligand interactions; (f) π-π stacking. Generally, supramolecular hydrogels are formed under mild environmental condi- Generally,tions, which supramolecular enables the direct hydrogels addition are offormed sensitive under molecules, mild environmental such as proteins, condi- during tions,hydrogel which enables formation. the direct The addition dynamic of nature sensitive ofnon-covalent molecules, such interactions as proteins, in supramolec-during hydrogelular formation. hydrogels, The allows dynamic their minimallynature of no invasiven-covalent delivery interactions by injection. in supramolecular In addition, the hydrogels,dense allows crosslinked their networkminimally can invasive prevent delivery diffusion by of injection. proteolytic In addition, enzymes the and dense is thus be- crosslinkedlieved network to protect can bioactive prevent therapeutics diffusion of proteolytic from premature enzymes degradation and is thus [6 ].believed The reversible to protectnature bioactive of noncovalent therapeutics crosslinking from premature also provides degradation repeated [6]. release The reversible on demand, nature as theyof are noncovalentable to disassemblecrosslinking andalso reassembleprovides repeated based onrelease environmental on demand, stimuli as they [7 ].are Figure able 2to high- disassemblelights the and properties reassemble and based medical on applicationsenvironmental of supramolecularstimuli [7]. Figure hydrogels. 2 highlights Compared the to supramolecular hydrogels, most hydrogels crosslinked by non-dynamic covalent bonds are unable to undergo crosslinking again after breaking and recover the original properties and function. Covalent bonding will decrease the flexibility of the hydrogels, making them Molecules 2021, 26, 873 3 of 31 difficult to integrate with the dynamic environment of native tissues [8,9]. Hence, the unique properties of dynamic and reversible noncovalent interactions make supramolec- ular hydrogels an ideal protein delivery system for TE applications. Table1 provides a Molecules 2021, 26, x FOR PEER REVIEW general comparison between hydrogels crosslinked by permanent covalent4 of 31 bonds and by supramolecular forces regarding their properties with relevance for protein delivery in TE applications. Figure 2. Schematic highlighting the properties and medical applications of supramolecular hydrogels. Figure 2. Schematic highlighting the properties and medical applications of supramolecular hydro- gels. Table 1. Comparison between hydrogels with permanent covalent and reversible
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