Search

A series of block copolymers comprising styrene and maleic acid (SMA) has been prepared using RAFT polymerisation. RAFT often results in a large hydrophobic alkylthiocarbonylthio end group and this work examines its effect on the solution behaviour of the copolymers. SMA variants with, and without, this end group were synthesised and their behaviour compared with a commercially-available random copolymer of similar molecular weight. Dynamic light scattering and surface tension measurements found the RAFT-copolymers preferentially self-assembled into higher-order aggregates in aqueous solution. Small angle neutron scattering using deuterated styrene varients add support to the accepted model that these agreggates comprise a solvent-protected styrenic core with an acid-rich shell. Replacing the hydrophobic RAFT end group with a more hydrophilic nitrile caused differences in the resulting surface activity, attributed to the ability of the adjoining styrene homoblock to drive aggregation. Each of the copolymers formed SMALP nanodiscs with DMPC lipids, which were found to encapsulate a model membrane protein, gramicidin. However, end group variation affected solubilisition of DPPC, a lipid with a higher phase transition temperature. When using RAFT-copolymers terminated with a hydrophobic group, swelling of the bilayer and greater penetration of the homoblock into the nanodisc core occurred with increasing homoblock length. Conversely, commercial and nitrile-terminated RAFT-copolymers produced nanodisc sizes that stayed constant, instead indicating interaction at the edge of the lipid patch. The results highlight how even minor changes to the copolymer can modify the amphiphilic balance between regions, knowledge useful towards optimising copolymer structure to enhance and control nanodisc formation.

There is a need for non-contact, real-time vapor detection of drugs to combat illicit transportation and help curb the opioid epidemic. The low volatility of drugs, like fentanyl, makes room temperature vapor detection of illicit drugs challenging, but feasible by atmospheric flow tube-mass spectrometry (AFT-MS). AFT-MS is a non-contact vapor detection approach capable of ultra-trace detection of drugs, including fentanyl and its analogs at low parts-per-quadrillion (ppq v ) levels. The determination of vapor pressure values of fentanyl is necessary to understand potential vapor concentrations that may be available for detection. In this paper, vapor pressures of fentanyl free base and fentanyl hydrochloride salt (a common form of the illicit drug) were measured as a function of temperature at or near ambient conditions using the transpiration (gas saturation) method and AFT-MS. Based on our measurements, the vapor pressure of fentanyl at 25 °C is 9.0 × 10 -14 atm (90 ppq v ), and the vapor pressure of fentanyl hydrochloride at 25 °C is 1.8 × 10 -17 atm (0.018 ppq v ). We also demonstrate non-contact, real-time vapor detection of fentanyl. Preconcentration of vapors can further extend the detection capabilities. The collection, desorption, and detection of fentanyl vapors at ambient conditions was demonstrated for sampling times of seconds to an hour resulting in increased signal. AFT-MS is a viable detection method of fentanyl and other drugs for screening of packages and cargo.

Thiodiglycol (TDG) is a synthetic precursor and an environmental degradation product of sulfur mustard (HD). Consequently, its presence can be indicative of illicit preparation or historical presence of chemical weapons, but its lower toxicity lends itself to use as an HD simulant for testing and method development. Detection of TDG vapor often proves elusive with existing techniques exhibiting undesirably high detection limits in the gas phase (>ppm). Moreover, traditional approaches to detecting TDG vapor rely upon non-specific approaches that do not provide the certainty afforded by mass spectrometry. Using atmospheric flow tube mass spectrometry (AFT-MS), which has previously demonstrated the capacity to detect parts-per-quadrillion levels of vapor, we evaluate the capacity of this approach for non-contact residue analysis based upon TDG vapor sampling and nitrate clustering chemistry. Furthermore, we discuss challenges with ambient vapor detection using the AFT-MS system and associated observations related to TDG degradation into 2,2'-sulfonyldiglycol from exposure to ambient conditions with vapor detection being possible even after 7-weeks of sample aging.

Real-time, non-contact detection of illicit drugs is a desirable goal for the interdiction of these controlled substances, but the relatively low vapor pressures of such species present a challenge for trace vapor detection technologies. The introduction of atmospheric flow tube-mass spectrometry (AFT-MS), which has previously been demonstrated to detect gas-phase analytes at low parts-per-quadrillion levels for explosives and organophosphorus compounds, also enables the potential for non-contact drug detection. With AFT-MS, direct vapor detection of cocaine and methamphetamine from ∼5 μg residues at room temperature is demonstrated herein. Furthermore, thermal desorption of low- to sub-picogram levels of cocaine, methamphetamine, fentanyl, and heroin is observed via AFT-MS using a carrier flow rate of several L min -1 of air. These low levels can permit non-contact sampling through collection of vapor, effectively preconcentrating the analyte before desorption and analysis. Quantitative evaluation of the thermal desorption approach has yielded limits of detection (LODs) on the order of 10 fg for cocaine and fentanyl, 100 fg for methamphetamine, and 1.6 pg for heroin. The LOD for heroin was lowered to 300 fg by using tributyl phosphate as a dopant to form a proton-bound heterodimer with heroin. When used with AFT-MS, the intentional formation of specific drug-dopant adducts has the potential to enhance detection limits and selectivity of additional drug species. Species that are prone to form adducts present a challenge to analysis, but that difficulty can be overcome by the intentional addition of a dopant. Molecules unlikely to form adducts will remain essentially unimpacted, but the adduct-forming species will interact with the dopant to compress the analyte signal into a single peak. This approach would be valuable in the application of non-contact screening for illicit substances via vapor collection followed by thermal desorption for analysis.