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Nanochemistry
A Chemical Approach to Nanomaterials

Geoffrey A. Ozin, André C. Arsenault and Ludovico Cademartiri

Department of Chemistry, University of Toronto, Canada
Nanoblog
Join the debate at the Nanochemistry blog, where you can have
your say, provide comment and feedback on the book and express
your opinions on the subject in general: www.rsc.org/nanoblog

Though this book has been diligently created and every effort made to ensure accuracy,
the authors and publishers do not warrant the contents of this manuscript to be free
from errors or omissions. The readers are reminded that statements, data, illustrations,
references, experimental details, or other items may inadvertently be inaccurate.

ISBN 978-1-84755-895-4

A catalogue record for this book is available from the British Library

r Geoffrey A. Ozin, André C. Arsenault and Ludovico Cademartiri 2009

All rights reserved

Apart from fair dealing for the purposes of research for non-commercial purposes or for
private study, criticism or review, as permitted under the Copyright, Designs and Patents
Act 1988 and the Copyright and Related Rights Regulations 2003, this publication may not
be reproduced, stored or transmitted, in any form or by any means, without the prior
permission in writing of The Royal Society of Chemistry, or in the case of reproduction in
accordance with the terms of licences issued by the Copyright Licensing Agency in the UK,
or in accordance with the terms of the licences issued by the appropriate Reproduction
Rights Organization outside the UK. Enquiries concerning reproduction outside the
terms stated here should be sent to The Royal Society of Chemistry at the address printed
on this page.

Published by The Royal Society of Chemistry,

Thomas Graham House, Science Park, Milton Road,
Cambridge CB4 0WF, UK

Registered Charity Number 207890

For further information see our web site at www.rsc.org

Guessing (Nano)Materials
LUDOVICO CADEMARTIRI

It is always hard to speak after illustrious scholars. You can imagine how hard it must
be to write after them. Usually the trick is to not try to say something intelligent.
I came from Italy, a beautiful country where research has been for many years
humiliated by famously poor policies, with no intention of doing anything nano.
Being trained in solid state physics and chemistry, I was having a real itch at
seeing those little tiny balls of humiliated inorganic bulk matter. And even more
so, I was determined to avoid anything containing sulphur after having spent a
month of my life inhalating hydrogen sulphide with the ‘‘high’’ purpose of
visually determining the start of nucleation of some ZnS colloids. I really wanted
to keep doing some nicely colored and odorless chemistry, after doing my Laurea
thesis on opals. Two weeks after moving to Canada I found myself somehow
working on black solutions of lead sulfide nanocrystals . . . I guess this more
than anything else testifies to Geoff’s ability to transmit unbridled enthusiasm as
well as it testifies to the validity of the statement that most of the times you don’t
like something because you don’t know enough about it (true about everything,
even doughnuts). Being enrolled in a program in interdisciplinary chemistry I
tried and sometimes succeeded in maintaining this approach in my work, where I
had the privilege to be allowed to contribute to fields as diverse as quasicrystals,
mesoporous materials, photonic crystals, nanocrystals, nanowires and gels.
The curiosity-driven aspect of my research is what I enjoyed the most as it is
something that keeps you guessing and allows you to dodge explaining your objec-
tives. Having no objective, no goal, removes constraints from your reasoning: not
confined by funding, applicability and deadlines, you can just follow the trail of
breadcrumbs that Nature always disseminates in front of us. A task both enter-
taining and nutritional! I strongly believe that this component of research should
be preserved as it reminds scientists that science can not only be the answer to the
questions ‘‘why?’’ and ‘‘how?’’ but also to the question ‘‘what if?’’. After all, relati-
vity was the answer to such question, why shouldn’t we use it in chemistry as well?
I had the privilege to be invited by Geoff to contribute to this second edition
and it has been from then on a very new, exciting challenge for me. Writing a
book was one of my many childhood’s dreams (maybe not this kind of book,
but still . . . ), and there you have it: there are few things more surprising than
science and among those is definitely life.
xliv
SUBJECT INDEX

Index Terms Links

5CB see 4-pentyl-4'-cyanobiphenyl

AAO see anodized aluminum oxide

AAS/PLL see alginic acid-poly-L-lysine
hydrobromide
abalone shell 140
ACC see amorphous calcium carbonate
adamantanoid germanium sulfide
clusters 555 556
adenosine triphosphate (ATP) 694–5
aerosol-templating 547–8
AFM see atomic force microscopy
agarose stamps 75 84 85
see also PDMS stamps
aggregation, colloidal 453
aims of this book xviii–xix
air voids see nanobubbles; porous...
air–liquid interface 720–1 732–6 737
ALD see atomic layer deposition
alginic acid-poly-L-lysine hydrobromide
(AAS/PLL) 132–3
aligned patterns technique 298

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Index Terms Links

α,ω-alkanedithiols 399
α,ω-alkanehydroxyphosphonate 29
alkanethiolates
see also self-assembled monolayers
capped gold nanocrystals 346–8
diagnostics 350–1
dimer formation 403–4 405
surfactants 572–3
α,ω-alkanethiophosphonate 29
alkylammonium primer headgroups 118
alloy nanocrystals 387–90
alumina 100–2 237 541–2
aluminophosphates 656–7
aluminosilicates 20 27 623
624–6
aluminum 77 78 220
amino acids 599–602
aminopropyltrimethoxysilane (APS) 376
ammonia 411–12
amorphous calcium carbonate (ACC) 83
amorphous selenium 283–5
amphiphiles
ATP synthase 692 700–1
DNase 185–6
hierarchically ordered nanorods 234–5
Langmuir-Blodgett films 28–30
peptide-based 659 660
polymers, hydrophilic nanocrystals 375–6
tri-block copolymers 539 540–1 543–4
amplified photochemistry 496–501

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Index Terms Links

anchoring units 669 699–700

anionic layers 117–20 124 125
anionic living polymerization 596–8
anisotropic functionalization strategy 405–7
anodic oxidation 217–18 220–1
anodized aluminum oxide (AAO) 541–2
antibody-functionalized fingerprint
nanoparticles 386
antifogging surfaces 659–62 663
antireflection coatings 612–13 614 615
applications
see also individual applications
barcode metal nanorods 224
colloid microspheres 36
electrically-driven nanowire lasers 278–9
electroluminescent semiconductor
nanocrystals 368–70
future directions 758–61
hybrid multilayers 125
mesoporous materials 546
nanobubbles 138
nanorod devices 235–6
nanowires/rods/tubes 215
patterned microspheres 447
periodic mesoporous organosilica films 558 560
polyelectrolyte films 31
porous multilayers 129
SAM patterned opal marble arrays 88
shaped building blocks xii
slow photons 498–9

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Index Terms Links

applications (Cont.)
solid-state patterning materials 70
structural color 145
APS see aminopropyltrimethoxysilane
architectures
capped nanocrystals 353
linear coblock polymer self-assembly
behavior 596–7
nanowires 250–1
tetrapod 353 391–5
on wire nanorod 235 236
armchair nanotubes 289
arrays
2D nanowires 253–4
cantilever arrays 126–8 196–7 201–2
colloid arrays 296–7
crystal arrays 142–3 487–8
dip pen nanolithography arrays 182–3 184
ferromagnetic nanocrystal arrays 769
flexible cantilever arrays 126–8
HIV detection 182–3 184
microlens arrays 65–7
multicrystal zeolite-ordered 141
multi-walled carbon nanotube arrays 298 299
nanoring arrays 67–9
ordered carbon nanotube 296–7
SAM patterned opal marble arrays 88
arrested nucleation and growth 335 336–9 343–5
arsenic 753–4
aspect ratio 215–16 382–3

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Index Terms Links

assymetric shapes 734–6 737

atomic force microscopy (AFM)
DNA–silver wire 674
hexanethiol SAM on gold 61
nanocontact printing surfaces 170 177 178
179 181 185
188
nanoscale protein recognition 183
nanosoldering irons 193 194
organic light emitting diode tip 191–3
PDMS tipped cantilever 202 203
tip for piezoelectric mechanical stress 307–9
vertical pores 544
atomic layer deposition (ALD) 90–1 152 504
atoms 352
ATP see adenosine triphosphate
ATPase see ATP synthase
ATP synthase (ATPase) 692 700–1
auto-construction strategy 725–7 728
autonomous self-assembly 735–6
axial nanowire heterostructures 269–70
axial rotation 664
azobenzone 475
azobis-isobutyronitrile initiator 564

Bacillus spp.
B. sphaericus 682
B. stearothermophilus 682
B. subtilis 676

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Index Terms Links

back-reflectors 500–1 502

bacteria
Bacillus spp. 676 682
characteristics 697–8
directed materials self-assembly 676 678
Escherichia coli 75 77 699
700–1
flagellum 692 693
microcontact printing 75–7
polymer biofactories 601
power from 697–700
protein S-layer masks 681–3 684
ballistic conductance 291–2
Ball, Philip xli 26
barcodes
block copolymers 612
C4, sequential PACMAC process 494
magnetic nanorods self-assembly 231 769
metal nanorods 218–21 222 231
769
nanorods orthogonal self-assembly 221–4
oligonucleotides 384–5
Barrer, Richard xx 19 20
basic principles 3–41 53–4
Big Bang 10
clever clusters 32–4
colloids 35–8
curved crystals 24–5
form-is-function concept 22–4

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Index Terms Links

basic principles (Cont.)

genealogy of self-assembling
materials 16–19
hierarchical assembly 14–15
integrated systems self-assembly 40–1
large/small nanomaterials 11–12
materials chemistry 3–5
mesoscale self-assembly 38–40
molecular vs. materials self-assembly 13–14
multilayer polymer films 30–1
Nanofood for thought 53–4
nano- prefix meaning 10–11
nanowires 34–5
patterns 25–6
porous solids 19–22
quantum mechanics 12–13
self-assembled monolayers 31–2
supramolecular vision 14 15–16
synthesis methods 5–9
synthetic natural forms 26–8
two-dimensional structures 28–31
BBF see blown bubble film
BDC see 1,4-benzene-dicarboxylate
beakers, nano-sized 345–6
Belousov–Zhabotinsky reaction (BZ) 488 489
1,4-benzene-dicarboxylate (BDC) 525–6
benzenesilica 558
bicontinuous microemulsions 653–4
Big Bang 10
Bigelow, W.C. 776

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Index Terms Links

binary codes 224–5

binary colloidal crystals 453 454
binary nanocrystal superlattices 362–3
binding studies 348–50 686–8
bioanalytical nanocrystals 385–7
biocompatibility 658–9
biofactories 601–2
bioinspiration 662–8
biological labels 383
biomaterials 643–702 714–15
see also biominerals
aluminophosphates 656–7
ATPase nanopropellers 700–1
bacterial-directed self-assembly 676 678
bacteria power 697–700
bioinspiration 662–8
biomimicry 648–60
biomolecular motors 689–95 700–1
bone analogues 657–9 660
capped semiconductor nanocrystal
applications 377–9
composite fiber/laminate
morphologies 650
DNA-based 670–8
dynamic self-assembly 732
echinoderm-like block copolymers 655–6
evolutionary optimization 643–4
faux fossils 646–7
gold–nickel–gold nanorods 232–3
integrated self-assembly 40

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Index Terms Links

biomaterials (Cont.)
magnetic spider silk 680–1
microcontact printing 183–5
mineralizing nanofibers 659 660
molecule trapping in multilayers 128–9
morphosynthesis comparisons 652–5
mosquito eye 659–62 663
muscle-powered nanomachines 696–7
Nanofood for thought 714–15
nanowire evolution 688–9
new materials 668–701
photonic crystals 683–5
polymer life forms 685–6
protein S-layer masks 681–3
structural experiments 771–2
surface binding through direct
evolution 686–8 690
top-down photonic crystals 683
viral cage-directed nanocluster
synthesis 667–8
virus alignment 678–80
virus capsid anchoring 669
biomimetics 644–52
biominerals
brittlestar skeleton 80–1
coccolithophores 653
Cymbela mexicana 37–8
form-is-function concept 22–4
Harting, Pieter xvi 16–19
Haversian bone 644 657–9 660

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Index Terms Links

biominerals (Cont.)
history 16–21
molluscan shells 650–1
SAM crystal engineering 78–83
biomolecular motors 689–95 700–1
bio-sensing 460
biotin–streptavidin bioconjugation 730 750 751
bipolar building blocks 760
bipyridinium alkanethiols 372–3
bismuth citrate 248–9
bismuth colloidal crystal 471
block copolymers 595–632 639–40
aluminosilicate nanoshapes 624–6
bulk state 595–608
ceramics 623–4
colloidal crystal templating 37
color tunable gel Bragg mirrors 620–2
copolypeptides 598–601
decoration 627–8 629
echinoderm-like 655–6
hierarchical Bragg mirrors 619–20
lightscale 618–19
lithography 626–7 628 771
living copolymer cylindrical micelles 611–12
mesochannel orientation 543–4
mesoporous material length scale
tuning 539 540
mesostructure/dimensionality 540–1
micelles 608–13 614 615
nanoepitaxy 607–8 609

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Index Terms Links

block copolymers (Cont.)

Nanofood for thought 639–40
nanowires 598 631–2
Nature 601–2
one-dimensional block copolymer
spatial confinement 619–20
rod–coil 622–3
spatial confinement 604–5 606
supramolecular assemblies 613 615–18
thin films 602–3
three-dimensional spatial confinement 605–7 608
tri-block copolymers 36–7 539 540–1
543–4 562
wettability 602 603 607
628–30
blocking temperature 364
Blodgett, Catherine 775
blotters, nanoinkwells 197–8 199
blown bubble film (BBF) process 255–6
bonding forces 14 15 150–1
bone 644 657–9 660
boronic acid 526–7
bottom-up methods x–xii xix 273–4
649 663–6
see also synthesis
bovine serum albumin (BSA) 129–30
BPEI see branched poly(ethyleneimine)

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Index Terms Links

Bragg diffraction
liquid crystal photonic crystals 479 486 487–8
one-dimensional photonic lattice 433
polymer opal sheet 456 457
rod–coil block copolymers 622–3
Bragg mirrors 619–22
Bragg stacks 143–5 146
Bragg–Snell equation 458 462–3 479
branched poly(ethyleneimine) (BPEI) 149
branched structures 269 271 391–7
613 615–16
brittle bacteria 676
brittlestar skeleton 80–1
BSA see bovine serum albumin
bubbles 135–8 254–7 443–4
see also porous materials
buckling patterns 533 551
buckminsterfullerene 409–12
buckyballs (carbon nanoclusters) 409–12
building blocks
basic principles 9–10
buckyballs 410–11
concept 215–16
large 719–37 740
nanoclusters 335–6
porous materials 521–77 590–2
synthesis vii
bulk materials 4–9 336 595–608
bundles of magnetic nanorods 229

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Index Terms Links

butterfly wings 431–2 436 504

505
butylisonitrile 222–3
BZ see Belousov–Zhabotinsky reaction

C4 crystal capillary columns 492–3 494

CaDDP see calcium dodecylphosphate
cadmium selenide 396 397–8
cadmium sulfide
nanoclusters 682–3 684
nanocrystals 569–70
nanorods 266–8
nanowires 245–6 278–9 689
690
cadmium sulfide–cadmium selenide
system 394
cadmium–selenium capped
semiconductor nanocrystals
electroluminescent 369–70 378 379
growth observation 343–5
synthesis 337–9
tri-layer solvent diffusion
crystallization 358
cadmium–telluriumtetrapods 391–3
calcareous synthetic formations 647–8
calcite 79–80 82 83
650–1 653
calcium dodecylphosphate (CaDDP) 658
calix[4]resorcinarene 92 93

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Index Terms Links

Cambridge Structural database 523

cancer 380–1
cantilever arrays 126–8 196–7 201–2
capillaries see micromolding in
capillaries
capillary columns 771
capillary interactions
2D/3D electrical circuits/devices 721–2 723
hexagonal-shaped plates 724 726
many-faced nanocubes 746 748 749
polyhedral-shaped blocks 721 722
polyhedra with patterned faces 725–7 728
supra-micron shape assembly 720–1
capped nanocrystals as swelling agent 571–3
capped semiconductor nanocrystals 335–412 426–8
alkanethiolate capped silver
nanocrystal superlattices 353–5
architectures/morphologies 353
biological applications 377–9
biological labels 383
films, basic principles 33–4
full color nanocrystal–polymer
composites 370–2
gold 346–50
growth observation 343–5
magnetic superlattices 363–4
periodic tables 351–2
soft lithography 364–5
synthesis 336–9
water-soluble 374–7

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