Dendrimer-encapsulated metal nanoparticles: synthesis, characterization, and applications to catalysis.

This Account reports the synthesis and characterization of dendrimer-encapsulated metal nanoparticles and their applications to catalysis. These materials are prepared by sequestering metal ions within dendrimers followed by chemical reduction to yield the corresponding zerovalent metal nanoparticle. The size of such particles depends on the number of metal ions initially loaded into the dendrimer. Intradendrimer hydrogenation and carbon-carbon coupling reactions in water, organic solvents, biphasic fluorous/organic solvents, and supercritical CO2 are also described.

[1]  A. Datye,et al.  Bimetallic palladium-platinum dendrimer-encapsulated catalysts. , 2003, Journal of the American Chemical Society.

[2]  J. H. van den Berg.  Poly(propylenimine) dendrimers: large-scale synthesis via heterogeneously catalyzed hydrogenation , 2003 .

[3]  H. Dai,et al.  Delivery of Catalytic Metal Species onto Surfaces with Dendrimer Carriers for the Synthesis of Carbon Nanotubes with Narrow Diameter Distribution , 2002 .

[4]  Robert M Dickson,et al.  Individual water-soluble dendrimer-encapsulated silver nanodot fluorescence. , 2002, Journal of the American Chemical Society.

[5]  Paul C J Kamer,et al.  Dendrimers as support for recoverable catalysts and reagents. , 2002, Chemical reviews.

[6]  R. Crooks,et al.  Dendrimer-Mediated Immobilization of Catalytic Nanoparticles on Flat, Solid Supports , 2002 .

[7]  Amy S. H. King,et al.  Catalysis Using Peripherally Functionalized Dendrimers , 2002 .

[8]  I. Simon,et al.  The role of hydrophobic microenvironments in modulating pKa shifts in proteins , 2002, Proteins.

[9]  Anil K Patri,et al.  Dendritic polymer macromolecular carriers for drug delivery. , 2002, Current opinion in chemical biology.

[10]  H. Dijkstra,et al.  The use of ultra- and nanofiltration techniques in homogeneous catalyst recycling. , 2002, Accounts of chemical research.

[11]  Interactions between dendrimers and charged probe molecules. 1. Theoretical methods for simulating proton and metal ion binding to symmetric polydentate ligands , 2002 .

[12]  Jean M. J. Fréchet,et al.  Dendrimers and supramolecular chemistry , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[13]  Amy S. H. King,et al.  Catalysis inside dendrimers. , 2002, Chemical Society reviews.

[14]  A. Biffis,et al.  Catalysis by metal nanoparticles supported on functional organic polymers , 2001 .

[15]  Valérie Cabuil,et al.  Designed Hybrid Organic−Inorganic Nanocomposites from Functional Nanobuilding Blocks , 2001 .

[16]  T. Early,et al.  Palladium-catalysed cross-coupling reactions in supercritical carbon dioxide. , 2001, Chemical communications.

[17]  P. Floriano,et al.  Cu(0) nanoclusters derived from poly(propylene imine) dendrimer complexes of Cu(II). , 2001, Journal of the American Chemical Society.

[18]  D. Astruc,et al.  Dendritic catalysts and dendrimers in catalysis. , 2001, Chemical reviews.

[19]  M. El-Sayed,et al.  The Effect of Stabilizers on the Catalytic Activity and Stability of Pd Colloidal Nanoparticles in the Suzuki Reactions in Aqueous Solution , 2001 .

[20]  R. Crooks,et al.  Size-selective hydrogenation of olefins by Dendrimer-encapsulated palladium nanoparticles , 2001 .

[21]  J. Reek,et al.  Transition Metal Catalysis Using Functionalized Dendrimers. , 2001, Angewandte Chemie.

[22]  P. Rinaldi,et al.  Structure and conformation of DAB dendrimers in solution via multidimensional NMR techniques. , 2001, Journal of the American Chemical Society.

[23]  C. H. Walker,et al.  Synthesis and size control of gold nanoparticles stabilized by poly(methylphenylphosphazene). , 2001, Journal of the American Chemical Society.

[24]  D. Tomalia,et al.  Poly(amidoamine) (PAMAM) dendrimers: from biomimicry to drug delivery and biomedical applications. , 2001, Drug discovery today.

[25]  R. Crooks,et al.  Characterization of Poly(amidoamine) Dendrimers and Their Complexes with Cu2+ by Matrix-Assisted Laser Desorption Ionization Mass Spectrometry , 2001 .

[26]  B. Bauer,et al.  Nanoparticle Formation within Dendrimer-Containing Polymer Networks: Route to New Organic−Inorganic Hybrid Materials , 2001 .

[27]  James R. Baker,et al.  The Synthesis and Testing of Anti-Cancer Therapeutic Nanodevices , 2001 .

[28]  R. Ispasoiu,et al.  Ultrafast time-resolved photoluminescence from novel metal–dendrimer nanocomposites , 2001 .

[29]  R. Crooks,et al.  Heck Heterocoupling within a Dendritic Nanoreactor , 2001 .

[30]  R. Crooks,et al.  Dendrimer-Encapsulated Metals and Semiconductors: Synthesis, Characterization, and Applications , 2001 .

[31]  A. Mayer.  Colloidal metal nanoparticles dispersed in amphiphilic polymers , 2001 .

[32]  S. Zimmerman,et al.  Supramolecular Chemistry of Dendrimers , 2001 .

[33]  R. Crooks,et al.  Preparation and Characterization of Dendrimer-Encapsulated CdS Semiconductor Quantum Dots , 2000 .

[34]  Wei Chen,et al.  Unusual pH-Dependent Polarity Changes in PAMAM Dendrimers:  Evidence for pH-Responsive Conformational Changes , 2000 .

[35]  K. Kono,et al.  Synthesis of polyamidoamine dendrimers having poly(ethylene glycol) grafts and their ability to encapsulate anticancer drugs. , 2000, Bioconjugate chemistry.

[36]  Suzuki,et al.  Preparation of Hydrophobically Modified Poly(amidoamine) Dendrimer-Encapsulated Gold Nanoparticles in Organic Solvents. , 2000, Journal of colloid and interface science.

[37]  K. Torigoe,et al.  Preparation of Platinum Nanoparticles in Ethyl Acetate in the Presence of Poly(amidoamine) dendrimers with a Methyl Ester Terminal Group , 2000 .

[38]  A. Chan,et al.  Highly Effective and Recyclable Dendritic BINAP Ligands for Asymmetric Hydrogenation. , 2000 .

[39]  B. Bauer,et al.  Dendrimer Templates for the Formation of Gold Nanoclusters , 2000 .

[40]  K. Inoue,et al.  Functional dendrimers, hyperbranched and star polymers , 2000 .

[41]  E. W. Meijer,et al.  Energy transfer in supramolecular assemblies of oligo(p-phenylene vinylene)s terminated poly(propylene imine) dendrimers , 2000 .

[42]  G. Koten,et al.  Fluorous Versions of Wilkinson's Catalyst : Activity in Fluorous Hydrogenation of 1-Alkenes and Recycling by Fluorous Biphasic Separation , 2000 .

[43]  Zhengguo Zhu,et al.  Correlated Excimer Formation and Molecular Rotational Dynamics in Phenylacetylene Dendrimers , 2000 .

[44]  R. Murray,et al.  Monolayer-protected cluster molecules. , 2000, Accounts of chemical research.

[45]  K. Kono,et al.  Water-soluble dendritic unimolecular micelles: their potential as drug delivery agents. , 2000, Journal of controlled release : official journal of the Controlled Release Society.

[46]  A. Suzuki,et al.  Role of Poly(amidoamine) Dendrimers for Preparing Nanoparticles of Gold, Platinum, and Silver , 2000 .

[47]  Z. Sideratou,et al.  Quaternized Poly(propylene imine) Dendrimers as Novel pH-Sensitive Controlled-Release Systems , 2000 .

[48]  R. Crooks,et al.  Dendrimer-Encapsulated Pd Nanoparticles as Fluorous Phase-Soluble Catalysts , 2000 .

[49]  Graham R. Fleming,et al.  Light Harvesting and Energy Transfer in Laser-Dye-Labeled Poly(aryl ether) Dendrimers , 2000 .

[50]  H. Ploehn,et al.  Aggregation Kinetics of Dendrimer-Stabilized CdS Nanoclusters , 2000 .

[51]  Paul L. Dubin,et al.  Counterion Binding on Charged Spheres: Effect of pH and Ionic Strength on the Mobility of Carboxyl-Terminated Dendrimers , 2000 .

[52]  Arjan W. Kleij,et al.  The "Dendritic Effect" in Homogeneous Catalysis with Carbosilane-Supported Arylnickel(II) Catalysts: Observation of Active-Site Proximity Effects in Atom-Transfer Radical Addition. , 2000, Angewandte Chemie.

[53]  M. Moskovits,et al.  Composite Nanostructures Based on Template-Grown Boron Nitride Nanotubules , 2000 .

[54]  E. W. Meijer,et al.  Host-Guest Chemistry of Dendritic Molecules , 2000 .

[55]  J. Fréchet,et al.  Preparation, MALDI-TOF analysis, and micelle-like behavior of alkyl-modified poly(propylene imine) dendrimers , 1999 .

[56]  S. Quici,et al.  Palladium-catalyzed heck reaction in perfluorinated solvents , 1999 .

[57]  Jonathan A. Iggo,et al.  Preparation and characterisation of solvent-stabilised nanoparticulate platinum and palladium and their catalytic behaviour towards the enantioselective hydrogenation of ethyl pyruvate , 1999 .

[58]  R. Crooks,et al.  Intradendrimer Exchange of Metal Nanoparticles , 1999 .

[59]  J. Fréchet,et al.  Designing dendrimers for drug delivery. , 1999, Pharmaceutical science & technology today.

[60]  B. Bauer,et al.  Probing the Location of the Terminal Groups of Dendrimers in Dilute Solution , 1999 .

[61]  J. Fréchet,et al.  Modular Approach to the Accelerated Convergent Growth of Laser Dye-Labeled Poly(aryl ether) Dendrimers Using a Novel Hypermonomer , 1999 .

[62]  K. Kono,et al.  Water-soluble dendrimer-poly(ethylene glycol) starlike conjugates as potential drug carriers , 1999 .

[63]  M. Shirai,et al.  Heck reactions using water-soluble metal complexes in supercritical carbon dioxide , 1999 .

[64]  Gerard V. Smith,et al.  Heterogeneous Catalysis in Organic Chemistry , 1999 .

[65]  R. Crooks,et al.  SELF-ASSEMBLED INVERTED MICELLES PREPARED FROM A DENDRIMER TEMPLATE : PHASE TRANSFER OF ENCAPSULATED GUESTS , 1999 .

[66]  E. W. Meijer,et al.  About Dendrimers: Structure, Physical Properties, and Applications. , 1999, Chemical reviews.

[67]  T. Tilley,et al.  Dendrimers as Building Blocks for Nanostructured Materials: Micro- and Mesoporosity in Dendrimer-Based Xerogels , 1999 .

[68]  F. Vögtle,et al.  Dendrimers: From Design to Application-A Progress Report. , 1999, Angewandte Chemie.

[69]  C. Wai,et al.  Synthesizing and Dispersing Silver Nanoparticles in a Water-in-Supercritical Carbon Dioxide Microemulsion. , 1999, Journal of the American Chemical Society.

[70]  R. Crooks,et al.  Dendrimer‐Encapsulated Pt Nanoparticles: Synthesis, Characterization, and Applications to Catalysis , 1999 .

[71]  T. Emrick,et al.  Self-assembly of dendritic structures , 1999 .

[72]  R. Crooks,et al.  Homogeneous Hydrogenation Catalysis with Monodisperse, Dendrimer-Encapsulated Pd and Pt Nanoparticles. , 1999, Angewandte Chemie.

[73]  R. Crooks,et al.  Preparation of Highly Impermeable Hyperbranched Polymer Thin-Film Coatings Using Dendrimers First as Building Blocks and Then as in Situ Thermosetting Agents , 1999 .

[74]  Jawwad A. Darr,et al.  New Directions in Inorganic and Metal-Organic Coordination Chemistry in Supercritical Fluids. , 1999, Chemical reviews.

[75]  R. Crooks,et al.  Chemically grafted polymeric filters for chemical sensors : Hyperbranched poly(acrylic acid) films incorporating β-cyclodextrin receptors and amine-functionalized filter layers , 1999 .

[76]  O. Platonova,et al.  Hydrogenation of dehydrolinalool with novel catalyst derived from Pd colloids stabilized in micelle cores of polystyrene-poly-4-vinylpyridine block copolymers , 1999 .

[77]  J. Reek,et al.  Catalysis in the core of a carbosilane dendrimer , 1999 .

[78]  C. Helm,et al.  Dendrimer-Encapsulated Pt Nanoparticles : Synthesis , Characterization , and Applications to Catalysis , 1999 .

[79]  L. A. Baker,et al.  Preparation and characterization of dendrimer-gold colloid nanocomposites. , 1999, Analytical chemistry.

[80]  K. Suslick,et al.  Shape-Selective Ligation to Dendrimer−Metalloporphyrins , 1999 .

[81]  A. L. Gray,et al.  Novel sulfonic acid-modified starburst dendrimer used as a pseudostationary phase in electrokinetic chromatography , 1998 .

[82]  D. Goodman,et al.  Onset of catalytic activity of gold clusters on titania with the appearance of nonmetallic properties , 1998, Science.

[83]  Donald A. Tomalia,et al.  Visualization of Dendrimer Molecules by Transmission Electron Microscopy (TEM): Staining Methods and Cryo-TEM of Vitrified Solutions , 1998 .

[84]  E. W. Meijer,et al.  Amphiphilic dendrimers as building blocks in supramolecular assemblies , 1998 .

[85]  Lajos P. Balogh,et al.  Poly(Amidoamine) Dendrimer-Templated Nanocomposites. 1. Synthesis of Zerovalent Copper Nanoclusters , 1998 .

[86]  M. Pileni.  Colloidal self-assemblies used as templates to control size, shape and self-organization of nanoparticles , 1998 .

[87]  A. Suzuki,et al.  Preparation of Gold Colloids with UV Irradiation Using Dendrimers as Stabilizer , 1998 .

[88]  Richard M. Crooks,et al.  Preparation of Cu Nanoclusters within Dendrimer Templates , 1998 .

[89]  Richard M. Crooks,et al.  Preparation and characterization of dendrimer monolayers and dendrimer - Alkanethiol mixed monolayers adsorbed to gold , 1998 .

[90]  V. Balzani,et al.  Azobenzene-Functionalized Cascade Molecules: Photoswitchable Supramolecular Systems , 1998 .

[91]  W. Heineman,et al.  Separation of aromatic acids, DOPA, and methyl-DOPA by capillary electrophoresis with dendrimers as buffer additives. , 1998, Journal of chromatographic science.

[92]  Joseph Klafter,et al.  Geometric versus Energetic Competition in Light Harvesting by Dendrimers , 1998 .

[93]  Markus Antonietti,et al.  Amphiphilic Block Copolymers in Structure-Controlled Nanomaterial Hybrids , 1998 .

[94]  Joseph Klafter,et al.  Dendrimers as light harvesting antennae , 1998 .

[95]  Marc D. Porter,et al.  Alkanethiolate Gold Cluster Molecules with Core Diameters from 1.5 to 5.2 nm: Core and Monolayer Properties as a Function of Core Size , 1998 .

[96]  L. A. Baker,et al.  Structural Distortion of Dendrimers on Gold Surfaces: A Tapping-Mode AFM Investigation , 1998 .

[97]  W. Tumas,et al.  Palladium-catalyzed cross-coupling reactions in supercritical carbon dioxide , 1998 .

[98]  F. Cotton,et al.  Catalysis by di- and polynuclear metal cluster complexes , 1998 .

[99]  L. Ronchin,et al.  Hydrogenation of mandelic acid derivatives to the corresponding phenyl acetic acid derivative catalysed by Pd/C. A kinetic study , 1997 .

[100]  F. Diederich,et al.  New Cyclophanes as Initiator Cores for the Construction of Dendritic Receptors: Host‐guest complexation in aqueous solutions and structures of solid‐state inclusion compounds , 1997 .

[101]  R. Crooks,et al.  Molecule-Sized Gates Based on Surface-Confined Dendrimers. , 1997 .

[102]  D. Bergbreiter,et al.  Water-soluble polymer-bound, recoverable palladium(0)-phosphine catalysts , 1997 .

[103]  D. Tsiourvas,et al.  Study of Poly(amidoamine) Starburst Dendrimers by Fluorescence Probing , 1997 .

[104]  R. Crooks,et al.  Interactions between Organized, Surface-Confined Monolayers and Vapor-Phase Probe Molecules. 12. Two New Methods for Surface-Immobilization and Functionalization of Chemically Sensitive Dendrimer Surfaces , 1997 .

[105]  A. Cooper,et al.  Extraction of a hydrophilic compound from water into liquid CO2 using dendritic surfactants , 1997, Nature.

[106]  Michael R. Shortreed,et al.  Directed Energy Transfer Funnels in Dendrimeric Antenna Supermolecules , 1997 .

[107]  Steven C. Zimmerman,et al.  Dendrimers in Supramolecular Chemistry: From Molecular Recognition to Self-Assembly. , 1997, Chemical reviews.

[108]  M. Reetz,et al.  Systhesis and Catalytic Activity of Dendritic Diphosphane Metal Complexes , 1997 .

[109]  P. M. Tomchuk,et al.  Optical absorption by small metallic particles , 1997 .

[110]  C. Mak,et al.  Dendritic Bis(oxazoline)copper(II) Catalysts. 2.1 Synthesis, Reactivity, and Substrate Selectivity , 1997 .

[111]  E. W. Meijer,et al.  Protonation Mechanism of Poly(propylene imine) Dendrimers and Some Associated Oligo Amines , 1997 .

[112]  Rupert Huber,et al.  TEMPLATE SYNTHESIS OF NANOWIRES IN POROUS POLYCARBONATE MEMBRANES: ELECTROCHEMISTRY AND MORPHOLOGY , 1997 .

[113]  A. Kaifer,et al.  Multisite Inclusion Complexation of Redox Active Dendrimer Guests , 1997 .

[114]  A. Schenning,et al.  Well‐Defined Metallodendrimers by Site‐Specific Complexation , 1997 .

[115]  D. Bergbreiter,et al.  Amphoteric, water-soluble polymer-bound hydrogenation catalysts , 1997 .

[116]  Notker Rösch,et al.  From clusters to bulk: A relativistic density functional investigation on a series of gold clusters Aun, n=6,…,147 , 1997 .

[117]  D. Tomalia,et al.  Hydrophobically modified poly(amidoamine) (PAMAM) dendrimers: their properties at the air–water interface and use as nanoscopic container molecules , 1997 .

[118]  E. W. Meijer,et al.  Liquid-liquid extractions using poly(propylene imine) dendrimers with an apolar periphery , 1997 .

[119]  K. Suslick,et al.  Shape selective epoxidation of alkenes by metalloporphyrin-dendrimers , 1996 .

[120]  J. V. Hest,et al.  Synthesis, characterization, and guest-host properties of inverted unimolecular dendritic micelles , 1996 .

[121]  D. Tomalia,et al.  Characterization of Starburst Dendrimers by EPR. 4. Mn(II) as a Probe of Interphase Properties , 1996 .

[122]  Mona C. Wells,et al.  Interactions between Organized, Surface-Confined Monolayers and Vapor-Phase Probe Molecules. 10. Preparation and Properties of Chemically Sensitive Dendrimer Surfaces , 1996 .

[123]  G. Grest,et al.  Molecular Dynamics Study of Dendrimer Molecules in Solvents of Varying Quality , 1996 .

[124]  Martin W. Brechbiel,et al.  MOLECULAR DYNAMICS OF ION-CHELATE COMPLEXES ATTACHED TO DENDRIMERS , 1996 .

[125]  P. Jessop,et al.  Homogeneous catalysis in supercritical fluids. , 1999, Science.

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

[127]  B. Gates.  Supported Metal Clusters: Synthesis, Structure, and Catalysis , 1995 .

[128]  R. Crooks,et al.  Interactions between Organized, Surface-Confined Monolayers and Liquid-Phase Probe Molecules. 3. Fundamental Aspects of the Binding Interaction between Charged Probe Molecules and Organomercaptan Monolayers , 1995 .

[129]  E. Meijer,et al.  The dendritic box, shape-selective liberation of encapsulated guests , 1995 .

[130]  E. Meijer,et al.  Encapsulation of Guest Molecules into a Dendritic Box. , 1995 .

[131]  I. Horváth,et al.  Facile catalyst separation without water: fluorous biphase hydroformylation of olefins. , 1994, Science.

[132]  G. Kaupp.  Reactions in Supercritical Carbon Dioxide , 1994 .

[133]  J. Wintterlin.  D. A. Bonnell (Ed.): Scanning tunneling microscopy and spectroscopy, theory, techniques and applications, VCH, New York, Weinheim, 1993 , 1994 .

[134]  J. Fréchet,et al.  Functional polymers and dendrimers: reactivity, molecular architecture, and interfacial energy. , 1994, Science.

[135]  G. Schmid.  Clusters and Colloids , 1994 .

[136]  P C Lauterbur,et al.  Dendrimer‐based metal chelates: A new class of magnetic resonance imaging contrast agents , 1994, Magnetic resonance in medicine.

[137]  Mathias Brust,et al.  Synthesis of thiol-derivatised gold nanoparticles in a two-phase liquid-liquid system , 1994 .

[138]  N. Turro,et al.  Characterization of Starburst Dendrimers by the EPR Technique. 1. Copper Complexes in Water Solution , 1994 .

[139]  L. Lewis.  Chemical catalysis by colloids and clusters , 1993 .

[140]  R. Augustine,et al.  Enantioselective heterogeneous catalysis I. A working model for the catalyst:modifier:substrate interactions in chiral pyruvate hydrogenations , 1993 .

[141]  M. Pileni,et al.  Synthesis of copper metallic clusters using reverse micelles as microreactors , 1993 .

[142]  John J. Bozzola,et al.  Electron microscopy : principles and techniques for biologists , 1992 .

[143]  J. C. Roberts,et al.  Using starburst dendrimers as linker molecules to radiolabel antibodies. , 1990, Bioconjugate chemistry.

[144]  R. Petter,et al.  Cooperative binding by aggregated mono-6-(alkylamino)-.beta.-cyclodextrins , 1990 .

[145]  William A. Goddard,et al.  Starburst Dendrimers: Molecular‐Level Control of Size, Shape, Surface Chemistry, Topology, and Flexibility from Atoms to Macroscopic Matter , 1990 .

[146]  A. Kirkland,et al.  A Morphology‐Selective Copper Organosol , 1988 .

[147]  James R. Dewald,et al.  A New Class of Polymers: Starburst-Dendritic Macromolecules , 1985 .

[148]  R. Heck.  PALLADIUM-CATALYZED VINYLATION OF ORGANIC HALIDES , 1983 .

[149]  V. Barone,et al.  Thermodynamics of protonation and complex formation of multifunctional polymers. , 1982 .

[150]  W. H. Jones.  Catalysis in organic syntheses , 1980 .

[151]  M. Graetzel,et al.  Projection, size factors, and reaction dynamics of colloidal redox catalysts mediating light induced hydrogen evolution from water , 1979 .

[152]  Hidefumi Hirai,et al.  Formation and Catalytic Functionality of Synthetic Polymer-Noble Metal Colloid , 1979 .

[153]  P. Rylander.  Catalytic Hydrogenation in Organic Syntheses , 1979 .

[154]  E. Buhleier,et al.  "Cascade"- and "Nonskid-Chain-like" Syntheses of Molecular Cavity Topologies , 1978 .

[155]  A. Vieux,et al.  Organic phase species in the extraction of hydrochloric acid by triisooctylamine in various organic diluents , 1976 .

[156]  U. Mayer.  Solvent effects on ion-pair equilibria , 1976 .

[157]  M. Hayat,et al.  Positive staining for electron microscopy , 1975 .

[158]  R. Heck,et al.  Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides , 1972 .