Immobilization of quantum dots in multiple responsive microgels for biomedical applications

A novel type of smart hybrid materials based on the in situ immobilization of quantum dots (QDs) on a responsive microgel template was prepared and investigated. Firstly, a temperature and pH dual responsive hybrid microgel was developed through the in-situ immobilization of CdS QDs in the interior of a copolymer microgel of poly(Nisopropylacrylamide- acrylamide-acrylic acid) [p(NIPAM-AAm-AA)]. The amino groups of the pAAm segments in the microgels are designed to sequester the precursor Cd2+ ions for in situ formation of CdS QDs in the interior of the microgels and stabilize the CdS QDs embedded in the microgels. We demonstrated that the carboxyl groups on the p(NIPAM-AAm-AA)-CdS hybrid microgels can be used for further coupling with 3-aminophenyl boronic acid for optical glucose sensing. The glucose concentration change can induce a reversible swelling/shrinkage of the hybrid microgels, which can further modify the physicochemical environment of the QDs immobilized inside the microgels, resulting in a reversible quenching/antiquenching in photoluminescence (PL). The method is extendable to other QDs with different emission wavelengths and other targeting ligands, thus it is possible to develop multifunctional hybrid micro-/nano-gels for additional important biomedical applications.

[1]  B. Chu,et al.  Laser Light Scattering , 1974 .

[2]  Michael Vollmer,et al.  Optical properties of metal clusters , 1995 .

[3]  E. Kumacheva,et al.  Zwitterionic Poly(betaine-N-isopropylacrylamide) Microgels: Properties and Applications , 2008 .

[4]  Yongjun Zhang,et al.  Permeability control of glucose-sensitive nanoshells. , 2007, Biomacromolecules.

[5]  Paul Mulvaney,et al.  Surface Plasmon Spectroscopy of Nanosized Metal Particles , 1996 .

[6]  Robert Pelton,et al.  Engineering Glucose Swelling Responses in Poly(N-isopropylacrylamide)-Based Microgels , 2007 .

[7]  Shuiqin Zhou,et al.  Synthesis and Volume Phase Transition of Poly(methacrylic acid-co-N-isopropylacrylamide) Microgel Particles in Water , 1998 .

[8]  Weitai Wu,et al.  Optical detection of glucose by CdS quantum dots immobilized in smart microgels. , 2009, Chemical communications.

[9]  Y. Liu,et al.  Highly Photoluminescent CdTe/Poly(N‐isopropylacrylamide) Temperature‐Sensitive Gels , 2005 .

[10]  Helmuth Möhwald,et al.  Incorporating Fluorescent CdTe Nanocrystals into a Hydrogel via Hydrogen Bonding: Toward Fluorescent Microspheres with Temperature-Responsive Properties , 2005 .

[11]  Shuming Nie,et al.  Cell-penetrating quantum dots based on multivalent and endosome-disrupting surface coatings. , 2007, Journal of the American Chemical Society.

[12]  R. Yoshida,et al.  Preparation of Thermosensitive Submicrometer Gel Particles with Anionic and Cationic Charges , 1999 .

[13]  Weitai Wu,et al.  Tunable Photoluminescence of Ag Nanocrystals in Multiple-Sensitive Hybrid Microgels , 2009 .

[14]  C. Ratcliffe,et al.  Interfacing Supramolecular Gels and Quantum Dots with Ultrasound: Smart Photoluminescent Dipeptide Gels , 2008 .

[15]  V. Cimrová,et al.  Switchable photoluminescence of CdTe nanocrystals by temperature-responsive microgels. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[16]  E. Kumacheva,et al.  Polymer microgels: reactors for semiconductor, metal, and magnetic nanoparticles. , 2004, Journal of the American Chemical Society.

[17]  Leonid Ionov,et al.  Fast and Spatially Resolved Environmental Probing Using Stimuli‐Responsive Polymer Layers and Fluorescent Nanocrystals , 2006 .

[18]  Jeff Blyth,et al.  Holographic glucose sensors. , 2005, Biosensors & bioelectronics.

[19]  W. Knoll,et al.  Rapid and Highly Efficient Preparation of Water-Soluble Luminescent Quantum Dots via Encapsulation by Thermo- and Redox-Responsive Hydrogels , 2008 .

[20]  R. Pelton,et al.  Highly pH and temperature responsive microgels functionalized with vinylacetic acid , 2004 .

[21]  Jess P. Wilcoxon,et al.  Photoluminescence from nanosize gold clusters , 1998 .