Control and calibration of atmospheric pressure chemical ionisation processes in ion mobility spectrometry using piezoelectric dispensers

If the analyses of trace components in complex organic samples are to be optimised, then these compounds must be isolated either physically or chemically from surrounding matrices. Ion mobility spectrometry (IMS) is an analytical technique used worldwide for the detection of on-site trace compounds. The technique can be optimised to isolate the target species from complex matrices through both physical separation, based on the mobility of the analyte ions at ambient pressure, and chemical discrimination through preferential ionisation of the target. Optimisation of the latter is commonly achieved through doping the spectrometer with a selective reagent gas, termed a dopant. The chemical processes required to optimise the responses of target analytes are dependent on the identity and concentration of the dopant. As such, a variety of dopants have been successfully implemented in ion mobility spectrometers. The technology for the deliverance of dopants in IMS is commonly through permeation sources, which provide a stable chemical environment in the ion mobility cell. Althoughrelatively inexpensive and durable, these devices are difficult to change and generally deliver a single dopant concentration. As a result, only one type of chemistry is possible and the responses cannot be optimised for a range of analytical applications. Such limitationsbecome increasingly significant when IMS is hyphenated to a chromatograph where a range of different dopant conditions may be sought over the course of a chromatographic run. This thesis sought to overcome these limitations through the development and implementation of piezoelectric dispensers, interfaced directly to the transport gas regions of IMS cells. The study demonstrates for the first time the ability to use piezoelectric dispensing as a dopant introduction methodology in IMS for controlling and calibrating a range of dopant chemistries. 2-butanol, acetone, dichloromethane, 1-chlorohexane, 4-heptanone and 1-bromohexane were the candidate dopants chosen for the studies, covering a wide range of physical and chemical properties. The novel technology was used to dispense the target dopants into IMS cells at concentration ranges over three orders of magnitude. Dopant chemistries were achieved within three seconds from the point of dispensing, administered in drop-ondemand formats, and could be delivered either transiently or at steady-state concentrations. The concept was validated through integrated spectral dopant responses. In transient control, dynamic linear relationships of R2 = 0.991 – 0.998 were achieved between dispensed dopant mass and peak area. Under continuous operation, the RSD of the dopant level was < 18% for all dopants. Clear out times for dopant responses were in the order of 3-5 seconds, indicating negligible hysteresis effects. The study also proved the concept of controlling monomer and dimer ion chemistries from 2-butanol actuations when interfaced to a differential mobility spectrometer at mass fluxes between 21 – 1230 ng m-3 , and the simultaneous control of dopants in negative and positive ionisation modes to RSDs <10%. This thesis describes the techniques used to optimise the piezoelectric dispensing of the full dopant range, as well as the full design protocols required to interface to mobility spectrometers. The outcomes from these studies provide a realisation for piezoelectric dispensers as a future mainstream dopant introduction technique for the analysis of complex samples