Antiterrorism and Homeland Defense. Polymers and Materials 9780841239647, 9780841221130

Citation preview

August 4, 2012 | http://pubs.acs.org Publication Date: December 31, 2007 | doi: 10.1021/bk-2007-0980.fw001

Antiterrorism and Homeland Defense

In Antiterrorism and Homeland Defense; Reynolds, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007.

August 4, 2012 | http://pubs.acs.org Publication Date: December 31, 2007 | doi: 10.1021/bk-2007-0980.fw001

In Antiterrorism and Homeland Defense; Reynolds, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007.

August 4, 2012 | http://pubs.acs.org Publication Date: December 31, 2007 | doi: 10.1021/bk-2007-0980.fw001

A C S S Y M P O S I U M SERIES

980

Antiterrorism and Homeland Defense Polymers and Materials John G. Reynolds, Editor Lawrence Livermore National Laboratory

Glenn E . Lawson, Editor Naval Surface Warfare Center

Carolyn J. Koester, Editor Lawrence Livermore National Laboratory

Sponsored by the

Division of Polymeric Materials: Science and Engineering, Inc.

American Chemical Society, Washington, D C In Antiterrorism and Homeland Defense; Reynolds, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007.

August 4, 2012 | http://pubs.acs.org Publication Date: December 31, 2007 | doi: 10.1021/bk-2007-0980.fw001

ISBN: 978-0-8412-3964-7 The paper used in this publication meets the minimum requirements of American National Standard for Information Sciences—Permanence of Paper for Printed Library Materials, A N S I Z39.48-1984. Copyright © 2007 American Chemical Society Distributed by Oxford University Press A l l Rights Reserved. Reprographic copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Act is allowed for internal use only, provided that a per-chapter fee of $36.50 plus $0.75 per page is paid to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, M A 01923, U S A . Republication or reproduction for sale of pages in this book is permitted only under license from A C S . Direct these and other permission requests to A C S Copyright Office, Publications Division, 1155 16th Street, N.W., Washington, D C 20036. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by A C S of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN T H E U N I T E D S T A T E S OF A M E R I C A

In Antiterrorism and Homeland Defense; Reynolds, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007.

August 4, 2012 | http://pubs.acs.org Publication Date: December 31, 2007 | doi: 10.1021/bk-2007-0980.fw001

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 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. Before agreeing to publish a book, the proposed table of contents is reviewed for appropriate and comprehensive coverage and for interest to the audience. Some papers may be excluded to better focus the book; others may be added to provide comprehensiveness. When appropriate, overview or introductory chapters are added. Drafts of chapters are peer-reviewed prior to final acceptance or rejection, and manuscripts are prepared in camera-ready format. As a rule, only original research papers and original review papers are included in the volumes. Verbatim reproductions of previously published papers are not accepted.

A C S Books Department

In Antiterrorism and Homeland Defense; Reynolds, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007.

Chapter 1

Polymers and Materials for Antiterrorism and Homeland Defense: An Overview John G . Reynolds and Glenn E. Lawson 1

2

August 4, 2012 | http://pubs.acs.org Publication Date: December 31, 2007 | doi: 10.1021/bk-2007-0980.ch001

1

Forensic Science Center, Lawrence Livermore National Laboratory, P.O. Box 808, L-178, Livermore, C A 94551 ([email protected]) Chemical/Biological Defense Center, 17320 Dahlgren Road, Building 1480, Code Z21, Naval Surface Warfare Division, Dahlgren, V A 22448-5000 ([email protected])

2

Polymers and materials play key roles in national security through detection and decontamination addressing chemical, biological, radiological, nuclear and explosives threats. Proposed detection and decontamination methods utilize polymers and other materials to combat terrorist threats. Because today's detectors are not sufficiently sensitive and selective and decontamination agents are not selective enough for all threats and every scenario, research is being conducted to bridge the scientific and technical gaps. Collected in this volume are papers that elucidate specific efforts in developing new polymers and new materials that can be used as platforms in detectors, as the matrix to incorporate specific detection sites, as recognition elements for detection, as detectors themselves, as decontamination agents and as key components in detection systems. The chapters are divided into the categories of chemical detection, biological detection, and decontamination. Although these groupings are primarily based on the applications, much of the design of the polymers and materials can be broadened into other pertinent detection and decontamination scenarios. A variety of polymeric materials and the methodology to produce them are described. These polymers include cross© 2008 American Chemical Society

In Antiterrorism and Homeland Defense; Reynolds, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007.

3

August 4, 2012 | http://pubs.acs.org Publication Date: December 31, 2007 | doi: 10.1021/bk-2007-0980.ch001

4 linked divinyl benzene-substituted methacrylate polymers, polycarbosilanes, non-aqueous chemically cross-linked polybutadiene gels, conducting polyaniline nanofibers, organically doped polystyrene and polyvinyltoluene, electroplated polymer cast resins, amphiphilic functionalized norbornene polymers, cross-linked divinyl-benzamide phospholipids, silica and organo-silyl polymers. Other materials include metal chelating complexes, functionalized porous silicon, siloxyl immobilized enzymes with porphyrins, polycarbosilanes, quantum dots and nano-crystalline oxides, dendritic complexing sites, amphiphilic functionalized norbornene polymers, reactive glass surfaces, and self assembled monolayers.

Introduction Since, the tragedy that occurred on September 11, 2001, there have been dramatic increases in research activities to develop chemical and biological detection systems for anti-terrorism and homeland defense. To protect military personnel and the general public, chemical and biological warfare detection systems are rapidly becoming an essential part of the homeland security and defense strategies of the United States. Critical research is being conducted in government, academic, and industrial laboratories. The majority of this research activity has been in the collection, detection and mitigation of chemical, biological, nuclear and explosive (CBNE) materials related to weapons of mass destruction (WMD). The aim of this research is concentrated in two different directions; one is concerned with protection and decontamination on the battlefield, the other, protection within civilian populated centers. Battlefield protection and decontamination encompasses rapid detection, neutralization and removal of chemical and biological agents from military vehicles, equipment, personnel, and facilities (1-3). Protection of civilian centers encompasses rapid detection and removal of chemical and biological agents from public buildings, equipment, and civilians, to concentrations that are lower than those required for military applications. A t this time, new detection systems are necessary because current technology is not sufficient in warning of the presence of such weapons. New mitigation methods are necessary for protecting military personnel and the civilian population from attack, as well as securing facilities from contamination. The chemical warfare agents (Figure 1) of main focus in this book are H D , V X , G B , and G D . H D is a blistering agent that attacks the mucous membranes and is lethal at high doses. V X , G B , and G D are nerve agents that have the

In Antiterrorism and Homeland Defense; Reynolds, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007.

5 Ο

S.

.CH(CH ) CH3CH2O-P-SCH2CH2N' CH(CH ) CH 3

CH2CH2CI

2

N

(

3

2

3

2 Ο CH C(CH ) CH(CH )0-P-F 3

3

2

3

CH

August 4, 2012 | http://pubs.acs.org Publication Date: December 31, 2007 | doi: 10.1021/bk-2007-0980.ch001

3

3

4 Figure L Chemical structures of warfare agents sulfur mustard (1), VX (2), GB (3), and GD (4).

ability to stop respiratory and nerve functions, as well as kill in only minutes, even in fairly low concentrations (4, 5). Due to the toxic nature of the chemical warfare agents, compounds used during initial investigations of new materials and sensors are often simulants or surrogates. Simulants mimic one or more of the physical properties (for example, vapor pressure) of a chemical warfare agent and have significantly lesser toxicities than those of the chemical agents. Surrogates are compounds that are similar in chemical structure (i.e., contain common functional groups) to chemical agents and, for this reason, might have significant, albeit lesser, toxicities. For example organophosphorous pesticides are often used as surrogates for the organophosphorus nerve agents. The use of simulants and surrogates makes it possible to more safely study decontamination mechanisms, like oxidation, at pentavalent phosphorus atoms as substitutes for nerve agents. The results of these studies can then be extrapolated to chemical warfare agents. Although, simulants and surrogates can facilitate detoxification and decontamination studies, critical final testing must be performed with actual agents. Such testing is extremely dangerous, time consuming and expensive. Detection and decontamination of biological threat agents is also covered in this book. Biological agents cover a broad range of pathogens that either attack organisms directly or produce large toxins, which also debilitate and kill. Detection and decontamination is often studied using surrogates, as in the case of chemical warfare agents. Table I, shows a partial list of these threats from the Centers for Disease Control and Prevention (500, (>49) 200, (20) 25, (2.5) 200, (19)

>500, (>49) 300, (30) 25, (2.5) 200, (19)

Selectivity

HCso [Mg/mL, (μΜ)] E. coli >1000, (>98) >4000, (>400)