Supramolecular hybrid hydrogel based on host-guest interaction and its application in drug delivery.

In this work, we developed a simple, novel method for constructing gold nanocomposite supramolecular hybrid hydrogels for drug delivery, in which gold nanocrystals were utilized as building blocks. First, methoxypoly(ethylene glycol) thiol (mPEG-SH, molecular weight (MW)=5 K) capped gold nanocrystals (nanospheres and nanorods) were prepared via a facile one-step ligand-exchange procedure. Then, the homogeneous supramolecular hybrid hydrogels were formed, after adding α-cyclodextrin (α-CD) into PEG-modified gold nanocrystal solutions, due to the host-guest inclusion. Both gold nanoparticles and inclusion complexes formed between α-CD and PEG chain provided the supra-cross-links, which are beneficial to the gelation formation. The resulting hybrid hydrogels were fully characterized by a combination of techniques including X-ray diffraction, rheology studies, and scanning electron microscopy. Meanwhile, the hybrid hydrogel systems demonstrated unique reversible gel-sol transition properties at a certain temperature caused by the temperature-responsive reversible supramolecular assembly. The drug delivery applications of such hybrid hydrogels were further investigated in which doxorubicin was selected as a model drug for in vitro release, cytotoxicity, and intracellular release studies. We believe that the development of such hybrid hydrogels will provide new and therapeutically useful means for medical applications.

[1]  Jing Yu,et al.  Tunable temperature-responsive supramolecular hydrogels formed by prodrugs as a codelivery system. , 2014, ACS applied materials & interfaces.

[2]  Ali Khademhosseini,et al.  Nanocomposite hydrogels for biomedical applications. , 2014, Biotechnology and bioengineering.

[3]  Jing Yu,et al.  Prodrugs forming multifunctional supramolecular hydrogels for dual cancer drug delivery. , 2013, Journal of materials chemistry. B.

[4]  N. Chand,et al.  In situ formation of silver nanoparticles in poly(methacrylic acid) hydrogel for antibacterial applications , 2013 .

[5]  B. Tiersch,et al.  “One‐Pot” In Situ Formation of Gold Nanoparticles within Poly(acrylamide) Hydrogels , 2013 .

[6]  H. Allcock,et al.  Injectable and Biodegradable Supramolecular Hydrogels by Inclusion Complexation between Poly(organophosphazenes) and α-Cyclodextrin , 2013 .

[7]  Guosong Chen,et al.  Supramolecular Hybrid Hydrogels from Noncovalently Functionalized Graphene with Block Copolymers , 2011 .

[8]  H. Duan,et al.  Plasmonic vesicles of amphiphilic gold nanocrystals: self-assembly and external-stimuli-triggered destruction. , 2011, Journal of the American Chemical Society.

[9]  Brendan D. Smith,et al.  DNA-functionalized monolithic hydrogels and gold nanoparticles for colorimetric DNA detection. , 2010, ACS applied materials & interfaces.

[10]  Yong Qian,et al.  In Situ controllable preparation of gold nanorods in thermo-responsive hydrogels and their application in surface enhanced Raman scattering , 2010 .

[11]  Mingyu Guo,et al.  Dual Stimuli-Responsive Supramolecular Hydrogel Based on Hybrid Inclusion Complex (HIC) , 2010, Macromolecules.

[12]  Hong Ding,et al.  Biocompatible PEGylated gold nanorods as colored contrast agents for targeted in vivo cancer applications , 2010, Nanotechnology.

[13]  Jun Li,et al.  Self-assembled supramolecular hydrogels based on polymer-cyclodextrin inclusion complexes for drug delivery , 2010 .

[14]  Yong‐Ill Lee,et al.  Development of semi-interpenetrating carbohydrate polymeric hydrogels embedded silver nanoparticles and its facile studies on E. coli , 2010 .

[15]  C. Tsitsilianis Responsive reversible hydrogels from associative “smart” macromolecules , 2010 .

[16]  Rajesh Singh,et al.  Nanoparticle-based targeted drug delivery. , 2009, Experimental and molecular pathology.

[17]  T. Pal,et al.  Alginate Gel-Mediated Photochemical Growth of Mono- and Bimetallic Gold and Silver Nanoclusters and Their Application to Surface-Enhanced Raman Scattering , 2009 .

[18]  K. Narayanan,et al.  Coriander leaf mediated biosynthesis of gold nanoparticles , 2008 .

[19]  M. Guo,et al.  Supramolecular Hydrogels Made of End-Functionalized Low-Molecular-Weight PEG and α-Cyclodextrin and Their Hybridization with SiO2 Nanoparticles through Host−Guest Interaction , 2008 .

[20]  Alaaldin M. Alkilany,et al.  Gold nanoparticles in biology: beyond toxicity to cellular imaging. , 2008, Accounts of chemical research.

[21]  Virander S. Chauhan,et al.  Stimuli responsive self-assembled hydrogel of a low molecular weight free dipeptide with potential for tunable drug delivery. , 2008, Biomacromolecules.

[22]  Chaoliang He,et al.  In situ gelling stimuli-sensitive block copolymer hydrogels for drug delivery. , 2008, Journal of controlled release : official journal of the Controlled Release Society.

[23]  Akira Harada,et al.  Construction of chemical-responsive supramolecular hydrogels from guest-modified cyclodextrins. , 2008, Chemistry, an Asian journal.

[24]  Heikki Tenhu,et al.  Recent advances in polymer protected gold nanoparticles: synthesis, properties and applications. , 2007, Chemical communications.

[25]  Takeshi Karino,et al.  Gelation Mechanism of Poly(N-isopropylacrylamide)−Clay Nanocomposite Gels , 2007 .

[26]  Y. Takashima,et al.  Chemically-responsive sol-gel transition of supramolecular single-walled carbon nanotubes (SWNTs) hydrogel made by hybrids of SWNTs and cyclodextrins. , 2007, Journal of the American Chemical Society.

[27]  V. Vittoria,et al.  Potential perspectives of bio-nanocomposites for food packaging applications , 2007 .

[28]  M. Bruening,et al.  Catalytic membranes prepared using layer-by-layer adsorption of polyelectrolyte/metal nanoparticle films in porous supports. , 2006, Nano letters.

[29]  Kam W Leong,et al.  Self-assembled supramolecular hydrogels formed by biodegradable PEO-PHB-PEO triblock copolymers and alpha-cyclodextrin for controlled drug delivery. , 2006, Biomaterials.

[30]  N. Flynn,et al.  Thermoresponsive behavior of poly(n-isopropylacrylamide) hydrogels containing gold nanostructures. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[31]  Frank Bates,et al.  Shrinkage of a rapidly growing tumor by drug-loaded polymersomes: pH-triggered release through copolymer degradation. , 2006, Molecular pharmaceutics.

[32]  A. Miller,et al.  Nanostructured Hydrogels for Three‐Dimensional Cell Culture Through Self‐Assembly of Fluorenylmethoxycarbonyl–Dipeptides , 2006 .

[33]  J F Hainfeld,et al.  Gold nanoparticles: a new X-ray contrast agent. , 2006, The British journal of radiology.

[34]  Hongwei Liao and,et al.  Gold Nanorod Bioconjugates , 2005 .

[35]  E. Gil,et al.  Stimuli-reponsive polymers and their bioconjugates , 2004 .

[36]  A. Ojida,et al.  Molecular recognition in a supramolecular hydrogel to afford a semi-wet sensor chip. , 2004, Journal of the American Chemical Society.

[37]  Hua Ai,et al.  Micellar carriers based on block copolymers of poly(ε-caprolactone) and poly(ethylene glycol) for doxorubicin delivery , 2004 .

[38]  D. Astruc,et al.  Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. , 2004, Chemical reviews.

[39]  Kam W Leong,et al.  Injectable drug-delivery systems based on supramolecular hydrogels formed by poly(ethylene oxide)s and alpha-cyclodextrin. , 2003, Journal of biomedical materials research. Part A.

[40]  K. Leong,et al.  Formation of Supramolecular Hydrogels Induced by Inclusion Complexation between Pluronics and α-Cyclodextrin , 2001 .

[41]  Itamar Willner,et al.  Gold Nanoparticle/Hydrogel Composites with Solvent‐Switchable Electronic Properties , 2001 .

[42]  K. Noguchi,et al.  A Novel Pseudo-Polyrotaxane Structure Composed of Cyclodextrins and a Straight-Chain Polymer: Crystal Structures of Inclusion Complexes of β-Cyclodextrin with Poly(trimethylene oxide) and Poly(propylene glycol) , 2000 .

[43]  A. Tonelli,et al.  Study of the inclusion compounds formed between α-cyclodextrin and high molecular weight poly(ethylene oxide) and poly(ϵ-caprolactone) , 1998 .

[44]  P. Baglioni,et al.  α-Cyclodextrin/Polyethylene Glycol Polyrotaxane: A Study of the Threading Process , 1997 .

[45]  A. Harada,et al.  Preparation and properties of inclusion complexes of polyethylene glycol with .alpha.-cyclodextrin , 1993 .

[46]  Akira Harada,et al.  Complex formation between poly(ethylene glycol) and α-cyclodextrin , 1990 .