Electrochemical detection of chemical warfare agents
| dc.contributor.advisor | Kraatz, Heinz-Bernhard | en_US |
| dc.creator | Khan, Mohammad Abdul Kader | en_US |
| dc.date.accessioned | 2007-05-22T10:45:56Z | en_US |
| dc.date.accessioned | 2013-01-04T04:31:16Z | |
| dc.date.available | 2007-05-22T08:00:00Z | en_US |
| dc.date.available | 2013-01-04T04:31:16Z | |
| dc.date.created | 2007-05 | en_US |
| dc.date.issued | 2007-05-22 | en_US |
| dc.date.submitted | May 2007 | en_US |
| dc.description.abstract | 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. 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. 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. | en_US |
| dc.identifier.uri | http://hdl.handle.net/10388/etd-05222007-104556 | en_US |
| dc.language.iso | en_US | en_US |
| dc.subject | Chemical warfare agents | en_US |
| dc.subject | Electrochemical detection | en_US |
| dc.subject | Cyclic voltammetry | en_US |
| dc.title | Electrochemical detection of chemical warfare agents | en_US |
| dc.type.genre | Thesis | en_US |
| dc.type.material | text | en_US |
| thesis.degree.department | Chemistry | en_US |
| thesis.degree.discipline | Chemistry | en_US |
| thesis.degree.grantor | University of Saskatchewan | en_US |
| thesis.degree.level | Masters | en_US |
| thesis.degree.name | Master of Science (M.Sc.) | en_US |