In situ reaction rate measurements help to define the role of product inhibition in the asymmetric alkylation of benzaldehyde with diethylzinc using (-)-MIB as a chiral reagent. Reaction calorimetry and kinetic modeling demonstrated that the rate behavior over consecutive reactions may only be rationalized when reversible binding of the product alkoxide is taken into consideration. These results may have implications for the conversion dependence of product enantioselctivity in reactions using enantioimpure catalysts.
In this publication we work towards providing fast, sensitive and selective analysis of explosive compounds collected on swabs using paper spray mass spectrometry. We have (a) increased the size of the paper spray substrate to 1.6×2.1 cm for compatibility with current practise in swabbing for explosive material; (b) developed a method for determining a successful extraction of analyte from the substrate to reduce false negative events; and (c) expanded the range of analytes that can be detected using paper spray to include the peroxide explosive HMTD, as well as nitroglycerine (NG), picric acid (PA) and tetryl. We report the development of a 30 s method for the simultaneous detection of 7 different explosive materials using PS‐MS with detection limits below 25 pg, as well as detection of HMTD at 2500 pg, showing an improvement on previously published work.
Rationale
Paper spray offers a rapid screening test without the need for sample preparation. The incomplete extraction of paper spray allows for further testing using more robust, selective and sensitive techniques such as liquid chromatography/mass spectrometry (LC/MS). Here we develop a two‐step process of paper spray followed by LC/MS to (1) rapidly screen a large number of samples and (2) confirm any disputed results. This demonstrates the applicability for testing medication adherence from a fingerprint.
Methods
Following paper spray analysis, drugs of abuse samples were analysed using LC/MS. All analyses were completed using a Q Exactive™ Plus Orbitrap™ mass spectrometer. This two‐step procedure was applied to fingerprints collected from patients on a maintained dose of the antipsychotic drug quetiapine.
Results
The extraction efficiency of paper spray for two drugs of abuse and metabolites was found to be between 15 and 35% (analyte dependent). For short acquisition times, the extraction efficiency was found to vary between replicates by less than 30%, enabling subsequent analysis by LC/MS. This two‐step process was then applied to fingerprints collected from two patients taking the antipsychotic drug quetiapine, which demonstrates how a negative screening result from paper spray can be resolved using LC/MS.
Conclusions
We have shown for the first time the sequential analysis of the same sample using paper spray and LC/MS, as well as the detection of an antipsychotic drug from a fingerprint. We propose that this workflow may also be applied to any type of sample compatible with paper spray, and will be especially convenient where only one sample is available for analysis.
The catalytic reduction of NO has been studied over novel supported uranium oxide catalysts which exhibit comparable activity and selectivity to that of conventional supported Pt catalysts and for which in situ XRD identifies the active phase to be UO x (2 < x < 2.25).
The development of ambient ionization mass spectrometry (AIMS) has transformed analytical science, providing the means of performing rapid analysis of samples in their native state, both in and out of the laboratory. The capacity to eliminate sample preparation and pre‐MS separation techniques, leading to true real‐time analysis, has led to AIMS naturally gaining a broad interest across the scientific community. Since the introduction of the first AIMS techniques in the mid‐2000s, the field has exploded with dozens of novel ion sources, an array of intriguing applications, and an evident growing interest across diverse areas of study. As the field continues to surge forward each year, ambient ionization techniques are increasingly becoming commonplace in laboratories around the world. This annual review provides an overview of AIMS techniques and applications throughout 2022, with a specific focus on some of the major fields of research, including forensic science, disease diagnostics, pharmaceuticals and food sciences. New techniques and methods are introduced, demonstrating the unwavering drive of the analytical community to further advance this exciting field and push the boundaries of what analytical chemistry can achieve.
This thesis proposes an integrated simulation tool to evaluate the impact of future in-space additive manufacturing (ISAM) and recycling technologies on the responsiveness of an on-orbit servicing (OOS) infrastructure to random failures of satellites distributed over an orbit. The considered OOS infrastructure is composed of a mothership and a servicer (i.e., daughtership); the mothership serves as a depot for spares, whereas the servicer travels with the spares to randomly failed satellites and provides a service. All satellites are assumed to be modularized, and thus the service type considered within the infrastructure is the replacement of a failed module with a new spare one. Additionally, an ISAM facility can be added to the mothership, which can scavenge material that makes up the failed module. This obtained feedstock from failed modules, along with raw material supplied from Earth, could be used to manufacture a new spare. The key parameters in this analysis include the technology level of ISAM, in terms of the types of material it can manufacture, and the scavenge rate, defined as the percent of material mass able to be recycled from the failed module to the new module. The two metrics for evaluation are the required resupply launch mass to the mothership and the average waiting time of the satellites before it is serviced. Simulations results showed that the ISAM and recycling technology provides a large impact in terms of both reduction in resupply launch mass and responsiveness of its service to the randomly failed satellites. v TABLE OF CONTENTS CHAPTER
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