The supramolecular chemistry of organic inorganic hybrid materials

The Supramolecular Chemistry of Organic – Inorganic Hybrid Materials The Supramolecular Chemistry of Organic – Inorganic Hybrid Materials Edited by Knut Rurack and Ramo´n Martı´nez-Ma´n˜ez Copyright # 2010 by John Wiley & Sons, Inc All rights reserved Published by John Wiley & Sons, Inc., Hoboken, New Jersey Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web at www.copyright.com Requests to the Publisher for permission should be addressed to the Permissions Department, John 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contact our Customer Care Department within the United States at (800) 762-2974, outside the United States at (317) 572-3993 or fax (317) 572-4002 Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronic formats For more information about Wiley products, visit our web site at www.wiley.com Colored versions of Figures 3.1– 3.5, 3.7–3.17, 3.19, 3.20, 3.22, 3.24– 3.29, 4.9, 4.12, 5.2, 5.10, 6.1–6.3, 6.5, 6.10, 6.12, 6.14, 7.2–7.5, 7.7– 7.11, 8.3, 8.5, 8.9–8.11, 8.13– 8.16, 9.3, 9.6, 9.8, 9.10, 10.2, 10.7, 10.10, 11.9–11.11, 11.14–11.16, 11.18, 12.2, 12.4– 12.7, 13.1–13.19, 15.2–15.6, 15.9, 16.2, 16.5– 16.12, 19.1–19.6, 19.8, 19.12, 19.13, 19.15–19.19, 20.1, 20.4, 20.5, 21.1, 21.2, 21.5– 21.10, 21.12, 21.13, 21.15, 21.21, 21.24, 21.25, 22.1, 22.2, 22.5, 23.9, 24.2, 25.1, 25.2, 25.4–25.6 and Schemes 5.1– 5.5, 5.8, 5.9, 6.3, 6.4, 20.1 are available from the FTP site Library of Congress Cataloging-in-Publication Data: The supramolecular chemistry of organic-inorganic hybrid materials / edited by Knut Rurack and Ramo´n Martı´nez-Ma´n˜ez p cm Includes index ISBN 978-0-470-37621-8 (cloth) Supramolecular chemistry Nanochemistry Nanostructured materials I Rurack, Knut II Ramo´n Martı´nez-Ma´n˜ez QD882.S87 2010 620.10 1—dc22 2009019352 Printed in the United States of America 10 Contents Preface ix Editors and Contributors xiii Abbreviations xix Hybrid (Nano)Materials Meet Supramolecular Chemistry: A Brief Introduction to Basic Terms and Concepts Knut Rurack and Ramo´n Martı´nez-Ma´n˜ez Supramolecular Chemistry at the Mesoscale 11 Katsuhiko Ariga, Gary J Richards, Jonathan P Hill, Ajayan Vinu, and Toshiyuki Mori Part One Organic – Inorganic Hybrid Nanomaterials Silica-Based Mesoporous Organic Inorganic Hybrid Materials 39 Frank Hoffmann and Michael Froăba Modified Gold Nanoparticles and Surfaces 113 Paolo Pengo and Lucia Pasquato Organically Functionalized Semiconductor Nanocrystals: Synthesis, Properties and System Design for Optoelectronic Applications 155 Peter Reiss, Julia de Girolamo, and Adam Pron v vi Contents Functionalized Carbon Nanotubes for Bioapplications 197 Lingrong Gu, Fushen Lu, Pengju G Luo, Haifang Wang, Mohammed J Meziani, and Ya-Ping Sun Metal – Organic Frameworks (MOFs) and Coordination Polymers 235 Shin-Ichiro Noro and Susumu Kitagawa Part Two Improvement of Signaling and Sensing by Organization on Surfaces Nanoparticle and Biomolecular – Nanoparticle Hybrid Supramolecular Complexes for Electrochemical Signaling 273 Ronen Polsky, Jason C Harper, and Susan M Brozik Modified Nanoparticles as Nanoelectrocatalysts and Amplifying Sensors 297 Shaojun Guo, Erkang Wang, and Xiurong Yang 10 Signal Generation with Gold Nanoparticles: Photophysical Properties for Sensor and Imaging Applications 319 Qingshan Wei and Alexander Wei 11 Optical Signaling with Silica Nanoparticles 351 Fabrizio Mancin, Paolo Tecilla, and Umberto Tonellato 12 Organically Modified Quantum Dots in Chemical and Biochemical Analysis 377 Marı´a Teresa Ferna´ndez Arguăelles, Jose M Costa-Fernandez, Rosario Pereiro, and Alfredo Sanz-Medel Part Three Control of Supramolecular Nanofabrication, Motion, and Morphology 13 Chemically Directed Self-Assembly of Nanoparticle Structures on Surfaces Xing Yi Ling, David N Reinhoudt, and Jurriaan Huskens 407 Contents 14 Immobilization and Patterning of Biomolecules on Surfaces vii 433 Dorota I Roz˙kiewicz, Bart Jan Ravoo, and David N Reinhoudt 15 Switchable Host – Guest Chemistry on Surfaces 467 Jilie Kong, Chunming Jiang, and Li Mu 16 Nanogated Mesoporous Silica Materials 479 Igor I Slowing, Brian G Trewyn, and Victor S.-Y Lin 17 Building Molecular Machines on Surfaces 503 Alberto Credi, Serena Silvi, and Margherita Venturi 18 Control of Morphology in Mesoporous and Mesostructured Hybrid Materials 531 Darren R Dunphy, Bernd Smarsly, and C Jeffrey Brinker Part Four Biomimetic Chemistry 19 Biomimetically Inspired Signaling 549 Knut Rurack, Ramo´n Martı´nez-Ma´n˜ez, Fe´lix Sanceno´n, and Ana B Descalzo 20 Imprinted Functionalized Silica 581 Maryanne M Collinson 21 Bioinspired Block Copolymer-Based Hybrid Materials 599 Marleen Kamperman and Ulrich Wiesner Part Five Interfacial Chemistry, Multifunctionality, and Interdisciplinarity 22 Emerging Concepts in Interfacial Chemistry of Hybrid Materials: Nanocontainer-Based Self-Healing Coatings Dmitry G Shchukin, Daria V Andreeva, Katja Skorb, and Helmuth Moăhwald 639 viii Contents 23 Molecular Schizophrenics: Switchable Materials with Multiple Functions 653 Robert Byrne and Dermot Diamond 24 Hybrid Nanomaterials Research: Is It Really Interdisciplinary? 673 Ismael Rafols, Martin Meyer, and Jae-Hwan Park 25 Supramolecular Chemistry Meets Hybrid (Nano)Materials: A Brief Look Ahead 689 Knut Rurack and Ramo´n Martı´nez-Ma´n˜ez Appendix 701 Index 707 744 Index Particle, 592 array of, 408, 410, 420 –422 microparticle/microsphere/microbead, 389, 574, 594 see magnet; MagMOON; MCM-41; quartz; silica particle heating, 650 particle-substrate interactions, 420 see aluminosilicate; coupling; interface; nanoparticle; polymer; printing; single-molecule Particle-in-a-box model, 157 Particle size distribution, 97– 98, 130– 134, 158, 165, 167, 174, 242, 358, 398, 603, 605–606, 621 Partioning, hydrophilic/lipophilic, phase, 533–534, 555 see KOW Passivation, 6, 61–62, 65, 128, 159 –161, 168, 170, 279, 385, 398, 426, 443, 461 Pathogen, 127, 228 Patterning pattern enlargement (during printing), 447 pattern density, 456, 463 see channel; CBED; lithography; mask; micropatterning; nanopatterning; replica; resist; SAED; SAM PEBBLEs, 357–364, 368 see diameter Penetration depth (of light in tissue), 329, 332 Penicillin 6-aminopenicillanic acid, 98 benzylpenicillin, 94 native, 98 Pentafluorophenyl esters, 122 Peptide, 22, 28, 70, 114, 125, 127, 132, 135–136, 138, 144, 201, 203, 212–213, 282–284, 382, 392, 397, 418, 425, 434, 436, 438, 441, 448, 452–453, 470, 523, 543, 558, 690 amphiphilic peptide, 28 CALNN peptide, 136– 138 cell adhesive peptide, 455 GBP, 449 isolation and analysis (from human plasma), 489 NLS peptide, 144 peptide and printing, 448 peptide chain, 436 peptide nanotube, 472 ferrocene-appended, 470 cobaltocene-appended, 471 peptide synthesis, 452–453 RGD peptide (cyclic Arg-Gly-Asp), 125, 213, 225 UW-1 peptide, 201 see biotin; GEPI; lipid; oligopeptide; polypeptide Peptide nucleic acid (PNA), 434, 438, 452 Periodicity, 336 framework, 536 mesoscopic, 42, 75– 76 molecular, 76– 78, 89, 535 see organosilica Permeability, 370, 641, 651 see EPR; water Permeation, 21– 22 Permittivity, 82, 336 Permselectivity, 258 Perovskite, 24 Peroxidase, 99, 285, 362 chloroperoxidase (CPO), 99–100 heme peroxidase, 99 horseradish peroxidase, 285–288, 691 micro-peroxidase, 11, 285 Peroxynitrile, determination of, 362 Personal computer (PC); see computer Personal digital assistant (PDA), 2, 654 see computer; phone pH, 47, 57, 71, 99, 123, 134, 139, 201, 242, 287, 310, 369, 411, 414, 420, 425, 482, 489, 491–494, 498, 542, 556, 570, 585, 646–647, 651 pH as stimulus, 513, 537, 540, 640–643, 646–647, 649, 656, 660, 663 pH sensing, 71, 357, 359–360, 362, 364, 366, 371–372 pH stability, 99, 395 see corrosion; drug; dye; gated; hydrogel; imaging; molecular logic function; molecular motor; nanovalve; polymer; rotaxane Pharmaceutics/pharmaceuticals, 63, 98, 294, 581, 584, 595 see tablet Phase hexagonal phase, 16, 42, 48, 71, 91, 97, 481, 626 lamellar phase, 16, 42, 96– 97 micellar phase, 41 phase diagram, 42, 622 phase separation, 46, 60, 69, 77, 83, 90, 118, 141–142, 171, 174, 540 phase transfer agent, 130 transition, 22, 116, 126, 249 see chromatography; copolymer; crystal; Au; iron oxide; liquid crystal; M41S phase; mesophase; organosilica; oxygen; partioning; polymer; SBA phase; semiconductor NC; surfactant Phenanthroline, 562 bis-phenanthroline catenane, 516 Phenol alkylphenol, 555–556 p-aminophenol (pAP), 292 4-mercaptophenol, 130 p-nitrophenol (pNP), 292 adsoption of, 70 4-nonylphenol, 63 see thiophenol Index Phenosafranine, 359 Phenoxazinone, 64– 65 urea phenoxazinone, 552–553 Phenylalanines 3,4-dihydroxyphenylalanine, 591 1,4-Phenylenediisothiocyanate (PDITC), 437, 444 N,N -(1,4-Phenylenedimethylidyne) bis(1,4-benzenediamine), 66 Phenylenevinylenes, 542 see oligo(p-phenylene vinylene), PPV Phone landline phone, 654 mobile phone, 654 see PDA Phonon, 159 acoustic phonon emission, 160 phonon lattice, 338 see coupling Phosphanes bis( p-sulfonatophenyl)phenylphosphane dehydrate, dipotassium salt, 136 Phosphates, 491–492, 523, 552 adsorption of, 63 determination of, 573 organic phosphates, 552 alkylphosphate, long-chain, 50 polyphosphate, 382–383 see ADP; AMP; ATP; binaphthyls; guanidine; GMP; metal; phosphoric acid Phosphine/phosphine oxide, 428 bis( p-sulfonatophenyl)phenylphosphine, 307 p-bromobenzyl-di-n-octylphosphine oxide (DOPO-Br), 175– 176 triarylphosphines, 136 tributylphosphine (TBP), 166–167 trioctylphosphine (TOP), 166– 167 trioctylphosphine oxide (TOPO), 160–161, 166–167, 170– 171, 173– 175, 187, 313, 384, 387– 388, 425 tris(2-cyanoethyl)phosphine, 69 Phosphite triethylphosphite, 69 Phospholipid, 2, 283, 461 glycerophospholipid, 552 phospholipid micelle, 170 phospholipid-poly(ethylene glycol) hybrids (PL-PEG), 207, 212–215, 218, 225–227 phospholipid-poly(ethylene glycol)-folic acid hybrids (PL-PEG-FA), 214– 215 phospholipid-poly(ethylene glycol)-FITC hybrids (PL-PEG-FITC), 214– 215 Phosphonic acid/phosphonate alkenediphosphonate, 535 diethylphosphonate, 67 octadecylphosphonic acid (ODPA), 166 tetradecylphosphonic acid (TDPA), 166 Phosphorescence, 159, 394, 396, 399 room temperature (RTP), 396 see luminescence 745 Phosphoric acid, 595 see phosphate Photoacid generator (PAG), 535 amphiphilic PAG, 543 Photoacoustic tomography (PAT); see contrast agent; tomography Photoacoustic effects, NIR-induced, 329 Photoactivation/photoatcive, 240–241, 649 Photobleaching, 162, 327, 339, 359, 362, 378, 380, 389, 690 see photostability Photocatalysis/photocatalyst; see catalysis/ catalyst Photochemical radical addition, 428 Photochromic/photochromism; see azo compounds; diarylethene; dye; MCM-41; polymer; spirobenzopyran; spironaphthopyran; spiropyran Photocurrent, light induced, 415 Photodamage (of tissue), 329 Photodegradation, 162, 379, 649 see degradation Photodimerization; see anthracene Photodiode system, biomolecular, 449 Photo-electrorheological (PER) effect, 657 see electrorheological effect Photohole (in titania), 648– 649 Photoisomerization, 472, 491, 535, 537, 539, 542, 661–663, 668 see azo compounds; molecular rotor Photoluminescence; see luminescence Photolysis, 241 Photon, 157– 159 see absorption; coupling; energy; excitation; fluorescence; imaging; irradiation; luminescence; 3PL; TPA; TPL Photonic stop gap, 421 Photooxidation, 161, 173, 460 Photoprotection, 420 Photosaturation, 327 Photosensitizer/photosensitization, 496 Photostability, 163, 168 of dye, 354–355, 374 of Au, 339 of ND, 692 of fluorescent polystyrene NPs, 692 of semiconductor NCs, 381 see photobleaching Photostimulation, 383 Photoswitch; see rotaxane; switch Photosynthesis, bacterial, 523– 524 Photothermal, 327 –331 see actuation; contrast agent; imaging; transducer Photovoltaics, 263 Photovoltaic cell, 2, 156, 170, 173, 179, 183, 185–189, 378, 624 Phthalaldehyde, 372 terephthaldialdehyde, 444 746 Index Phthalates 2-aminoterephthalate (atp), 244 5-sulfoisophthalate (sip), 256 see anthracene; poly(ethylene terephthalate) o-Phthalic hemithioacetal (OPTA), 372, 489, 553 Phthalocyanine; see Fe Physical vapor deposition (PVD); see deposition Physisorption, 98, 116, 489 of biomolecules onto ND, 690 of lipid bilayers, 436 of oxygen, 26 of rotaxane, 515 of thiols, 116 of surfactants, 130 see nitrogen adsorption isotherm Picolinamide, 368 Pigment, photodestructible, 648 see cell Pins, metallic (contact printing), 457 Piranha solution, 437, 441 pKa, 253, 363– 364, 420 Place exchange, 119–120, 125, 132, 134 –135, 145, 276, 283– 284 see ligand displacement; synthesis Plasma (biological) human plasma, 393, 489 see cytoplasma Plasma (nonbiological) argon-oxygen plasma, 630–631 oxygen plasma, 437, 449–450 UV plasma (for cleaning), 441 see polymerization Plasmid, GFP-promoting, 487– 488 Plasmon/plasmonic, 333, 336 interparticle plasmon, 324 plasmon absorption/resonance band, 143, 146, 289, 326–327, 329–330, 332– 333, 336, 338–339, 341– 343, 373, 574, 649 shift in, 143 plasmon enhanced heating, 327–329 plasmonic ruler, 324 plasmonic waveguide, 144 surface plasmon/mode/wave, 320– 326 see coupling; field; LSPR; probe; quenching; scattering; silver; spectroscopy; SPR Plasticizer, 63 Platinum/ion/salts, 299, 308 adsorption of, 63 Pt acetylide, 508 Pt complex chain, 18 Pt electrode, 275– 276, 308, 313, 632 Pt film, macroporous, 302 Pt hybrids, 306 Pt monolayer, 308 Pt nanocube, 306–307 PtNCs, 631 PtNPs on electrodes, 299, 301, 306, 309 hybrids with biomolecules, 283, 290 with dendrimers, 306 with inorganic materials, 301, 308– 309 with polymers, 299 with semiconductor NCs, 413, 420 with silica, 302, 309 see CNT tetrahexahedral NPs, 306–307 Pt nanostructure, hollow, 307 –308 Pt nanotube array, 302 Pt-C hybrids, 629–632 Pt drug complex, 213 see alloy nanoparticle; catalyst; citrate; copolymer; graphite; metal; porphyrin; Ru Pluronics; see copolymer PMO (periodical mesoporous organosilica); see organosilica Polarity, 62, 551– 552, 555 Polarization, 342 see ferroelectricity; luminescence; tomography Polaron, 16 Policy drivers, 686 issue, 675 makers, 674 report/study, 674 –675 Pollution; see environmental Poloxamer, 48 Poly(acrylic acid) (PAA), 357, 415 Poly(N-acryloxysuccinimide), 495 Poly(alkylmethacrylate), 190 Poly(allylamine hydrochloride), 492 Poly(amidoamine) (PAMAM); see dendrimer Polyamine (receptor), 363, 438 Polyaniline (PANI), 71, 171, 288, 299, 658– 659 Poly(butyl methacrylate) (particle), 420 Polycarbonate (membrane), 565 Poly(carboxylbetaine methacrylate), 126 Polycondensation, 44, 46, 67, 71, 91, 95 see condensation Polycyclic aromatic hydrocarbons (PAH), 384, 509 separation/extraction of PAHs, 98, 697 Poly(decylmethacrylate), 357– 358 Poly(diacetylene) (PDA), 15, 80 Poly(2-(dimethylamino)ethyl methacrylate), 174 Poly(diallyldimethylammonium) chloride (PDDA), 21, 24, 286– 287, 492 Poly(dimethylsiloxane) (PDMS), 422–424, 447–456, 462– 463, 565, 659, 663 see stamp Poly(3,300 -dioctyl-2,20 :50 ,200 -terthiophene), 174 Poly[(4,400 -dioctyl-2,20 :50 ,200 -terthiophene-30 yl)ethylacetate], 183– 184 Polydispersity; see dispersity Poly(divinylbenzene), 244 Polyelectrolyte, 21, 23–24, 32, 285, 410 –412, 424–425, 451, 492, 641 –644 polyanion, 410, 642, 646 polycation, 410, 642, 647 polyelectrolyte film, 642 Index polyelectrolyte-inhibitor complex, 644 polyelectrolyte shell, 647– 651 stimuli-responsive polyelectrolyte, 642– 644 see adsorption; CNT; Au Polyester (production), 253 Polyethylene, 475–476 porous, 475– 476 Poly(3,4-ethylenedioxythiophene) (PEDOT), 187 Poly(ethylene glycol) (PEG), 73– 74, 117, 133, 144, 328, 332– 333, 341, 358, 440, 450, 452–453, 474, 487, 499, 574– 575 amphiphilic perfluorinated (HS-F8-PEG), 133–134, 142 antibody conjugates, 145 fluorescein-modified, 219 PEG aggregate, 74 thiloated PEG (PEG-SH), 117, 456 see oligo(ethylene glycol) derivatives; phospholipid; siloxanes; succinic acids; transfection Poly(ethylene imine) (PEI), 498, 642, 648– 649 linear, 425 Poly(ethylene oxide) (PEO), 49, 51, 126, 482, 607, 609 –611 alkyl ethers, 49 aryl ethers, 49 see disulfide chemistry; silanes; stamp Poly(ethylene oxide)-poly(DL-lactic acid-coglycolic acid)-poly(ethylene oxide) (PEO-PLGA-PEO), 48, 88 Poly(ethylene oxide)-poly(propylene oxide)poly(ethylene oxide) (PEO-PPO-PEO), 48–49 Poly(ethylene oxide-block-n-hexyl methacrylate) (PEO-b-PHMA), 610 Poly(ethylene-alt-propylene-block-ethylene oxide-block-n-hexyl methacrylate) (PEP-bPEO-b-PHMA), 603, 609–619 Poly(ethylene terephthalate), 455, 566 Polyfluorene, 174 see dendrimer Polyglycerol, hyperbranched, 126 Poly(3-hexylthiophene) (P3HT), 171, 173, 175–176, 186– 188 Poly(3-hexylthiophene-co-3-(6-oxy-2,4-diaminopyrimidine)-hexylthiophene) (P3HT-coP3(ODAP)HT), 177–180, 183 Poly(hydroxyethylmethacrylate-acrylic acid), 663 Polyions; see polyelectrolytes Poly(isoprene-block-dimethylaminoethyl methacrylate) (PI-b-PDMAEMA), 603, 629–632 Poly(isoprene-block-ethylene oxide) (PI-b-PEO), 602–605, 620, 624, 628 Poly(N-isopropylacrylamide) (PNIPAAm), 64, 475–477, 489, 541, 567 PNIPAAm clay, 541 spirobenzopyran-modified, 663– 664 see cylcodextrin Poly(lactic acid) (PLA), 372, 489– 490 see coating 747 Poly(laurylmethacrylate), 190 Polylysine, 450 coating on ND, 690 see hydroxyapatite-CNT-polylysine hybrid Poly(L-lysine)-g-poly(ethylene glycol), 452 Polymer, 7, 100, 130–131, 174– 175, 183, 186, 189, 243– 244, 259, 337, 357, 397, 410, 423, 462, 475 –476, 489–490, 495, 521, 524, 532, 534 –535, 540, 574, 582, 601–603, 609, 616, 619, 622, 624, 629, 633, 640, 657–658, 663, 667–668 acrylic polymer, 584 amphiphilic polymer, 170 antifouling polymer, 328 biocompatible polymer, 565 conductive/conducting/conjugated polymer, 6, 540, 542, 657– 659 electroactive, 640 see semiconductor NC cross-linked polymer, 170, 357, 495 crown ether polymer, 476–477 dextran polymer, 366 elastomeric polymer, 447 homopolymer, 601 industrial polymer, 189 nonabrasive polymer, 658 particle-reinforced polymers, 698 photochromic polymer, 669 polymer as delivery system, 212 polymer assembly, polymer bead; see polymer particle polymer coating/film/layer, 282, 423, 426, 566, 595, 640 polymer fiber, polymer for recognition, 177 polymer hybrids, with AuNPs and silica, 325 with AuNPs and CdTe NCs, 574 with inorganic NPs, 605, 620– 629, 632 film, 623, 630 mesophase, 622– 623 with ionophore, 563, 694 with metal/metal NPs, 629, 631 with TiO2 NPs, 423 with TiO2 NPs and CdS NCs, 411 size effects, 601 see CNT; Au; LED; Pt; PCP; semiconductor NC; silica; Ag; Ti polymer membrane, 522, 565, 694 thermosensitive, 475 polymer microgel, 574 polymer oxidation/reduction, 657– 658 polymer particle/bead, 145, 354, 399, 423, 574 microparticle, 574 NPs, 410 streptavidin-conjugated, 291 see diameter polymer– polymer interactions, 658 748 Index Polymer (Continued) polymer pump, 670 polymer resin, 640 polymer surface, 144, 449, 455, 456, 459, 595 polymer valve, 670 reactive polymer, 438 retardant polymer, 647 semiconducting polymer, 540, 657 spiropyran-modified polymer, 663, 668–670 stimuli-responsive/sensitive/switchable polymer, 468, 475, 567, 574 electrochemical/redox, 468 pH, 662 photo, 468 thermo, 64, 475– 477, 541 thermoplastic polymer, 425 see actuator; biopolymer; ceramic; coordination polymer; copolymer; degradation; hydrogel; interface; ion exchange; ion-imprinted polymer; metal; microvalve; miscibility; MIP; PCP; Ru; sol–gel; stabilizer; templating Polymer-nucleated metal-organic framework (PNMOF); see MOF Polymerase polymerase chain reaction (PCR), 290 RNA polymerase, 207 Polymerization, 176, 585, 588, 590, 592– 595, 640, 661 atom-transfer radical polymerization (ATRP), 64, 489, 567 copolymerization, 175, 593 free radical polymerization, 582–583, 592, 595 heat activated polymerization, 541 plasma-grafting polymerization, 475–476 polymerization of acetylene, 25– 26 polymerization of silanes/silicon derivatives/ orthosilicic acid, 352–353, 359, 361–363, 370, 372, 481, 483 see silanes; silica; silicon; sol– gel post-film synthesis, 540– 541 photo-polymerization, 663 radical polymerization, 190, 540 reversible addition-fragmentation chain transfer (RAFT) polymerization, 495 topo-/topotactic polymerization, 80, 259 see sol– gel Poly(methacrylic acid) (PMAA), 409 alkylthioether-functionalized, 131 see iron oxide Poly(methacrylic acid-co-divinylbenzene) (MAA-co-DVB), 244 Poly[2-methoxy-5-(30 ,70 -dimethyloctyloxy)-1,4phenylene-vinylene] (MDMO-PPV), 184, 188 Poly(2-methoxy-5-(20 -ethylhexyloxy)-1,4-phenylene-vinylene) (MEH-PPV), 186– 187 Poly(methyl methacrylic acid)/poly(methyl methacrylate) (PMMA), 384, 426, 668 Polymorphism of mesoporous SiC, 694 of PCP, 244 see SNP Polyolefine plastomers (POPs), 452 Poly(L-ornithine), 221 Polyoxometallate, 24 Polypeptide, 445, 450 see GBP Poly( p-phenylene vinylene) (PPV), 171, 174–176, 187 Poly(propylene imine) (PPI), 416, 439, 451, 471 see dendrimer Polypyrrole (PPY), 16, 542, 658– 659 Polyradical ion, 183 Polysaccharide, 453, 600 see carbohydrate; sugar Polysilsesquioxanes, imprinted, 593 Polystyrene diaminotriazine-functionalized, 177 (nano)particles, 203, 289, 331, 421, 423– 424, 426–427 fluorescent, 692 streptavidin-coated, 291 see HSMA; diameter; latex/latex beads; photostability Poly(styrene sulfonate) (PSS), 144, 187, 286–287, 411, 492, 642, 644, 649 Polysulfone, 258 Poly(3-(30 -thienyloxy)propyltrimethylammonium bromide) (P3TOPA), 180 Poly(thiophene), 171, 173, 180, 542 poly(alkylthiophene), 173, 177, 182 containing diaminopyrimidine, 177 containing tetrahydro-4H-thipyran-4ylidene, 173 Poly(3-thiophene acetic acid) (PTAA), 415 Polytype/polytypism of mesoporous SiC, 694 wurtzite-zinc blende, 161 Polyurethane production, 253 Poly(vinyl alcohol), 440 Poly(vinyl-N-methylpyridinium) (PVMP), 420 Poly(4-vinylpyridine) (P4VP), 415 Poly(4-vinylpyridine-co-divinylbenzene) (P4VP-co-DVB), 244 Poly(vinyl pyrrolidone) (PVP), 136, 146, 440 Poly(vinylidene fluoride) (PVDF), 659 Poly(vinylsulfonic acid) (PVSA), 244 Porcine liver esterase, 499 Pore, 482, 533, 537, 551, 563, 571 inner pore texture, 576 see diameter; interface; mesopore; micropore; nanopore; protein; surface Pore blocking/closure, 55–56, 485, 570 Pore size distribution (PSD), 26, 42–43, 52, 89, 237, 531, 585, 693 Index Porogen, 95– 96, 582, 592, 606 Porosity, 41–42, 45, 55, 72, 74, 83, 236, 543, 582–583, 587– 588, 591, 594, 628 dynamic porosity, 237, 246, 249– 252, 259, 263 hierarchical porosity, 243 homogeneous porosity, 573 interstitial porosity, 585 microporosity, 53 open/accessible porosity, 243, 538 ordered (meso)porosity, 78, 537, 628 permanent porosity, 248, 260 rigid porosity, 246 –249 Porous coordination polymer (PCP), 4, 237 –264 bistable PCP, 237, 262 chiral PCP, 240, 260 PCP and counter anion, 236, 242 PCP and guest inclusion, 236– 238, 248–252 PCP hybrids, with polymers, 258 interdigitated PCP, 252 Li-doped PCP, 256 mesoporous PCP, 243 pillard-layer frameworks, 246, 248 a-Po-type frameworks, 246, 248 PCP magnet (PCPM), 260– 262 PCPM and guest inclusion, 260 stimuli-responsive PCPM, 260 postmodification of PCP, 240– 241 shape and size selectivity of PCP, 238, 244 stability of PCP, 237, 241 chemical, 248 thermal, 248 switchable PCP, 249 toxicity, 264 transformations crystalline-to-amorphous, 261 single crystal-to-single crystal, 262 zeolitic frameworks, 246, 248 see bipyridines; boron; Cd; Cr; Cu; framework node; Fe; lanthanides; Mn; MIL; metal; Nd; Ni; polymorphism; Rh; Ru; Na; Ti; Zn; Zr Porphyrin octaethylporphine, 359 Pt octaethylporphine ketone, 359 porphyrin receptor, 13 tetrakis(1-methylpyridinium-4-yl) porphine (TMPyP), 559–560 Co TMPyP, 305 –306 tetraphenylporphine tetrasulfonic acid (TPPS), 559 Zn porphyrin, 65–66 Portable device/instrument, 654, 656 Positron emission tomography (PET); see tomography Potassium/ions/salts, 72, 131, 136, 313, 563 see Pt Potential chemical potential, 114, 118 749 electrode potential, 183, 185 electrical potential, 467–468 potential cycling, 278 potential energy surface, 507 transmembrane electrochemical potential, 524 see redox; UPD Potentiometry, 565, 655 stripping potentiometry, 289 Power conversion efficiency, 186 –187 electrical power generation, 304 power input/source, 304, 658, 663 power plant, 252 Principal component analysis, 384 Printer microselenoid/magnetic, 458 piezoelectric, 458 thermal, 458 Printing of biomolecules, 447 –450, 458, 462 of particles, 459 see cell; channel; contamination; deformation; ink-jet printing; lithography; mold; oligonucleotide; patterning; peptide; pins; resolution; SPCP; stamp; swelling; tip Probe; see scanning probe techniques neutron as probe, 245 probe (bio)molecule, 21, 136, 284, 288– 293, 328, 333, 337, 357, 388, 398, 435, 439, 457, 536, 552 density of, 414, 434, 457, 556 electrochemical/redox-active, 274, 280, 289– 290, 297– 298, 537, 539, 563– 565 see Fe; Mo; Ru fluorescent; see fluorophore pen-like probe, 665 plasmon-based (Raman), 332, 334, 336, 396 radical (for ESR), 140, 142 RI probe, 326 see cell; MagMOON; optical label Processor/central processing unit (CPU), 654, 665 Proline, 94, 584, 588 Propanolol, 583, 591 Propargyl bromide, 498 Propionic acids mercaptopropionic acid (MPA), 141 –142, 164, 382, 392, 485, 495 3-(propyldisulfanyl)propionic acid, 487 3-(2-pyridylthio)propionate, 445 Propyl Orange, 588 see azo compound Prostate specific antigen (PSA); see antigen Protamine (determination of), 563– 565 Protease, 393 a-Proteasome, 446 750 Index Protein, 4, 11, 19, 22, 24, 27, 98– 100, 124–127, 129, 135 –136, 139, 141, 144, 169, 200–204, 206, 210, 212, 216, 227–228, 283–285, 288– 293, 314, 325– 326, 328, 332, 357, 362, 385, 386–388, 390–393, 395–397, 413, 418, 434, 436– 437, 439–441, 443, 446, 461, 468– 470, 488, 524, 543, 550– 551, 558, 565– 567, 585, 594–595, 600, 619 amphiphilic protein, 201 C-reactive protein, 293 channel protein, 510, 563 cytophilic protein, 452 leucine zipper protein, basic, 283 maltose binding protein (MBP), 391, 446 positive leucine zipper domain-appended (MBP-zb), 385–387 motor protein, 522 p53 protein, 279– 280 protein A, 289, 393, 436, 462 protein G, 385, 436, 462, 566 protein aggregate, 73 protein-carbohydrate interactions, 124, 457 protein cavity/binding pocket, 13 protein denaturation/folding/refolding/ structure/dynamics, 73–74, 98, 366, 390, 558 protein-DNA interactions, 457 protein-metal cluster, 558 protein pore, 563 protein-protein interactions, 449 protein separation, 98, 100, 469–470 protein-substrate interactions, 550– 551, 581 protein synthesis, ribosomal, 11 recombinant protein, 127, 221–222, 392 see biotin; channel; Au; GFP; immunoassay; layer; metalloprotein; microarray; silica; Ag Protein imprinted xerogels with integrated emission sites (PIXIES), 595 Proteolytic activity, 392 Proteomics, 291, 435, 457 Proteosilica, 28– 29 Protocell; see cell Proton conductivity/conductor, 263 Protonation/deprotonation, 498 Protoplast, 487 Protozoan, parasitic, 329 Prussian blue complexes, 237 NPs, 286– 287 Pteridin granule, 573 Public engagement, 675 Pump biomimetic pump, 524 technological devices, 168, 655– 656, 659, 670 pumps in biological systems, 523– 524, 567–568 see Ca; ion pump; polymer Pyrazine (pyz), 243– 244, 249 pyrazine-2,3-dicarboxylate (pzdc), 244, 248–249 Pyrenes attached to ND, 692 2,7-diazapyrenium derivatives, 366–368 tetrahydroxypyrenedicarboxylate (thpdc), 256 pyrenebutanoic acid, 584 Pyridines, 276– 277 2-aminopyridine, 583 1,2-bis(4-pyridyl)ethane (bpethe), 249 cyanopyridine, 242– 243 4-dimethylaminopyridine (DMAP), 691 hexadecylpyridinium bromide (CPB), 50, 59 hexadecylpyridinium chloride (CPC), 50, 59, 75, 77 4-methylpyridine, 237 pyridinecarboxaldehyde, 242 pyridine-3,5-dicarboxylate (pdc), 696 –697 4-vinylpyridine (4VP), 244, 582 Pyrogallol red, 559 –560 Pyrolysis, 631 Pyrylium dye, 554–555 aniline, 554 –555 styryl, 555 QSY9 dye (nonfluorescent quencher dye), 391 see rhodamine Quantum chemical calculations; see calculation Quantum confinement effect, 156– 158, 160, 183, 378–379, 396 see confinement Quantum dot (QD), 23, 124, 129, 156, 170, 176, 217 –218, 274, 276, 298, 313–314, 326, 333, 337, 354–355, 373, 377–400, 574, 674, 678– 681, 683, 685, 690, 694 see laser; semiconductor NC; transistor Quantum efficiency, 189 Quantum yield (QY) fluorescence QY, 160– 163, 168, 170, 190, 337–338, 367, 374, 381, 385 enhancement, 160– 161, 337, 354 luminescence QY, 378, 380, 383, 391, 393, 396 Quartz Au coated quartz crystal, 595 quartz crystal microbalance (QCM), 124 quartz microparticle, 222 see cell; impedance techniques Quenching (of fluorescence, luminescence), 183, 185, 187, 189, 212, 337, 363, 397, 510, 574, 697 collisional quenching, 354 plasmon-induced quenching, 574 quenching and sensing, 66, 71, 219, 337, 359, 363– 364, 366, 368– 371, 382–384, 391– 392, 397, 491, 556, 697 quenching by defect sites, 218 dangling bonds, 162, 169 surface traps, 160, 168 self quenching, 395 Index static quenching, 384 Stern-Volmer quenching, 384 transient signal quenching; see blinking p-Quinone imine (QI), 292 Rabbit, 228 Radicals lipid peroxyl radical, 361 methyl radical, 261 nitroxide radical, amphiphilic, 140 radical chain reaction, 361 thiyl radical, 139 (4,40 ,400 -tricarboxydodecachlorotriphenyl)methyl radical (ptmtc), 260– 261 see bipyridine; disulfide chemistry; initiator; oligo(aniline); photochemical radical addition; polymerization; polyradical ion Radioactivity tracing/radioactive agent/label, 217, 224 –226 see carbon; CNT; Cu; In; iodine; waste Radioisotope; see isoptope Random access memory (RAM); see memory Rao– Stirling diversity, 677, 683, 685 Rare-earth emitter, 696–698 see lanthanides; luminescence; sensitizer Rat, 226 Reactive oxygen species (ROS), 203, 361– 362 Reaction vessels, nanosized, 259– 260 Rearrangement of binding sites, 555– 556 of molecules, 4, 237, 521, 555– 556, 669 of particles, 420 –422 Recalibration; see calibration Receptor, incl receptor unit, –3, 368– 370, 381, 391–392, 434, 556, 565– 569, 571, 573 adaptable receptor, 504 anion receptor, 552 biological/biomimetic receptor, –4, 576, 581 CD4 receptor, 207 CXCR4 co-receptor, 207 cell surface receptor, 218 cognate receptor, 341 epidermal growth factor receptor (EGFR), 328, 455 estrogen receptor, 63 glutamate receptor, 576 Hamilton-type, 414 see biomimetic; electrode; ligand-receptor interactions; polyamine; porphyrin; thiourea; urea Recombination nonradiative, 159, 383 radiative, 160, 339 see electron; electron-hole pair Recruitment, 676, 686 Redox, 170, 183, 191 redox-active ligand/site, 239–240, 256, 507, 655 redox actuated valve, 537 751 redox mediator, 280–281 redox potential, 537 see catalysis; catenane; cross-linking; disulfide chemistry; enzyme; gated system; host-guest; Fe; molecular muscle; Mo; polymer; probe; rotaxane; Ru; silica; surface; switch; volume change Reduction rate, 563 Referencing, internal, 669 Reflection absorption infrared spectroscopy (RAIRS); see spectroscopy Refractive index (RI), 127, 396, 588, 694 see probe; sensing Refrigerator, 44 Regiochemistry, 142, 259 Reichardt’s dye, 65 Relaxation, non-radiative, 327, 379 see charge; deactivation Release; see corrosion; drug; dye; evaporation; gated systems; guest; vitamin Remote activation, 649–650 Repair/autorepair/self-repairing, 640 Replica (for patterning), 419 Replica molding (REM); see lithography Reptile, 573 Research facility, joint, 676 funding, 676 see funding body topic, 674, 676– 678, 680–681, 683, 685 transdisciplinary research, 675 see affiliation; cluster; Mode, Resist (for patterning), 419, 425 Resistance, 288 chemical, 436 ohmic, 413– 414 see fatigue resistance Resolution (in printing), 447, 456 Resolution, spatial, 329, 332, 340 Resorcinarene, 325, 334–335, 473– 474 Response cross-response, 655 slope, 665 spatial, 357, 373 time/temporal, 65, 81, 298, 301, 359, 375, 476, 583, 657 Reticuloendothelial system (RES), 224– 225, 227 Reversibility (of sensing), 65, 359 Review publication, 677, 679– 680, 682, 684–685 Rhenium, chiral Re complex, 506 Rhodamine; see QSY; Texas red rhodamine 6G, 379, 649 rhodamine B, 498– 499 rhodamine B isothiocyanate (RITC), 359, 393 sulforhodamine B, 70 tetramethylrhodamine (TMR), 390 tetramethylrhodamine isothiocyanate (TRITC), 217, 354, 372 752 Index Rhodium/ions/salts, 94 and PCP, 249 Ribosome; see protein synthesis Ricin/anti-ricin, 385 –386, 567, 595 Ripening, 45 Ostwald, 165 Rituxan, 218 RNA, 206– 207, 215, 392, 397 RNA and immobilization on surfaces, 434, 451, 457 short interfering (siRNA), 207, 215 see microarray; polymerase Rock, volcanic, 41 Rocksalt, 161– 162 Roman empire, 322 Rotator; see rotor Rotaxane, 5, 496–497, 499, 513–515, 518 bistable, 471, 515 palindromic, 512 photoswitchable, 514 redox/electrochemically switchable, 510– 511, 519– 521, 537 cationic, 517 pseudorotaxane, 474–475, 496, 498, 511–514, 537– 538 hydrogen-bonded, 513 pH-responsive, 474–475, 498 rotaxane dimer, 511 see physisorption Rotor; see molecular rotor altitudinal, 505– 506 dipolar, 507 nonpolar, 507 azimuthal, 505, 507 Rutile (crystal modification), 628 see anatase Ruthenium Ru and PCP, 260 as catalyst, 121, 125, 398 see cross-metathese Ru(bpy)3 311– 313, 354, 359– 360, 491– 492, 569–570 on electrodes, 311 PtNP hybrids, 312 silica NP hybrids, 312–313 magnetic Fe3O4 core-shell NPs, 313 multilayer film, 312 in polymer/composite film, 311 in sol–gel, 311 on CNTs, 311 Ru(dpp)3, 358– 359 Ru dye, 398 Ru(ppy)3, 496 Ru redox probe, 563, 565 see alloy nanoparticle; catalyst; Au; graphite Saccharides, 19, 63, 391 see carbohydrate; polysaccharide; sugar Salen (N,N -bis(salicylidene)ethylenediamine), 93 Saline, 326 Salmonella typhimurium, 203 see cell Sampling, 655– 656 SBA phase, 43, 48 SBA-15, 48–49, 54, 60, 62–63, 65–66, 68, 72–74, 79, 81, 93– 94, 98–99, 559 SBA-16, 99 Scanning electrochemical microscopy (SECM); see microscopy Scanning electron microscopy (SEM); see imaging; microscopy Scanning force microscopy (SFM); see microscopy Scanning near-field optical microscopy (SNOM); see microscopy Scanning probe contact printing (SPCP); see lithography Scanning probe lithography (SPL); see lithography Scanning probe techniques, 504 Scanning transmission electron microscopy (STEM); see imaging; microscopy Scanning tunneling microscopy (STM); see microscopy; molecular rotor; nanocar Scattering tunnelling spectroscopy (STS); see spectroscopy Scanning vibrating electrode technique (SVET), 643, 646, 649, 651 Scattering, 208, 323, 329, 332, 575, 646 elastic; see Rayleigh scattering Hyper-Rayleigh scattering (HRS), 338, 341–342 inelastic, 334 isotropic, 341 light scattering, resonant, 330–331 neutron scattering, inelastic, 245, 256 plasmon-resonant, 330– 332 Raman scattering, 334, 536 Rayleigh scattering, 330, 334 scattering cross-section, 323–324, 330–333 scattering of electrons and holes, 338 surface scattering, 322 see backscattering; background; SERS; X-ray Scherrer equation, 625 Schiff base, 93–94, 461 chiral, 94 Schizophyllan (SPG) schizophyllan and CNTs, 205 single chain s-SPG, 205 triple helix t-SPG, 205 Schottky barrier/contact, 210 Science-society contract, 686 Sea urchin; see spicule; spine Sebacates dibutylsebacate (DBS), 166 Secondary building unit (SBU), 238–239, 246 Sedimentation, 408 of particles, 657 Index Selected area electron diffraction (SAED) (patterns), 626 Selenium; see amplification; Cd; Cu; Pb Self-annealing; see self-healing Self-assembly, self-assembling, self-assembled, 4– 5, 12– 13, 18– 19, 22, 25–26, 46, 52, 75, 95–96, 100, 144, 146, 169, 177, 180, 183, 201, 207, 238, 242–243, 276, 299, 302, 311–312, 314, 320, 325, 334– 336, 366, 374, 399, 407– 408, 412, 416, 419, 421, 427–428, 467– 468, 470, 472–473, 477, 509, 514, 532– 537, 540– 543, 584, 588–590, 595, 600–601, 605, 607, 619–620, 633 cooperative, 48 see energy; EISA; SATI; surfactant; template Self-assembled monolayer (SAM), 4, 115– 146, 243, 274, 512– 513, 515, 521, 556, 563, 565, 680 biomolecule SAMs on surfaces, 439– 440, 447 coupling chemistries, 442, 446, 449, 451– 454 crystalline SAM, 119 growth of, 118 kinetics of SAM formation, 124, 135 low-density SAM (LD-SAM), 468– 469 mixed monolayer SAMs, 118– 120, 124, 131, 135–136 NP SAMs, 408, 410, 412– 419, 421– 426, 428 organization of SAMs, 118, 125 patterns of, 141, 146 SAMs at air-water interface, 201 stability of, 115–117, 119, 136 air, 126 aqueous media, 126 kinetic, 131 thermal, 116 thermodynamic, 131 switchable SAMs, 468– 475, thermodynamics of SAM formation, 114, 118 zwitterionic SAMs, 126 see benzoquinone; templating Self-assembly, transfer and integration (SATI) of NPs, 423 Self-calibrating; see calibration Self-condensation; see condensation Self-healing; see coating Self-indicating, 669 Self-organization; see self-assembly Self-sorting, 118 Semiconductor/semiconductivity, 11, 18 II–VI semiconductor, 156, 161, 163, 165–168, 274 III–V semiconductor, 156, 161, 163, 165–168, 274 IV– VI semiconductor, 156, 161, 163, 165–167 bulk semiconductor, 6, 57, 159, 162 semiconductor band gap, 157 753 semiconductor cluster, 42 semiconductor and molecular machines, 513 semiconductor material, 6, 157, 161, 168, 299, 379, 410, 657 semiconductor sensitization, 513 semiconductor technology, 11, 66 semiconductor wire, array of, 521 see Ga; polymer Semiconductor nanocrystal, 6– 7, 156–183, 186, 274, 285, 299, 326, 377 –400, 425, 694 array of, 409, 420 biocompatibility of, 378, 381, 385, 388 capping with organic layer/functionalization, 157, 169–170, 190, 382 –383 core-shell NCs, 6, 161–162, 168–169, 190, 379 epitaxial shell growth, 168 see Cd electronic properties of, 6, 186 film/layer/LbL of, 6, 42, 161, 185, 189, 410, 420 semiconductor NC hybrids with biomolecules (incl biotin), 169, 217– 218, 292– 293, 385 –395, 397 with polymers, 384, 387, 394, 397, 399, 425 with conjugated oligomers/ polymers, 156, 170– 191 characterization, 180–185 ligand-to-surface atom ratio, 182 electrochemically active, 182 film, 178, 180 solubility, 172 structure amorphous, 171 crystalline, 171 double cable, 173 interpenetrating network, 179, 187 multilayer, 179 lamellar domains, 171 semicrystalline, 171 synthesis, 170– 180 with metals/metal NPs, 392, 397 with silica/sol-gel, 389, 398– 399 stability of, 174, 188, 387 see CNT; cyclodextrin; Au hyperbranched NCs, 186– 187 multi-NC systems, 384 see multiplexing nanorod, 171, 186–188 nanosphere, 186 nanotetrapod, 186–188 nanowire of, 521 optical/spectroscopic properties of, 6, 159–161, 183, 326, 354, 378– 381, 384, 390 production, large-scale, 168 semiconductor industry, 66 on electrodes, 177, 189, 415 in photovoltaic cells, 185–186, 188 in optoelectronic devices, 378, 395, 398 754 Index Semiconductor nanocrystal (Continued) in sensors, 292, 381– 382, 391 size and shape dependence, 158, 169–170, 190, 274 structure/structuring of, 161, 168, 459 synthesis of, 7, 163– 169, 175 biphasic, 164 heating-up synthesis, 164 high-temperature synthesis, 164, 167, 174 hot-injection synthesis, 165, 167 homogeneous phase, 164 precipitation synthesis, 163, 168 stability, 378, 394, 398–399 toxicity of, 168, 190, 381 water solubility of, 378, 382–385, 387, 393 see aggregate; Al; Sb; Cd; Cu; diameter; FRET; Ga; In; Pb; LED; Hg; metal; Ni; oscillator strength; photostability; Pt; QD; Tb; Sn; Zn Semipermeable; see permeability Sensing (incl chemical and biosensing), 5, 81, 127, 207, 209–211, 228, 249, 274, 282, 288, 290, 294, 297– 299, 301 –302, 312, 314, 320, 324 –325, 331–333, 353– 354, 356–359, 362, 364, 366, 368, 371–374, 378, 382 –384, 391–395, 397– 400, 408, 477, 480, 482, 550, 552–562, 565, 568, 573–576, 584, 654–656, 665– 670, 678–680, 682– 686, 694, 696– 698 electrochemical sensing, 680 gas sensing, 66 optical sensing, 127, 373, 680 colorimetric, 369, 559– 560, 569– 571, 573 fluorometric, 64–66, 490, 556, 569, 573, 697 RI-based, 325– 326, 328, 332 ratiometric sensing, 358–359, 362, 364, 366, 371–372, 374 real-time sensing, 332, 357 sensing network, 654 sensing textile, 670 see biosensing; explosive; pH; quenching; reversibility; surface; temperature Sensitizer/Sensitization, 513 sensitizer for rare-earth emitters, 696– 697 see photosensitizer; semiconductor; titania Sensor, 6, 71, 190, 209, 263, 274, 292, 297–299, 300–303, 357– 364, 366, 368– 373, 381–382, 384– 385, 391– 392, 396, 398–400, 412, 476, 489 –491, 510, 536–537, 540, 559–561, 563, 565, 573, 576, 581, 584, 595, 623, 654– 656, 665–670, 693 amperometric, 285– 287, 290, 300– 302 chromic, 238 conductometric, 288 ECL, 310– 314 environmental, 654 enzyme-based, 285, 302 gas sensor, 238, 263, 384 immunochromatographic sensor, 288 microsensor array, 32 nanosensor, 66, 297, 326, 360, 368, 391, 393, 560 poisoning of sensor, 667 reagent-less sensor, 290 SPR, 325, 396 stability of sensor, 312– 313, 665, 667 stochastic, 565, 576 wearable, 654 see biosensor; channel; chemosensor; electrochemical; fluorophore; ICS; lifetime; semiconductor NC Sensornets, 654 Separation, 25, 31, 236, 355, 476, 480, 483, 536, 581, 584, 591, 595, 661, 674, 696 chromatographic, 77, 97 distillative, 77 enantioselective, 91, 96 gas separation, 236, 238, 251, 256–259, 263 immunomagnetic separation, 202– 203 magnetic separation, 202 –203, 289, 355, 487, 620 see acetylene; baseline; BTEX; channel; charge; DNA; drug; electron-hole pair; metal; phase; PAH; protein Sequencing/sequences, 209– 210, 457 promoter sequence, 207 Serines phosphatidylserine, 360 Serum, 225, 287– 288, 326, 449, 461 blood serum, 228, 360 human serum, 389 Serum albumin bovine serum albumin, 201–204, 213, 219, 223, 293, 313, 362, 382–383, 390–391, 393, 449, 453, 455, 567, 594 see biotin human serum albumin, 288, 595 Service life, 640 Set point (in DPN), 459 Shrimp, 574 Shrinkage; see volume change Siderophore, 558 Sieving/sieve/effect, 42, 582– 583, 587, 592 see molecular sieve; OFMS Signal signal amplification/enhancement, 280, 290–292, 342– 343, 418, 550, 563, 569 of electrochemical signals, 280, 288–292, 298– 310 of ECL signals, 298–299, 310– 314 of optical signals, 320, 333–334, 336, 339, 361– 364, 366 of SHG/MHG signals, 342– 343 of TPL signals, 339 see SEF; SERS signal drift, 655 signal losses, 82 Index signal overlap, 381 signal transduction, 510, 513–515, 656, 665, 696 see background; cross-talk; electronics; quenching Signaling/signal generation, 4, 294, 298, 314, 339, 369 –370, 550–552, 554–560, 562–563, 567– 569, 571– 576, 655 –656, 667, 691, 696, 698 see biomimetic Signaling unit, 370, 550, 554–557, 559, 569 see probe Signal-to-noise ratio, 331, 364, 366 Silanes, 420, 426, 428, 441, 459, 586, 592–593 carboxyethylsilanetriol sodium salt (CTES), 355, 591 organosilanes, 21– 22, 28, 53– 57, 61, 66– 68, 70–71, 77, 83, 88, 353, 427, 437, 439, 484, 533, 542, 594 alkoxysilanes, 354 alkoxysilane amphiphiles, 20 tetraalkoxysilanes; see silicon (alkoxide) tetraethoxysilane/tetraethylorthosilicate (TEOS), 26, 28, 43, 46, 48, 55–56, 59– 62, 66–69, 71, 75, 83, 91, 94, 99, 353, 358, 359, 361– 363, 370, 484–485, 491–492, 542, 562, 583, 588, 593– 595, 642 tetramethoxysilane (TMOS), 45– 46, 48, 53, 55, 59, 61, 66– 67, 71, 75, 83, 94, 96–97, 583, 585– 588, 590– 591, 698 alkyltrichlorosilanes, 437, 440 allylorganosilanes, 542 aminosilanes, 454 aminoalkylsilanes, 426 bis(trialkoxysilyl) bridges, 46, 52, 56–57, 59, 61, 66, 83–87, 484–485 bis-silylated carbazole, 58, 80 bis-silylated, 1,4-diureylenebenzene, 68 N,N -bis(4-tert-butylphenyl)- N,N -bis(4((E)-2-(triethoxysilyl)vinyl)phenyl) biphenyl-4,40 -diamine (BBDA), 88–89 1,3-bis(triethoxysilyl)benzene, 77 1,4-bis(triethoxysilyl)benzene (BTEB), 75, 89 1,4-bis(triethoxysilyl)biphenyl (BTEBP), 89 1,2-bis(triethoxysilyl)ethane (BTEE), 62, 88, 90 1,2-bis(triethoxysilyl)ethene (BTEY), 90, 95 1,2-bis(triethoxysilyl)methane (BTESM), 53 1,4-bis(triethoxysilyl)-2-(1-methoxyethyl)benzene (BTEMEB), 95 2,5-bis(triethoxysilyl)thiophene (BTET), 75 755 bis[3-(triethoxysilyl)propyl]tetrasulfide, 68 N,N -bis-[(triethoxysilyl)-propyl]-trans(1R,2R)-bis-(ureido)-cyclohexane, 96 N,N -bis(40 -(3-triethoxysilylpropylureido)phenyl)-1,4-quinone-diimine, 71–72 1,2-bis(trimethoxysilyl)ethane (BTME), 83, 94, 96, 100– 101 1,4-bis(trimethoxysilylethyl)benzene (BTMSEB), 67– 68 bis[3-(trimethoxysilyl)propyl]amine (BTMSPA), 99– 100 bis(3-trimethoxysilylpropyl)diazapyridinium diiodide, 71 a,v-bistrimethoxysilyl-4,5-dithiooctane, 67 1,3-bis-(tri-iso-propoxysilyl)benzoic acid, 79 1,3-bis-(tri-iso-propoxysilyl)-5-bromobenzene, 79-80 1,3-bis-(tri-iso-propoxysilyl)styrene, 79 with alkylene bridges, 58 with alkenylene bridges, 58 with aromatic bridges, 58 bis(trialkoxysilyl)organosilane bridges, 77, 83 bis(trisallyl)organosilanes, 77 chloroorganosilanes, organotrichlorosilanes, 54, 484, 542 chlorodimethylalkylsilanes, 437 nonadecenyltrichlorosilane (NTS), 428 octadecyltrichlorosilane (OTS), 428 mercaptosilanes, 449 multi-/cyclic/branched (trialkoxysilyl) bridges, 57– 58, 61, 66, 81, 84– 87 1,1,3,3,5,5-hexaethoxy-1,3,5trisilacyclohexane, 82 multi-silylated fullerene, 69 tetra-silylated cyclam, 68 1,3,5-tris(triethoxysilyl)benzene, 81 tris[3-(trimethoxysilyl)-propyl] isocyanurate (ICS), 68 octylsilane, 63 organobis-silanetriols, 77 benzene bridged, 77 1,4-bis(benzenesilyltriol), 77 organoalkoxysilanes (also alkoxyorganosilanes), 96, 353–354, 542, 583, 585– 587, 589, 594 organodialkoxysilanes dimethoxysilanes (mercaptopropyl)methyldimethoxysilane (MPMD), 409 organotrialkoxysilanes, 46, 54–56, 59–61, 66, 83–87, 96– 97, 367, 369, 437, 484 chiral, 83 756 Index Silanes (Continued) mono-silylated cyclam, 68 triethoxysilanes, 368, 420 3-aminopropyl triethoxysilane (APTES), 69, 71, 100, 359, 362, 450– 451, 453 bis-(2-hydroxyethyl)aminopropyltriethoxysilane, 595 1,2-bis(triethoxysilyl)ethane, 586 dansyl triethoxysilane, 370 5,6-epoxyhexyltriethoxysilane (EHTES), 372–373 (3-isocyanatopropyl)triethoxysilane (ICTES), 362, 494 –496, 537– 538 3-mercaptopropyltriethoxysilane (MPTES), 68, 88, 492, 562 n-octyl-triethoxysilane, 67 phenyl-triethoxysilane, 67 3-(triethoxysilyl)-N-methylpropan1-amine, 66 N-(3-triethoxysilylpropyl)-trans(1R,2R)-diaminocyclohexane, 83 N-(3-triethoxysilylpropyl)-4,5dihydroimidazole, 68 3-(triethoxysilyl) propyl isocyanate; see (3-isocyanatopropyl)triethoxysilane N-(3-triethoxysilylpropyl)-Lprolinamide, 83 11-(triethoxysilyl)undecanaldehyde, 283 11-(triethoxysilyl)undecanoic acid, 492 vinyltriethoxysilane (VTES), 67, 353, 362 trimethoxysilanes 3-[2-(2-aminoethylamino) ethylamino)propyltrimethoxysilane, 363 N-(2-aminoethyl)-3aminopropyl trimethoxysilane, 586, 592 3-aminophenyltrimethoxysilane, 94 3-aminopropyl trimethoxysilane (APTMS), 67, 93, 491, 583, 586, 588, 593–594, 691 3-tert-butyloxycarbonyl (aminopropyl)trimethoxysilane, 67 3-glycidyloxypropyltrimethoxysilane (GLYMO), 605, 620 isocyanatopropyltrimethoxysilane, 498 3-mercaptopropyltrimethoxysilane (MPTMS), 53, 88, 134, 302– 303, 372, 413, 443, 459, 485, 492, 562, 586 2-[methoxypoly(ethyleneoxy)propyl]trimethoxysilane (PEG-Si), 460 methyltrimethoxysilane (MTMOS), 358, 586, 590, 595, 698 octadecyltrimethoxysilane, 460 phenylethyl-trimethoxysilane, 53 phenyltrimethoxysilane (PTMOS), 58, 98, 358, 586, 590–591, 595 trimethoxy(7-octen-1-yl)silane, 541 1,4-bis(trimethoxysilylethyl)benzene (BTMSEB), 586, 593 N-[3-(trimethoxysilyl)-propyl-2aminoethyl]ethylenediamine, 492 N-[3-(trimethoxysilyl)-propyl] ethylenediamine, 485 N-trimethoxysilylpropyl-N,N,Ntrimethylammonium groups, 559 ureidopropyltrimethoxysilane, 68 PEO silanes, 450 trimethylsilane/trimethylsilyl (TMS), 62, 82, 166– 167, 552, 554– 555 bis(tert-butyldimethylsilyl) (BDMS), 166 2-cyanoethyltrimethylsilane, 67 TMS cyanide, 94 see polymerization Silathianes hexamethyldisilathiane, 168 Silazanes, 54, 62, 64 hexamethyldisilazane, 62, 65, 75, 82 Silica, 47, 82, 415, 420, 428, 440, 444, 448, 459–460, 479, 531, 534, 549, 677, 679–681, 683, 698 amorphous silica, 353, 619 –620 biological silica, 606 colloidal silica film, 439 fumed silica, 555–556 helical silica, 91 imprinted silica, 551, 586 mesoporous, 28–30, 40– 101, 479 –500, 534, 537–538, 561, 573, 620, 695 bifunctional, 67–68 biocompatibility, 100 biodegradability, 100 calcined, 495, 592 capsule, 32 chiral, 92– 93 classification, 59 containers, 642, 649, 651 cytotoxicity, 100 electroactive, 71– 72 film, 71, 96 gel, 43– 44 genealogy, 42–54 helical, 92 hybrids, 21, 28 chiral, 28 film, 15–17, 28 Index with biomolecules, 27– 28, 98–100 see proteosilica with ionic liquids, 697 with organic molecules, 17, 62–63, 558 with polymers, 15– 16, 537, 540–542 powders, 28 stimuli-responsive, 64–66 chemical, 15 mechanical, 15 photochemical, 64 thermal, 15, 64 see CNT; Au; hydrogel; iron oxide; lipid; Pt; polymer; semiconductor NC; zirconia mesoscopic order, 56, 94, 96 particles, 68, 70, 97, 483, 486, 488, 494, 498, 511, 592, 643, 649 functionalized with biomolecules/ oligomers/small molecules, 487– 488, 490, 492, 498 octahedral, 98 rod-like, 483 helical, 483 spherical, 98, 483 see templating redox-active, 71 stability (hydrothermal, kinetic, thermal, thermodynamic), 41–42, 50, 62, 94, 96–97, 484, 498 synthesis, 50–52 tubes, 27 see M41S; MCM-41; MCM-48; MCM-50; MSU-H; SBA; templating silica-block copolymer hybrids, 576, 618 mesostructured, 600 –602 silica containers, 643, 650 silica gel, 44, 139, 369, 555 silica microparticle/microsphere, 325, 409 silica multilayers, 640 silica-MWNT nanocable, 309–310 silica nanohelix, 698 silica NPs, 2, 68, 312–313, 351– 374, 421–424, 426, 510, 592 –593, 599–603, 605–609, 642, 644, 651 biocompatibility of, 352, 358 dye-doped/labeled silica NPs, 360– 371, 374, 487, 489, 573 hybrids with proteins, antibodies, agents, 353– 355 with magnetic NPs, 355 with organometallics, 289 with polymers, 358 monodispersity, 353 mutlishell NPs, 353, 371–372 nanoparticle array, 302 shapes/sizes, importance of, 353, 370 water solubility, 352 see aggregate; Co; cyclodextrin; diameter; ORMOSIL; Ru; templating 757 silica nanotubes, 559, 592– 593 see diameter silica particles dye-doped, 353– 356 porous, 585, 594– 595 silica polymer, 480 silica skeleton, 599 spiral silica, 91 see dendrisilica; interface; organosilica Silicate, 76–77, 352 polysilicate; see Kanemite A porous silicates, 252 sodium silicate, 44–45, 352, 588 see ceramic; interface; iron oxide; ORMOSIL Silicon, 53, 60, 81, 409, 415, 423, 425 –428, 440, 443, 447, 461, 471, 508, 614 amorphous silicon, 188 classification of, 60 monocrystalline silicon, 188 multicrystalline silicon, 188 nanocrystalline silicon, polycrystalline silicon electrode, 518– 520 silicon alkoxide, 352– 353, 533, 588, 592–593, 603, 605 see silanes silicon and ECL, 313 silicon carbide (SiC), mesoporous, 694–695 luminescence of, 694 nanotube/nanowire/nanocrystal, 694 surface functionalization, 694– 695 see ceramic; cluster silicon carbonitride (SiCN), mesoporous, 695 silicon chloride, 352 silicon dioxide; see silica silicon nitride, 440 see tip silicon oxide; see silica silicon oxycarbide (SiOC), mesoporous, 695 silicon substrate, 23, 180 silicon wafer polishing, 351 see lithography; polymerization Siloxanes, 20, 96 alkylsiloxane, 447– 448 long-chain siloxane, 482 organosiloxanes, 60, 644 PEG siloxane, 450 siloxane bridges, 53 siloxane-disilsesquioxane, 58, 60, 82 siloxy-trisilsesquioxane, 58, 82 see oligomer; PDMS Silsesquioxane, 46, 56–57, 59–60, 67, 71, 75, 80, 88–89, 99, 536, 543, 593 bridged silsesquioxane, 533 –535 chiral, 535 pendant silsesquioxane, 533–535 amphiphile, 533–534 see azo compounds; organosilanes; polysilsesquioxane; silanes; siloxanes 758 Index Silver/ions, 143, 418, 440 determination of, 382–384 Ag and surface plasmons, 321 as SERS substrate, 334, 336 Ag deposition, 419 on hybrid electrode, 303 –304 Ag film, 127 Ag monolayer, 308 Ag nanocube, 146 AgNPs, 5, 141, 285, 289, 412–413, 649– 650 hybrids with biomolecules, 283, 301 with inorganic materials, 307 with polymers, 281, 574 on Langmuir trough, 281 NP array, 336, 412 NPs and THG, 343 shape and size dependent properties, 326 see nanoparticle Ag-protein cluster, 558 see aggregate; alloy nanoparticle; amplification; Cd; metal; nanoparticle Silver/silver ion couple, 183–184 Silylation, 62 cyanosilylation (of aldehydes), 94, 260 Simulation; see calculation; molecular dynamics Single electron device, 11, 129 Single electron transistor, 131 Single molecule/particle, 129, 320, 393– 394, 427 detection/observation (optical), 328, 330, 333, 336, 339, 342, 354, 381, 392, 399, 424, 504, 517, 567 force spectroscopy, 473–474, 513 see molecular fishing rod layer, 281, 519 manipulation, 504, 508 see imaging; molecular switch Single nucleotide polymorphism (SNP), 210, 418, 457 Size exclusion, 257, 555 Size exclusion chromatography (SEC); see chromatography Shelf-life/long-term stability, 189, 314, 408 Skeletal parts/materials, 483, 599 Small angle X-ray scattering (SAXS); see X-ray Smart design/device/material, 115, 467– 470, 472, 477, 486, 648, 663, 665 see chip SNU-X, 52 Social benefit, 674 issue, 675, 686 process, 674 relevance, 686 Societal demand, 675 problem, 675 Sodium/ions, 3, 134, 136, 139, 143, 166, 352, 414, 449, 498, 524, 591 Na aluminate, 72 Na azide, 524 Na clay, 640 Na in PCP, 242, 256, Na salts and corrosion, 643– 646, 649, 651 Na salts as reducing agent borohydride, 130– 131, 135, 137, 143, 161, 292, 442 cyanoborohydride, 121, 453, 496 naphthalenide, 133 periodate, 124 see silanes; silicate; succinic acids Soil, contaminated, 392 Sol–gel, 80, 91, 285–286, 311, 531 –532, 542, 584–585, 587– 592, 594– 595, 679, 697 clusters, 45, 90 coating, 643–646 hybrid, 644, 646 fiber, 583 film/thin film, 513, 583, 587–588, 590– 591, 594, 642–645, 649–651 imprinted polymer/imprinting, 583–584, 589, 591–593, 595 matrix, 362, 396, 588, 644, 648 monolith, 583, 587– 588, 594 network, 286, 299, 643 particles, 358, 361 powder (mesoporous), 583, 587– 588 polymerization/process/processing/reaction/ route, –8, 16, 26, 28, 44–45, 52, 80, 96, 302, 362, 398– 399, 531, 583, 585, 588, 592, 594– 595, 608, 620– 621, 624, 642, 698 stability (chemical, electrochemical, photochemical), 585, 594, 643 see Au; Ru; semiconductor NC; zirconia Solar cell, 185, 187–188 bulk heterojunction, 186 –187 see photovoltaic cell Solar concentrators, 398 Solvatochromism/solvatromic, 17, 64–65 Solvent-assistant microcontact molding (SAMIM); see lithography Solvophilic–solvophobic interactions, 18 Sonication/sonochemical synthesis, 143, 201, 205, 219, 366, 384, 441, 620 Soot, Sorption/sorbents; see adsorption Soxhlet; see extraction Spectroelectrochemistry, 183– 185, 191 Spectroscopy absorption (UV-vis-NIR), 156, 169, 178–179, 181, 183, 244, 373, 539, 551, 562, 655 ATR, 584 CD, 208, 506 EDS, 631 EELS, 621 HREELS, 117 PEELS, 615 ESR, 135, 140, 142, 481 ... The Supramolecular Chemistry of Organic – Inorganic Hybrid Materials The Supramolecular Chemistry of Organic – Inorganic Hybrid Materials Edited by Knut Rurack... aspects of supramolecular chemistry related to hybrid materials and structures at the mesoscale in Chapter The chapters collected in the first thematic section on Organic – Inorganic Hybrid Nanomaterials... Ajayan Vinu, and Toshiyuki Mori Part One Organic – Inorganic Hybrid Nanomaterials Silica-Based Mesoporous Organic Inorganic Hybrid Materials 39 Frank Hoffmann and Michael Froăba Modified Gold Nanoparticles