Thesis (M.S.)--Air Force Institute of Technology, 2007. / AFIT/GIR/ENV/07-M9. Title from title page of PDF document (viewed on: Nov. 29, 2007). "March 2007." Includes bibliographical references (leaves 226-237).

Thesis (M.S. in computer science)--Washington State University, December 2007. / Includes bibliographical references (p. 77-79).

Thesis (Ph. D.)--University of Washington, 2006. / Vita. Includes bibliographical references (leaves 75-78).

There are some 15,000 known organophosphorus chemicals. Some of these OP’s, including VX and paraoxon, demonstrate an acute neurotoxicity due to the inhibition of cholinergic enzymes. Organophosphorus chemical warfare agents and pesticide neurotoxins are subject to hydrolysis by OP degrading enzymes. To be useful as a bioremediation or anti-chemical warfare agent, the enzyme must be tailored for, and integrated into, a practical application platform. Several studies have established enzyme-based countermeasures, describing such diverse applications as decontaminating foams for surface remediation, encapsulating enzyme with liposome for in vivo therapy, enzyme attachments to surfaces for biosensors and development of a corn expression system for large-scale enzyme production. The goal of the research described here is to select, investigate and improve the operational potential of organophosphate-degrading enzymes including Organophosphorus Hydrolase (OPH, 3.1.8.1) and Organophosphorus Acid Anhydrolase (OPAA, 3.1.8.2). Using saturation kinetics, the catalytic efficiencies of these two major detoxification enzymes were characterized with substrates representing each class of OP neurotoxin, phosphotriester, phosphothioate and phosphofluoridate. OPH presents superior kinetic parameters with each OP class tested. Variants of OPH were created to increase the operational effectiveness of OP hydrolytic enzymes against phosphorothioates. An H254S/H257L mutation in the active site resulted in an improvement in the kinetics (kcat/KM) for the phosphorothioate, demeton-S. To screen potential vascular protection therapies, an in vitro protocol was developed to predict enzymatic effectiveness for protection of acetylcholinesterase from acute OP-inhibition. The protection abilities of the enzymes were directly related to their second order rate constants as inhibitory levels of OP are below the KM of the enzymes. Consideration of contaminant nature concentration and enzyme kinetic parameters, kcat and KM, is critical to understanding decontamination and effective use of enzyme technology. These technologies continue to develop and provide promising new decontamination tools for OP compounds.

This thesis deals with issues of indigeneity, warfare and representation as they relate to the Zapatista struggle in Chiapas, Mexico between the years of 1994-2003 –a period widely known as a period of low intensity warfare. During this period, militants of the Zapatista National Liberation Army (EZLN) engaged fiercely in the creation and defence of de facto “indigenous” municipalities and territories, posing a direct challenge to the legitimacy of the Mexican “state” and its faculty to govern. The environment of war, accompanied by a prevalent Indianist discourse, highly structured the ways in which Zapatista lives came to be represented by activist and academic writings alike. Generic images of Zapatista militants came to dominate the literature. Within this context, my thesis argues for the importance of moving away from images of Zapatistas as public figures and investigating, instead, everyday Zapatista lives. I argue that a refocus on specific-situated-local-everyday politics necessarily entails engaging with “internal” conflict, division, hierarchies, and power differentials. Framed by an ethnographic approach, the analysis presented here is based on 17 months of fieldwork. My discussion on indigenous autonomy and self-determination, therefore, goes well beyond claims to indigenous rights and engages, instead, historical as well as on-the-ground expressions of what self-determination looked like on an everyday basis. My discussion on warfare, moves beyond condemnations of militarization in the area and pays attention to some of the ways in which warfare worked to structure peoples’ lives and daily perceptions as well as outsiders’ understanding of the conflict. While generally my analysis is confined by the particularities of time and space, a generous examination of an ample literature gives it theoretical depth and political relevance beyond the Zapatista case.

From 1939 to 1942 Canada, allied to the United Kingdom, prepared to defend itself against chemical attack by Nazi Germany. The Canadian preparations represented one of Canadas many contributions to the cause of the British Commonwealth, and may have been used as one method to counter British requests for additional ground troops. After the Japanese attack at Pearl Harbor, Canada became part of an alliance with the United States and the United Kingdom. Canadian chemical warfare preparations went from defensive to offensive following the attack on Pearl Harbor and the entry of the United States into the war. The chemical warfare preparations included preparation and testing of toxic gases and smokes, smoke screening and flame weapons.<p> One of the most important Canadian contributions to the alliance was the establishment of the Suffield Field Experimental Station in Alberta. This base was particularly useful in carrying out chemical weapon trials, during which approximately 2000 Canadian citizens and soldiers were exposed to toxic gases. At the beginning of the war chemical warfare volunteers were completely covered in protective clothing except for a patch to allow for controlled chemical burns. But by 1942 Suffield staff was given permission to rewrite the regulations for the trials, and volunteers often received significant chemical injuries, including to the eyes. It would appear that the full body of knowledge available to the wartime scientists, especially information relevant to the long-term health outcomes of exposure to vesicant agents, was not applied in the conduct of the human experimentation.

tert-butyl 1-methoxycarbonyl-1-ferrocenecarbamate, Boc-NH-Fc-COOMe, (1) was synthesized according to the literature procedure and modified to 1-amino-n′-ferrocenemethylcarboxylate, 1,n′-H2N-Fc-COOCH3 (2) by removing the Boc-group with TFA/Et3N mixture in dichloromethane. Compound 2 reacted with alkylating agents like MeI, EtI, EtSCH2CH2Cl (MA) and (CN)(EtO)2P(O) (NA) to form MeNH-Fc-COOMe (3), EtNH-Fc-COOMe (4), EtSCH2CH2NH-Fc-COOMe (5), (EtO)2P(O)NH-Fc-COOMe (6), respectively. Cyclic voltammetry (CV) of these compounds showed different half-wave potential characteristics compared to aminoferrocene and was dependent on the nature of the substituents, which was rationalized by molecular orbital calculations. Electron donating groups (Me, Et and 2-chloroethyl ethylsulfide, MA) shifted the half-wave potential towards the cathodic direction while electron withdrawing group like diethyl cyanophosphonate, NA, shifted it toward anodic direction. Anodic to cathodic peak separation were found to be within 62-88 mV indicating a quasi-reversible system. <p>Hydrolysis of compound 1 resulted in the formation of tert-butyl 1-methoxycarbonyl-1-ferrocenecarboxylic acid, Boc-NH-Fc-COOH, (11) which was coupled with cystamine using the EDC/HOBt protocol to synthesize the cystamine conjugate [BocHN-Fc-CO-CSA]2 (12). This molecule is equipped with an amino group that directly linked to the redox receptor. Compound 12 was fully characterized by spectroscopic methods and by single crystal x-ray diffraction. The cystamine conjugate 12 formed films on gold substrates, which upon deprotection of the amino group, reacted with chemical warfare agents (CWAs) mimics, such as EtSCH2CH2Cl (MA), a simulant for the sulfur mustard HD, and (CN)(EtO)2P(O) (NA), a simulant for the nerve agent Tabun. Their reaction with the surface-bound ferrocene derivative results in the formation of N-substituted products. <p>CV measurements showed anodic shifts of the Fc redox potentials by 50 (±5) mV after exposure to MA, and NA. Measurements by quartz crystal microbalance (QCM) showed an increase in mass upon exposure to MA and NA. Ellipsometry measured a film thickness increase from 6 (±1) Å for the deprotected film to 10 (±4) Å for the film modified with MA and to 7 (±2) Å for the film modified with NA. The surfaces were analyzed by x-ray photoelectron spectroscopy (XPS) and clearly showed the attachment of the cystamine conjugate on the surface and its reaction with CWAs mimics.

Maritime conflict in the next decade or three, when it happens, will not be the full-blown war that our carriers and strategic submarines are designed for. Instead, it will be economic warfare through the interdiction of maritime trade, harassment of naval vessels as rising nations attempt to expand their sphere of influence, and development of cheap (or uncounterable) technologies that keep potential adversaries or rivals at bay. All of this will take place in blue-water environments as access to the littorals is effectively denied by these new technologies. As it stands, the United States is inadequately prepared to face this possibility. This paper will examine how and why this strategy will arise, identify the most likely locations and actors, and explore how these scenario are likely to play out. Additionally, this paper will examine potential remedies that the United States (or other interested powers) could undertake to reduce the impact of these strategies, perhaps even avoiding their occurrence altogether.

This thesis deals with issues of indigeneity, warfare and representation as they relate to the Zapatista struggle in Chiapas, Mexico between the years of 1994-2003 –a period widely known as a period of low intensity warfare. During this period, militants of the Zapatista National Liberation Army (EZLN) engaged fiercely in the creation and defence of de facto “indigenous” municipalities and territories, posing a direct challenge to the legitimacy of the Mexican “state” and its faculty to govern. The environment of war, accompanied by a prevalent Indianist discourse, highly structured the ways in which Zapatista lives came to be represented by activist and academic writings alike. Generic images of Zapatista militants came to dominate the literature. Within this context, my thesis argues for the importance of moving away from images of Zapatistas as public figures and investigating, instead, everyday Zapatista lives. I argue that a refocus on specific-situated-local-everyday politics necessarily entails engaging with “internal” conflict, division, hierarchies, and power differentials. Framed by an ethnographic approach, the analysis presented here is based on 17 months of fieldwork. My discussion on indigenous autonomy and self-determination, therefore, goes well beyond claims to indigenous rights and engages, instead, historical as well as on-the-ground expressions of what self-determination looked like on an everyday basis. My discussion on warfare, moves beyond condemnations of militarization in the area and pays attention to some of the ways in which warfare worked to structure peoples’ lives and daily perceptions as well as outsiders’ understanding of the conflict. While generally my analysis is confined by the particularities of time and space, a generous examination of an ample literature gives it theoretical depth and political relevance beyond the Zapatista case.

tert-butyl 1-methoxycarbonyl-1-ferrocenecarbamate, Boc-NH-Fc-COOMe, (1) was synthesized according to the literature procedure and modified to 1-amino-n′-ferrocenemethylcarboxylate, 1,n′-H2N-Fc-COOCH3 (2) by removing the Boc-group with TFA/Et3N mixture in dichloromethane. Compound 2 reacted with alkylating agents like MeI, EtI, EtSCH2CH2Cl (MA) and (CN)(EtO)2P(O) (NA) to form MeNH-Fc-COOMe (3), EtNH-Fc-COOMe (4), EtSCH2CH2NH-Fc-COOMe (5), (EtO)2P(O)NH-Fc-COOMe (6), respectively. Cyclic voltammetry (CV) of these compounds showed different half-wave potential characteristics compared to aminoferrocene and was dependent on the nature of the substituents, which was rationalized by molecular orbital calculations. Electron donating groups (Me, Et and 2-chloroethyl ethylsulfide, MA) shifted the half-wave potential towards the cathodic direction while electron withdrawing group like diethyl cyanophosphonate, NA, shifted it toward anodic direction. Anodic to cathodic peak separation were found to be within 62-88 mV indicating a quasi-reversible system. <p>Hydrolysis of compound 1 resulted in the formation of tert-butyl 1-methoxycarbonyl-1-ferrocenecarboxylic acid, Boc-NH-Fc-COOH, (11) which was coupled with cystamine using the EDC/HOBt protocol to synthesize the cystamine conjugate [BocHN-Fc-CO-CSA]2 (12). This molecule is equipped with an amino group that directly linked to the redox receptor. Compound 12 was fully characterized by spectroscopic methods and by single crystal x-ray diffraction. The cystamine conjugate 12 formed films on gold substrates, which upon deprotection of the amino group, reacted with chemical warfare agents (CWAs) mimics, such as EtSCH2CH2Cl (MA), a simulant for the sulfur mustard HD, and (CN)(EtO)2P(O) (NA), a simulant for the nerve agent Tabun. Their reaction with the surface-bound ferrocene derivative results in the formation of N-substituted products. <p>CV measurements showed anodic shifts of the Fc redox potentials by 50 (±5) mV after exposure to MA, and NA. Measurements by quartz crystal microbalance (QCM) showed an increase in mass upon exposure to MA and NA. Ellipsometry measured a film thickness increase from 6 (±1) Å for the deprotected film to 10 (±4) Å for the film modified with MA and to 7 (±2) Å for the film modified with NA. The surfaces were analyzed by x-ray photoelectron spectroscopy (XPS) and clearly showed the attachment of the cystamine conjugate on the surface and its reaction with CWAs mimics.