Currently, DNA profiling is the gold standard to identify an individual. However, determining body fluid origin is important in criminal investigations, offering additional information surrounding the circumstances of a crime. However, crime labs can only definitively identify blood and semen and presumptively saliva using techniques that consume time and sample and do not simultaneously identify all forensically relevant body fluids. This causes many crime labs to want to bypass body fluid identification altogether. Therefore, advances into more definitive molecular-based body fluid methods are necessary. One such technique is mRNA profiling because it provides a highly sensitive and specific approach to definitively identifying all relevant body fluids in parallel. Although advancements have been made, improvements to mRNA profiling methodologies still need to be researched such as 1) possible mRNA recovery from established DNA workflows and 2) possible integration of mRNA profiling into an upfront male DNA screening assay for triaging sexual-assault evidence likely to contain male DNA and reduce/eliminate a significant bottleneck in the standard DNA workflow of microscopic sperm identification. This study was designed to address these two issues by evaluating a novel way to recover RNA, for body fluid identification, from the waste fractions of a PrepFiler™ DNA extraction, and from the DNA extracts directly. Next, this study aimed to provide a relatively quick molecular-based approach for screening sexual-assault evidence. It involves extraction of RNA using the Dynabeads™ mRNA DIRECT™ Kit, while saving the extraction waste fractions for downstream male-DNA quantitation and STR profiling. The RNA is then used in a rapid and sensitive 1-step combined reverse transcription-HRM assay to positively detect the presence of sperm. Both non-conventional co-extraction methods successfully addressed current body fluid identification challenges and allowed for easy integration into existing workflows when single sourced, mixture and mock casework samples were analyzed.

Current methods in ignitable liquid identification and classification from fire debris rely on pattern recognition of ignitable liquids in total ion chromatograms, extracted ion profiles, and target compound comparisons, as described in American Standards for Testing and Materials E1618-10. The total ion spectra method takes advantage of the reproducibility among sample spectra from the same American Society for Testing and Materials class. It is a method that is independent of the chromatographic conditions that affect retention times of target compounds, thus aiding in the use of computer-based library searching techniques. The total ion spectrum was obtained by summing the ion intensities across all retention times. The total ion spectrum from multiple fire debris samples were combined for target factor analysis. Principal components analysis allowed the dimensions of the data matrix to be reduced prior to target factor analysis, and the number of principal components retained was based on the determination of rank by median absolute deviation. The latent variables were rotated to find new vectors (resultant vectors) that were the best possible match to spectra in a reference library of over 450 ignitable liquid spectra (test factors). The Pearson correlation between target factors and resultant vectors were used to rank the ignitable liquids in the library. Ignitable liquids with the highest correlation represented possible contributions to the sample. Posterior probabilities for the ASTM ignitable liquid classes were calculated based on the probability distribution function of the correlation values. The ASTM ignitable liquid class present in the sample set was identified based on the class with the highest posterior probability value. iv Tests included computer simulations of artificially generated total ion spectra from a combination of ignitable liquid and substrate spectra, as well as large scale burns in 20’x8’x8’ containers complete with furnishings and flooring. Computer simulations were performed for each ASTM ignitable liquid class across a range of parameters. Of the total number of total ion spectra in a data set, the percentage of samples containing an ignitable liquid was varied, as well as the percent of ignitable liquid contribution in a given total ion spectrum. Target factor analysis was them performed on the computer-generated sample set. The correlation values from target factor analysis were used to calculate posterior probabilities for each ASTM ignitable liquid class. Large scale burns were designed to test the detection capabilities of the chemometric approach to ignitable liquid detection under conditions similar to those of a structure fire. Burn conditions were controlled by adjusting the type and volume of ignitable liquid used, the fuel load, ventilation, and the elapsed time of the burn. Samples collected from the large scale burns were analyzed using passive headspace adsorption with activated charcoal strips and carbon disulfide desorption of volatiles for analysis using gas chromatography-mass spectrometry

The research presented in this dissertation describes the design and synthesis of substitutional-solid-solution-based multivariate metal-organic frameworks (SSS-based MTV MOFs) with functionalized organic linkers to study their emergent properties in the crystalline solid state. The synthetic versatility and tunability of organic chemistry coupled with the predictable organization of inorganic structures enables MTV MOF systems to further the fundamental understanding of structure-composition-property relationships for the targeted design of applied materials due to their ability to control the structure, composition, and property independently. To begin, a set of terphenyl linkers with varied steric and electronic properties were crystallized as a family of UiO-type MOFs to assess their effects on the uptake and separation of noble gases. This series was then isoreticularly expanded to PEPEP linkers and combined in a PIZOF-type MTV MOF system to evaluate its capability as a multivariate platform for linkers with different functional groups. Chapters 4, 5, and 6 each focus on a different advantageous aspect of the PIZOF system, first exploring the free volume in the pores where covalently bound redox active mediators demonstrate electron diffusion via charge-hopping mechanics to achieve redox conductivity. The next chapter studies the aggregate-induced emission properties that can arise from link-link interactions due to the interpenetrated structure of PIZOF-type frameworks by incorporating a pentacene-based linker in an MTV MOF series to determine its singlet fission potential. The last chapter utilizes the water stability of the PIZOF framework to investigate how increasing pore hydrophilicity through the inclusion of a rationally designed pentaerythritol-containing linker affects the water adsorption. This dissertation demonstrates the value of the SSS-based MTV MOF approach under the paradigm of reticular chemistry to enable the design of tunable and complex solid-state systems with the ability to deconvolute structure from composition and property, while still allowing for relationships between the structure, composition, and property.

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