Nanoparticles, simple yet groundbreaking objects have led to the discovery of invaluable information due to their physiological, chemical, and physical properties, have become a hot topic in various fields of study including but not limited to chemistry, biology, and physics. In the work presented here, demonstrations of various applications of chemical free nanoparticles are explored, from the determination of a non-invasive method for the study of the exposome via using soft-landing ion mobility (SLIM) deposited nanoparticles as a matrix-assisted laser desorption/ionization (MALDI-MS) matrix replacement, to the direct SLIM-exposure of nanoparticles onto living organisms. While there is plenty of published work in soft-landing at operating pressures of 1 Torr, the work presented here shows how this technology can be operated at the less common ambient pressure. The ease of construction of this instrument allows for various modifications to be performed for a wide array of applications, furthermore the flexibility in metallic sample, operating pressure, and deposition time only open doors to many other future applications. The work presented will also show that our ambient SLIM system is also able to be operated for toxicological studies, as the operation at ambient pressure opens the door to new applications where vacuum conditions are …

Portable mass spectrometry has become an important analytical tool for chemical detection and identification outside of a lab setting. Many variations and applications have been developed to benefit various fields of science. Membrane inlet mass spectrometry is used to allow certain analytes to pass into the mass spectrometer without breaking vacuum or letting in large particulate matter. These two important analytical tools have been applied to the detection of harmful chemicals in the air. Earth-based separations and reverse gas stack modelling are useful mathematical tools that can be used to locate the source of a chemical release by back calculation. Earth-based separations studies the way different molecules will diffuse and separate through the air. Reverse gas stack modelling refers to the concentration differences of a chemical in relation to its distance from its source. These four analytical techniques can be combined to quickly and accurately locate various harmful chemical releases. The same system can be used for many applications and has been tested to detect harmful chemicals within and air-handling system. The monitoring of air-handling systems can greatly reduce the threat of harm to the building occupants by detecting hazardous chemicals and shutting off the air flow to minimize human …

Molecular engineering of donor-acceptor dyads and multimodular systems to control the yield and lifetime of charge separation is one of the key goals of artificial photosynthesis for harvesting sustainably solar energy. The design of the donor-acceptor systems mimic a part of green plants and bacterial photosynthetic processes. The photochemical events in natural photosynthesis involve the capturing and funneling of solar energy by a group of well-organized chromophores referred to as an ‘antenna' system causing an electron transfer into the ‘reaction center,' where an electron transfer processes occur resulting a long-lived charge separated state. Over the last two to three decades, many efforts have been directed by the scientific community designing of multi-modular systems that are capable of capturing most of the useful sunlight and generating charge separated states of prolonged lifetimes with adequate amounts of energy. In this dissertation, we report on the design and synthesis of donor–acceptor conjugates with the goal of modulating the yield and lifetime of their charge separated states and hence, improving the conversion of light energy into chemical potential. In simple donor-acceptor systems, generally, the energy and electron transfer events originate from the singlet excited state of the donor or acceptor and can store the …

Metal-organic frameworks (MOFs) have been intensely researched over the past 20 years. In this dissertation, metal-inorganic frameworks (MIFs), a new class of porous and nonporous materials using inorganic complexes as linkers, in lieu of traditional organic linkers in MOFs is reported. Besides novel MIF regimes, the previously described fluorous MOF "FMOF-1", is re-categorized herein as "F-MIF1". F-MIF-1 is comprised of [Ag4Tz6]2- (Tz = 3,5-bis-trifluoromethyl-1,2,4-triazolate) inorganic clusters connected by 3-coordinate Ag+ metal centers. Chapter 2 describes isosteric heat of adsorption studies of F-MIF1 for CO2 at near ambient temperatures, suggesting promise for carbon capture and storage. We then successfully exchanged some of these Ag(I) centers with Au(I) to form an isostructural Au/F-MIF1. Other, nonporous MIFs have been synthesized using Ag2Tz2 clusters with bridging diamine linkers 4,4'-bipyridine, pyrazine, and a Pt(II) complex containing two oppositely-situated non-coordinating pyridines. This strategy attained luminescent products better-positioned for photonic devices than porous materials due to greater exciton density. Chapter 3 overviews work using an entirely inorganic luminescent complex, [Pt2(P2O5)4]4- (a.k.a. "PtPOP") to form new carbon-free MIFs. PtPOP is highly luminescent in solution, but as a solid shows poor quantum yield (QY ~0.02) and poor stability under ambient conditions. By complexing PtPOP to various metals, we have …

The unified learning model (ULM) focuses on students' engagement, motivation, prior knowledge, and working memory. This study employs the use of video games to assess students' learning through a 3D chemistry gaming environment. In this human-subjects research, students carried out missions and applied reasoning to solve problems appropriate for general chemistry content. For learning to occur, students must be engaged and motivated as stated in the ULM. Learning cannot necessarily be accomplished by experience alone, and critical thinking is required to turn the experience into learning. The interpretation of educational theory applied to video games and this proposed study are discussed. A moderately positive correlation was found between exam score and study time (playing the game). Essentially the more time spent playing the game or an online activity the higher the exam scores. There was an alpha level less than 0.05 (p < 0.05) between the experimental group and non-traditional group (no game or online activity). Supporting that there was a statistically significant difference between groups, the null hypothesis was accepted between the game and online activity. Furthermore, as stated under the ULM, engagement is necessary for optimal learning.

As part of the study, photosynthetic system constructs based on BF2-chelated dipyrromethene (BODIPY), BF2-chelated azadipyrromethene (AzaBODIPY), porphyrin, phthalocyanine, oxasmaragdyrin, polythiophene, fullerene (C60), single-walled carbon nanotube and graphene are investigated. Antenna systems of BODIPY dyads and oligomers having BODIPY as an excitation energy donor connected to different acceptors including BODIPY, azaBODIPY, oxasmaragdyrin and aluminum porphyrin are studied. Different synthetic methodologies are used to afford donor-acceptor systems either directly linked with no spacer or with short spacers of varying length and orientation. The effect of donor orientation, donor optical gap as well as nature of donor-acceptor coupling on the donor-acceptor spectral overlap and hence the rate of excitation energy transfer is investigated. In all these systems, an ultrafast energy transfer followed by electron transfer is observed. In particular, in a directly connected BODIPY-azaBODIPY dyad an unusually ultrafast energy transfer (~ 150−200 f) via Förster mechanism is observed. The observation of energy transfer via Förster instead of Dexter mechanism in such closely coupled donor-acceptor systems shows the balance between spatial and electronic coupling achieved in the donor-acceptor system. Moreover, in donor-acceptor systems involving semiconducting 1D and 2D materials, covalently functionalized single-walled carbon nanotubes via charge stabilizing (TPA)3ZnP and noncovalently hybridized exfoliated graphene via …

The increasingly complex world of illicit chemistry has created a need for rapid, selective means of determining the threat posed by new drugs as they are encountered by law enforcement personnel. To streamline this process, the entirety of the problem, from the production of illicit drugs all the way to the final analysis have been investigated. A series of N-alkylated phenethylamine analogues were synthesized in a shotgun method and subjected to direct-infusion analysis. A range of products were detected without the need for time-consuming purification steps, which was extended to novel pharmacological and receptor-binding assays where mass spectrometry is used as a detector. This direct-infusion technique was also applied to studies of methamphetamine and fentanyl production to preemptively determine improvements to common reaction conditions and explore the origins of common impurities. The ability to utilize these rapid techniques directly from the fume hood has also been critically reviewed to highlight gaps in current research and opportunities for improvement. When combined, these studies seek to provide a means for rapid, simplified analysis of illicit drugs to improve the quality of data and dramatically increase throughput.