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In Nanoscience and Nanotechnology for Chemical and Biological Defense; Nagarajan, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
1
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e 27, doi: 1
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In Nanoscience and Nanotechnology for Chemical and Biological Defense; Nagarajan, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
1016
ACS SYMPOSIUM SERIES
Nanoscience and
Nanotechnology for Chemical
and Biological Defense
1
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bs.acs.or9-1016.f Natick SoldierR Re. sNearachg, aDrevaeljoapmne,n tE &d Eintgoirne ering Center
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2012 | http://p0.1021/bk-20 Natick SoldierW Reaselatrechr, DZevuel kopamse,n tE &d Eintgoinre ering Center
e 27, doi: 1 T. Alan Hatton, Editor
on Jun2009 | Massachusetts Insti tute of Technology
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Sponsored by
The ACS Division of Colloid and Surface Chemistry
American Chemical Society, Washington DC
In Nanoscience and Nanotechnology for Chemical and Biological Defense; Nagarajan, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
Library of Congress Cataloging-in-Publication Data
Nanoscience and nanotechnology for chemical and biological defense / R.
Nagarajan ... [et al.], editor ; sponsored by the ACS Division of Colloid and Surface
Chemistry.
p. cm. -- (ACS symposium series ; 1016)
Proceedings of a symposium held at the 234th ACS National Meeting in
Boston, MA on August 19-23, 2007.
Includes bibliographical references and index.
ISBN 978-0-8412-6981-1 (alk. paper)
1
g w00 1. Nanotechnology--Congresses. 2. Biotechnology--Congresses. 3. Chemical
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e 27, doi: 1
n Jun009 | I SBN 978-0-8412-6981-1
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Doblic per-chapter fee of $40.25 plus $0.75 per page is paid to the Copyright Clearance
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PRINTED IN THE UNITED STATES OF AMERICA
In Nanoscience and Nanotechnology for Chemical and Biological Defense; Nagarajan, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
Foreword
The ACS Symposium Series was first published in 1974 to provide a
mechanism for publishing symposia quickly in book form. The purpose of the
series is to publish timely, comprehensive books developed from the ACS
sponsored symposia based on current scientific research. Occasionally, books
are developed from symposia sponsored by other organizations when the topic is
of keen interest to the chemistry audience.
1
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p://k-2 added to provide comprehensiveness. When appropriate, overview or
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63.35.42 mber 24, are not accepted.
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In Nanoscience and Nanotechnology for Chemical and Biological Defense; Nagarajan, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
Preface
This book results from the symposium “Nanoscience and
Nanotechnology for Chemical and Biological Defense” held at the 234th ACS
National Meeting in Boston, MA on August 19-23, 2007. The symposium was
sponsored by the ACS Division of Colloid and Surface Chemistry as part of its
continuing symposia series on nanoscience and nanotechnology. Approximately
80 papers were presented at this symposium and the book chapters represent a
1
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p://k-2 The first two chapters provide a broad view of the field. Chapters 3 to
2 | htt021/b 1b7io lodgeisccarli bthe reaa tsn. uCmhbaperte ros f1 8d teote 2c4ti odne scmriebteh oa dnsu mapbperli coaf balpep rtooa cchhees mtoi cparlo vaindde
11
27, 20oi: 10. pnroot teocntliyo no ufrtocmom cehse mofi cfauln adnadm ebniotalol griecsaela arcghe nbtsu.t aMlsaon yh oowf tthhei sc hreaspetaerrcs hd ecsacnr ibbee
une 9 | d transitioned to produce practical detection devices and novel protective
n J00 materials.
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63.mb vested with the responsibility to sponsor all research connected to chemical and
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89.Dec biological defense. This chapter by Charles Bass Jr. clearly outlines DTRA’s
by e: programmatic goals and the priority research needs. The second chapter is an
d at
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wnlocatio bniaonlootgeicchanl odloegfeyn rsees. e aZrcuhk eafsf oertt sa wl ihtahv pea rptircouvliadre edm ap hcaosmisp orenh tehnes ipvreo jvecietewd onfe eadlsl
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u and technology gaps for protection, detection and decontamination.
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The remaining chapters are devoted to specific research problems
concerning the detection of chemical and biological threats and protection
against such threats. In Chapter 3, Mutharasan et al report on their recent work
with piezoelectric-excited millimeter-sized cantilever (PEMC) sensor for
detecting biological threat agents. PEMC sensors immobilized with an antibody
specific to the target agent are shown to be highly sensitive for detecting 10 -100
Bacillus anthracis spores or the pathogen, E. coli O157:H7, in buffers and also
in complex food matrices. In Chapter 4, Dai et al report on recent progress on
electrospun polymers and polymer/CNT composite nanofibers, with an
emphasis on those based on conducting polymers. The electrospun nanofibers
based on polymer/carbon nanotube (CNT) composites are attractive
multifunctional nanomaterials for many potential applications. In Chapter 5,
Marcus Lay and coworkers describe the use of two dimensional networks of
SWNTs for gas sensing application. They show how the networks can be grown
xi
In Nanoscience and Nanotechnology for Chemical and Biological Defense; Nagarajan, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
by high temperature techniques, or room-temperature liquid deposition
techniques to generate highly aligned SWNT networks on a wide variety of
substrates.
Sooter et al report on their development of microfluidic sorting chips to
rapidly screen for molecular recognition elements that can be used in
immunochromatographic detection of biowarfare agents, in Chapter 6. The
result is a convenient handheld device for the assay of biological agents.
Another portable analytical system is described in Chapter 7. There Lin et al
describe on-site detection of exposure to organophosphate (OP) pesticides and
chemical nerve agents, using nanomaterials functioning as transducers. In
Chapter 8, Driskell et al. investigate the use of aligned Ag nanorod arrays, as
surface-enhanced Raman scattering (SERS) substrates for the identification and
quantitation of viral pathogens. Paresh Ray and collaborators report in Chapter 9
on the development of a miniaturized, and battery operated ultra-sensitive gold
1 nanoparticle-based surface energy transfer probe for screening of the bioagents
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pu00 codes for the 23S rRNA, based on this approach.
p://k-2 In Chapter 10, Samuel Hernandez-Rivera and coworkers show that
2 | htt021/b Raman detection of trace amounts of explosives and other hazardous materials
11 on surfaces can be improved by ten to one thousand times with the addition of
n June 27, 20009 | doi: 10. ccmooollllloeeacidguaulele ssm odenet maallo ivnci srtnuraas nteco aptphasarittd ioc elreglisam ntiionz eacdteo ssn pttaahmteia incl oadtmiesdmtr iobanrueltyaio sen. n ocBfo uaflnnuatoehrraeelsdlci epRnrtoa brtnelepam oar tnoedrf
o2 fluorescence quenching. Using such viral nanoparticles, they show in Chapter
63.35.42 mber 24, 1 1 that enKhyaunncged Sflouno reasncde nccoew foorrk tehres dhetaevcet iodne voef lporpoetde inm tiocxrion sc ihse pmoiscsaibl les.e nsor
1e nodes consisting of GaN HEMT (High Electron Mobility Transistor) sensors
d by 89.ate: Dec awnadr nai nRgF. cTohmeym urenpicoartti oinn lCinhka pfoter rl o1n2g, rraensguelt sc hoenm ihciaglh t hsreelaetc dtievtietcyt iodnet eacntdio ena rolyf
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adn chemical agents (stimulants) using the GaN HEMT sensors and optimal
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Dobli describe their work with polydiacetylene as a sensing material for point-
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with switchable fluorescence can be used either as coatings on nanoporous
membranes or as liposomes attached to fiber supports, for the detection of
biological targets. Weiss and Rong describe their development of a porous
silicon resonant waveguide biosensor in Chapter 14 for the selective detection of
DNA and other small molecules. Experimental demonstrations of the selective
detection of complimentary DNA oligos, with negligible response for both non-
complementary DNA and buffer controls, are reported.
Fan et al report on a method for detecting toxins that inhibit protein
synthesis in Chapter 15. To detect a toxin, a group of proteins are
simultaneously synthesized in a microfluidic array device. The production yields
of these proteins are inhibited differentially by the toxin. The toxin can thus be
identified based on the unique response pattern (or signature) of the array. The
limit of detection for ricin, a bioterrorism agent, is determined at 10 pM. In
xii
In Nanoscience and Nanotechnology for Chemical and Biological Defense; Nagarajan, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
Chapter 16, Samuel Hernandez-Rivera and coworkers focus on a new class of
SERS materials. They use crystalline nanoparticles of TiO , SnO and Sc O
2 2 2 3
and show that polymorphism plays an important role in the Raman signal
enhancement when using metal oxides. Nanoparticle structure and electronic
properties of these systems are expected to allow for applications in sensors
development for use in nitroaromatic explosives detection at sub-picogram level.
Samuel Hernandez-Rivera et al also show in Chapter 17 that bimetallic Au/Ag
nanoparticles can be used for detecting TNT in solution with high sensitivity and
molecular specificity. The detection was an indirect method via alkaline
hydrolysis of TNT using a strong base and the SERS signals can identify TNT
nitro degradation products at 10-15 g.
Chapters 18 to 24 describe nanotechnology based methods to provide
protection against chemical and biological threat agents. Peterson et al describe
in Chapter 18, a method to increase the mesoporosity of zeolites by treating
1 with sodium hydroxide. They show that an increase in mesoporosity, coupled
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pu00 nanocrystalline zeolites with crystal sizes less than 100 nm, possess enhanced
p://k-2 absorptive and catalytic properties and can very effectively deactivate chemical
2 | htt021/b warfare agent simulants. Kaiser and coworkers present their results on the
11 adsorption capacity and off gassing properties of activated carbon based fabrics
n June 27, 20009 | doi: 10. fCvoahrr ai aptbhteleer cc2ho0en mtarioncldal iln awgrg aaurdfesa orterhp aattig oetnhn etc aHapDvaec,r itaay g.ve e spiocaren t,s iazned offo rt hoen ec aorfb iotsn siism ua lacnrtisti,c ianl
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63.35.42 mber 24, dwehsicleri btehde inac Ctivhaatpetde r c2a1rb. o Tn hwe iftihltienr tihs es hsotrwunct utore r eitsa isnh ohwignh lteov edliss polfa ym iac rohbigehs
1e dynamic response as a chemical sorbent. In Chapter 22, Luzinov et al describe
d by 89.ate: Dec tghrea ftsiunrgf avcaer imouosd ipfioclaytmioenr so uf spinogly (theteh y“lgernaeft itnegre tpoh”t htaelcahten)i q(uPeE iTn) omrdeemr btora nreeds ubcye
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adn the permeability of the membrane to chemical agent vapors. Elabd and
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Dobli membranes in Chapter 23. The synthesis is done either by filling nanoporous
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polyelectrolyte nanofiber meshes within polymer membranes. These unique
membrane systems were shown to be have high permeability for water but low
for chemical agents and responsive to an electrical stimulus. They can be
candidates for protective clothing, electrochemical devices (e.g., fuel cells,
batteries, actuators, sensors) and other perm-selective membrane applications. In
the last chapter, Seong Kim et al report on the development of a scanning
atmospheric radio-frequency (rf) plasma source for surface decontamination and
protective coating deposition. This system was used for decontamination of
organophosphorus nerve agents and deposition of hydrophobic and
superhydrophobic coatings on various substrates including ceramics, metals,
fabrics, and nanofibers.
The editors are thankful to the numerous reviewers. The reviewers of
individual chapters contributed prompt critical reviews that have helped improve
xiii
In Nanoscience and Nanotechnology for Chemical and Biological Defense; Nagarajan, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
the quality of the manuscripts. The Editors acknowledge the support from their
institutions, Natick Soldier Research, Development & Engineering Center,
Massachusetts Institute of Technology and the US Army Research Office, that
allowed them to organize the symposium and develop this book based on
selected contributions.
R. Nagarajan
Molecular Sciences and Engineering Team
Natick Soldier Research, Development & Engineering Center
Natick, MA
Walter Zukas
Chemical Technology Team
Natick Soldier Research, Development & Engineering Center
1 Natick, MA
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pu00 Massachusetts Institute of Technology
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11 Stephen Lee
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In Nanoscience and Nanotechnology for Chemical and Biological Defense; Nagarajan, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
