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      • Stabilization of Polymer-Hydrogel Capsules via Thiol–Disulfide Exchange

        Chong, Siow-Feng,Chandrawati, Rona,Stä,dler, Brigitte,Park, Jeongju,Cho, Jinhan,Wang, Yajun,Jia, Zhongfan,Bulmus, Volga,Davis, Thomas P.,Zelikin, Alexander N.,Caruso, Frank WILEY-VCH Verlag 2009 Small Vol.5 No.22

        <P>Polymer hydrogels are used in diverse biomedical applications including drug delivery and tissue engineering. Among different chemical linkages, the natural and reversible thiol–disulfide interconversion is extensively explored to stabilize hydrogels. The creation of macro-, micro-, and nanoscale disulfide-stabilized hydrogels commonly relies on the use of oxidizing agents that may have a detrimental effect on encapsulated cargo. Herein an oxidization-free approach to create disulfide-stabilized polymer hydrogels via a thiol–disulfide exchange reaction is reported. In particular, thiolated poly(methacrylic acid) is used and the conditions of polymer crosslinking in solution and on colloidal porous and solid microparticles are established. In the latter case, removal of the core particles yields stable, hollow, disulfide-crosslinked hydrogel capsules. Further, a procedure is developed to achieve efficient disulfide crosslinking of multilayered polymer films to obtain stable, liposome-loaded polymer-hydrogel capsules that contain functional enzymatic cargo within the liposomal subcompartments. This approach is envisaged to facilitate the development of biomedical applications of hydrogels, specifically those including fragile cargo.</P> <B>Graphic Abstract</B> <P>Polymer-hydrogel capsules are stabilized via disulfide linkages whereby crosslinking relies on the thiol–disulfide exchange without the use of oxidizing agents (see image). The method permits the formation of hollow capsules as well as functional capsosomes, hydrogel capsules subcompartmentalized with enzyme-loaded liposomes, without the loss of activity of liposome-encapsulated enzymes. <img src='wiley_img/16136810-2009-5-22-SMLL200900906-content.gif' alt='wiley_img/16136810-2009-5-22-SMLL200900906-content'> </P>

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