A general synthetic approach for obtaining cationic and anionic inorganic nanoparticles via encapsulation in amphiphilic copolymers.

A series of amphiphilic copolymers with variable charge densities on their backbone is synthesized. Positively charged N,N,N-trimethylammonium-2-ethyl methacrylate iodide or negatively charged 2-(methacryloyloxy)ethylphosphonic acid and lauryl methacrylate are used as building blocks. When wrapped around hydrophobically capped inorganic nanoparticles (NPs), the latter are able to disperse in aqueous solutions. Using this method, positively as well as negatively charged colloidal NPs can be synthesized in a reliable way. The method presented herein allows the charge on the NPs to be adjusted to different negative and positive values by using polymers with a variable ratio of charged monomers and lauryl methacrylate. Virtually all kinds of hydrophobic inorganic NPs could be coated with these amphiphilic polymers. The coating procedure is demonstrated for Au particles as well as for CdSe/ZnS quantum dots. To date, wrapping amphiphilic polymers around NPs has led only to anionic NPs. The polymers synthesized in this work allow for positively charged NPs with a high colloidal stability.

[1]  Tim Liedl,et al.  On the development of colloidal nanoparticles towards multifunctional structures and their possible use for biological applications. , 2004, Small.

[2]  B. Alince,et al.  Cationic latex: Colloidal behavior and interaction with anionic pulp fibers , 2000 .

[3]  G. Xu,et al.  Preparation and assembly of colloidal gold nanoparticles in CTAB-stabilized reverse microemulsion , 2003 .

[4]  L. Ghitescu,et al.  Surface charge distribution on the endothelial cell of liver sinusoids , 1984, The Journal of cell biology.

[5]  Dmitri I Svergun,et al.  Hydrophilization of Magnetic Nanoparticles with Modified Alternating Copolymers. Part 2: Behavior in solution. , 2010, The journal of physical chemistry. C, Nanomaterials and interfaces.

[6]  Chung-Yuan Mou,et al.  Size effect on cell uptake in well-suspended, uniform mesoporous silica nanoparticles. , 2009, Small.

[7]  Peter Reiss,et al.  Highly Luminescent CdSe/ZnSe Core/Shell Nanocrystals of Low Size Dispersion , 2002 .

[8]  Martin Oheim,et al.  Ion and pH sensing with colloidal nanoparticles: influence of surface charge on sensing and colloidal properties. , 2010, Chemphyschem : a European journal of chemical physics and physical chemistry.

[9]  Wolfgang J Parak,et al.  A quantitative fluorescence study of protein monolayer formation on colloidal nanoparticles. , 2009, Nature nanotechnology.

[10]  Martin Oheim,et al.  Synthesis and characterization of polymer-coated quantum dots with integrated acceptor dyes as FRET-based nanoprobes. , 2007, Nano letters.

[11]  Christopher J. Kiely,et al.  Synthesis and reactions of functionalised gold nanoparticles , 1995 .

[12]  Warren C W Chan,et al.  Elucidating the mechanism of cellular uptake and removal of protein-coated gold nanoparticles of different sizes and shapes. , 2007, Nano letters.

[13]  M. Williams,et al.  Endocytosis in alveolar type II cells: effect of charge and size of tracers. , 1984, Proceedings of the National Academy of Sciences of the United States of America.

[14]  Sara Linse,et al.  Understanding the nanoparticle–protein corona using methods to quantify exchange rates and affinities of proteins for nanoparticles , 2007, Proceedings of the National Academy of Sciences.

[15]  N. Simionescu,et al.  Anionized and cationized hemeundecapeptides as probes for cell surface charge and permeability studies: differentiated labeling of endothelial plasmalemmal vesicles , 1985, The Journal of cell biology.

[16]  A Paul Alivisatos,et al.  DNA-Based Assembly of Gold Nanocrystals. , 1999, Angewandte Chemie.

[17]  M. Bruchez,et al.  Immunofluorescent labeling of cancer marker Her2 and other cellular targets with semiconductor quantum dots , 2003, Nature Biotechnology.

[18]  S. Mutsaers,et al.  Surface Charge of Macrophages and Their Interaction With Charged Particles , 1988, Journal of leukocyte biology.

[19]  W. Chan,et al.  Systematic investigation of preparing biocompatible, single, and small ZnS-Capped CdSe quantum dots with amphiphilic polymers. , 2008, ACS nano.

[20]  Igor L. Medintz,et al.  Modular poly(ethylene glycol) ligands for biocompatible semiconductor and gold nanocrystals with extended pH and ionic stability , 2008, Journal of Materials Chemistry.

[21]  Matthias Epple,et al.  TOXICITY OF SILVER NANOPARTICLES INCREASES DURING STORAGE BECAUSE OF SLOW DISSOLUTION UNDER RELEASE OF SILVER IONS , 2010 .

[22]  Rebekah Drezek,et al.  Forming biocompatible and nonaggregated nanocrystals in water using amphiphilic polymers. , 2007, Journal of the American Chemical Society.

[23]  Carsten Sönnichsen,et al.  Separation of nanoparticles by gel electrophoresis according to size and shape. , 2007, Nano letters.

[24]  C. McKenna,et al.  The facile dealkylation of phosphonic acid dialkyl esters by bromotrimethylsilane , 1977 .

[25]  Suntharampillai Thevuthasan,et al.  PEGylated inorganic nanoparticles. , 2011, Angewandte Chemie.

[26]  Joachim O. Rädler,et al.  Hydrophobic Nanocrystals Coated with an Amphiphilic Polymer Shell: A General Route to Water Soluble Nanocrystals , 2004 .

[27]  L. Bronstein,et al.  Water-soluble surface-anchored gold and palladium nanoparticles stabilized by exchange of low molecular weight ligands with biamphiphilic triblock copolymers. , 2008, Langmuir.

[28]  A. Cooper,et al.  Formation of spherical nanostructures by the controlled aggregation of gold colloids. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[29]  Walter H. Chang,et al.  Design of an amphiphilic polymer for nanoparticle coating and functionalization. , 2008, Small.

[30]  Dmitri I Svergun,et al.  Hydrophilization of Magnetic Nanoparticles with Modified Alternating Copolymers. Part 1: The Influence of the Grafting. , 2010, The journal of physical chemistry. C, Nanomaterials and interfaces.

[31]  Wolfgang J. Parak,et al.  Electrophoretic Separation of Nanoparticles with a Discrete Number of Functional Groups , 2006 .

[32]  William W. Yu,et al.  Quantifying the Influence of Surface Coatings on Quantum Dot Uptake in Cells , 2005 .

[33]  Dieter Braun,et al.  Size determination of (bio)conjugated water-soluble colloidal nanoparticles : A comparison of different techniques , 2007 .

[34]  Arezou A Ghazani,et al.  Determining the size and shape dependence of gold nanoparticle uptake into mammalian cells. , 2006, Nano letters.

[35]  K. Müllen,et al.  A Simple and Efficient Route to Transparent Nanocomposites , 2008 .

[36]  Jiaqi Lin,et al.  Penetration of lipid membranes by gold nanoparticles: insights into cellular uptake, cytotoxicity, and their relationship. , 2010, ACS nano.

[37]  C. Bustamante,et al.  Conjugation of DNA to Silanized Colloidal Semiconductor Nanocrystalline Quantum Dots , 2002 .

[38]  D. Buhler,et al.  Epimerization and Fragmentation of Glucose by Quaternary Ammonium Base Type Anion Exchange Resins 1 , 1955 .