Indiana University-Purdue University Indianapolis (IUPUI)

Blood is one of the most common biological fluids encountered at crime scenes and is therefore constantly being tested for in the laboratory. Confirming the presence of blood can illuminate essential elements of a case as well as allow for identification via downstream DNA analysis. This significant investigative value is why it is crucial to use robust forensic testing techniques for blood detection. In the forensic laboratory, blood is identified using serological techniques. A presumptive test, such as a colorimetric test, is performed first. A confirmatory test, such as an immunochromatographic assay, is often performed following a presumptive positive result. While both types of tests have numerous advantages, they have several limitations as well. These limitations have served as the basis for exploring alternative techniques for forensic blood detection, such as FTIR. FTIR spectroscopy is a qualitative, non-destructive, confirmatory analytical technique. This technique uses infrared light to characterize organic compounds based on molecular structure. There are also several different FTIR techniques, such as ATR and DRIFTS. ATR-FTIR analysis has been widely researched for the detection of blood and other biological fluids, across several applications. ATR-FTIR may be preferable to serological blood detection because it can be quicker than combined serological blood testing, it requires minimal sample preparation, it does not damage DNA downstream, and it can detect multiple biological fluids at once. Despite all the advantages that ATR-FTIR analysis has over traditional forensic blood techniques, it has not yet been implemented in casework. This may be due to skepticism in using subjective and complex spectroscopic data that results from ATR-FTIR analysis of body fluids. The initial objective of this research was to develop an optimized protocol using ATR-FTIR and chemometric analysis to identify blood on cotton round substrates. Using these techniques together would allow for a rapid, nondestructive, confirmatory approach, that would be more objective than serological testing or FTIR analysis alone. However, due to complications throughout the research process, this objective was altered. The revised objective was to develop an optimized protocol using DRIFTS and chemometric analysis to identify blood on cotton round substrates. An optimized DRIFTS protocol for forensic blood identification was successfully developed. Blood samples from multiple donors were tested using this protocol, and all samples showed similar data. Human biological samples other than blood as well as non-human samples were also tested. These samples showed dissimilar data from the donors’ blood sample data. Chemometric analysis was then performed using AnalyzeIQ Lab software. After testing 93 pair-wise combinations of pre-processing methods and algorithms, a model was developed. Unfortunately, this model was not completely optimized. It had a 9.09% error rate, resulting from the misclassification of one sample. Future research is needed before implementation into casework. Alternative cotton substrates and data collection software should be considered. Additional time should be spent using AnalyzeIQ Lab software, to develop a model with a 0% error rate. If this cannot be achieved, an alternative chemometric analysis software should be considered.

Coil coatings are durable  organic coatings used to protect metal sheets from corrosion and improve their aesthetic properties. Because of their extensive use, coil coatings have long been of interest for industrial and academic researchers. This interest has recently been furthered by a societal push towards the replacement of fossil-based raw materials with alternatives that are biobased and renewable. The aim of this licentiate thesis is to demonstrate how analyses on the macro-, micro-, and nanoscale can be used to better understand the degradation process of polyester-based coil coatings. The included manuscripts showcase methods for evaluating and comparing different coil coating formulations and for verifying accelerated weathering techniques. Multiple techniques, focusing on infrared (IR) spectroscopy and atomic force microscopy (AFM), were used to analyze coating systems before and after different types of weathering. IR data acquired from techniques without spatial resolution, such as attenuated total reflection (ATR) and photoacoustic spectroscopy (PAS) have been expanded upon with spatially resolved focal plane array (FPA) and s-SNOM  (scattering-type scanning near-field optical microscopy) measurements. Spatially resolved chemical data of coating cross sections were acquired and used to assess how the degradation at the surface and in the bulk was related. Additionally, differences between the degradation behavior of a standard fossil-based coating and a similar coating with biobased components as well as differences between the degradation caused by artificial and natural weathering was discussed. Nanoscale mechanical measurements of simplified coating surfaces showed that weathering increased nanomechanical stiffness and led to homogenization of mechanical properties on the local level. In addition, measurements with nanoscale FTIR correlated with macroscale FTIR. Even relatively minor changes in band intensities could be tracked on a local scale. Although the simplified samples were chemically homogeneous, nanoscale FTIR shows great promise for the assessment of local degradation of full systems. / Bandlackering är en process för att applicera stabila organiska beläggningar på metallytor för att skydda från korrosion och förbättra deras utseende. På grund av beläggningarnas omfattande användning så har utvärdering och analys av dem varit av intresse för både akademi och industri i flera årtionden. Detta långvariga intresse har ytterligare främjats av en ökade miljömedvetenhet och ett tryck att ersätta miljöfarliga och fossila råmaterial mot biobaserade och förnyelsebara alternativ. Målet med denna licentiatavhandling är att visa hur analysmetoder på makro-, mikro-, och nanonivå kan användas för att bättre förstå nedbrytning av bandlackerade beläggningar. Denna förståelse kan användas både för att utvärdera prestandan hos både nya redan befintliga system, men också för att kunna verifiera accelererade testmetoder vars mål är att minska tiden som krävs för utvärdering. Flera tekniker, med fokus på infraröd (IR) spektroskopi och atomkrafts-mikroskopi  (AFM) använts för att analysera beläggningar före och efter att de blivit utsatta för olika typer av aggressiva miljöer. Spektroskopiska data utan spatial upplösning som attenuerad totalreflektions FTIR (ATR) och fotoakustisk spektroskopi (PAS) har kompletterats med spatialt upplösta fokalplans array (FPA) och s-SNOM mätningar. Kemisk information med spatial upplösning har använts för att utvärdera hur nedbrytningen nära ytan relaterade till nedbrytningen längre ner i beläggningen. Likheter och skillnader i nedbrytningen som skedde i en standardbeläggning och ett system med biobaserade additiv jämfördes efter både väderbestendighets-testning som skedde utomhus och i labb. Skillnader mellan dessa exponeringsmetoder diskuterades också. Nanomekanisk analys med hjälp av atomkraftsmikroskopi användes för att bestämma lokala förändringar av mekaniska egenskaper i förenklade klarlacker. Mätningarna visade att exponeringar i aggressiva miljöer leder till en lokal homogenisering av mekaniska egenskaper och ökad styvhet. Utöver detta så utvärderades likheter och skillnader mellan FTIR spektra som tagits på makro- och nanonivå. Dessa mätningar gav lovande resultat för fortsatta ytanalyser. / <p>QC 2023-05-15</p>

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The broad use of plastics has resulted in the increase in both production and consequent plastic pollution in the environment. Microplastics, defined as particles &lt; 5 mm, is of special interest because of its wide existence in environment and potential hazards to our ecosystem. The degradation of microplastics can be studied using Fourier Transform Infrared spectroscopy (FTIR), where the optical absorption of different functional groups in a molecule can be detected and used for identification. By studying the change in intensity or peak area of certain functional groups (such as carbonyl, hydroxyl, or vinyl) in the spectrum, the degradation of microplastics can be quantified. In the past decades, carbonyl index (intensity or area change of carbonyl group in FTIR spectra), has been applied as a quantitative probe to monitor the extent of plastics degradation. However, the analysis of FTIR spectra requires expertise and comparison between different reports are often difficult due to non-standardized methods. Therefore, an automated method is urgently needed to ease the difficulty. This project has developed a program that automates and standardizes the analysis of the spectrum. The program calculates an index by using specified area under the band corresponding to a functional group peak and a reference peak. By comparing the indexes over time, degradation can be quantified. Additionally, poly(vinyl chloride) (PVC) particles were subjected to a heterogeneous photo-Fenton process for 116 hours to obtain data of microplastics degradation. Both optical imaging and FTIR were used to characterize the degradation of PVC, on aspects of size reduction and band changes, respectively. The obtained FTIR data were fed into the developed program to calculate carbonyl index, and the result suggests a degradation of the PVC particles. This implies that the program can effectively reduce the time of analysis for researchers and evaluate and/or calculate the degradation of plastics.

Nanocrystalline metal/metal oxide is an important class of transparent and electronic materials due to its potential use in many applications, including gas sensors. At the nanoscale, many of the phenomena observed that give nanocrystalline semiconducting oxide enhanced performance as a gas sensor material over other conventional engineering materials is still poorly understood. This study is aimed at understanding the low temperature electrical and chemical properties of nanocrystalline SnO2 that makes it suitable for room temperature gas detectors. Studies were carried out in order to understand how various synthesis methods affect the surfaces on the nano-oxides, interactions of a target gas (in this study hydrogen) with different surface species, and changes in the electrical properties as a function of dopants and grain size. A correlation between the surface reactions and the electrical response of doped nanocrystalline metal-oxide-semiconductors exposed to a reducing gas is established using Fourier Transform Infrared (FTIR) Spectroscopy attached to a specially built custom designed catalytic cell. First principle calculations of oxygen vacancy concentrations from absorbance spectra are presented. FTIR is used for effectively screening of these nanostructures for gas sensing applications. The effect of processing temperature on the microstructural evolution and on the electronic properties of nanocrystalline trivalent doped-SnO2 is also presented. This study includes the effect of dopants (In and Ce) on the growth of nano-SnO2, as well as their effects on the electronic properties and gas sensor behavior of the nanomaterial at room temperature. Band bending affects are also investigated for this system and are related to enhanced low temperature gas sensing. The role and importance of oxygen vacancies in the electronic and chemical behavior of surface modified nanocrystalline SnO2 are explored in this study. A generalized explanation for the low temperature gas sensor behavior of nanocrystalline oxide is presented that can be generalized to other nano-oxide systems and be useful in specific engineering of other nanomaterials. Deeper understanding of how nano-oxides react chemically and electronically would be extremely beneficial to issues present in current low cost, low temperature sensor technology. Ability to exactly monitor and then engineer the chemistry of nanostructures in the space charge region as well as the surface is also of great significance. Knowledge of the mechanisms responsible for enhanced sensor response in this material system could viably be applied to other material systems for sensor applications.

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The prevention of waterborne diseases requires rapid detection of pathogens in drinking water, with an ultimate goal of in-line monitoring in real time. Standard cultivation-based methods are too time-consuming and thus not suitable for this purpose. Many technologies were proposed to achieve this goal, such as ELISA, PCR, FISH, FTIR and flow cytometry. However, they still have limitations of non-specificity, complexity and high cost. Therefore, an optical system is proposed and developed towards the in-line monitoring of bacteria, which combines the advantages of FTIR and micro-flow cytometer for bacterial identification and precise quantification. The in-line use requires obtaining IR spectra of bacterial cells directly in water, which is achieved using a CaF2 liquid cell. The spectra of a series of bacterial samples are collected and analyzed using principal component analysis for their differentiation. A preliminary study on fabricating a CaF2 concentrator is conducted, in which a novel phenomenon on stress release of silicon nitride film on CaF2 substrate is discovered and studied. To determine the concentration of bacteria in drinking water, a micro-flow cytometer is built based on a micro-fabricated device that integrates on-chip beam-shaping optics and microfluidic channels. With this micro-flow cytometer and optimized data analysis for counting particles in real time, linearity with correlation coefficient of over 0.99 is achieved for the dependences of throughput on both volumetric flow rate and concentration of sample. With a one-dimensional hydrodynamic focusing, no degradation of the counting efficiency is demonstrated when the focused sample stream expands. The high accuracy of counting makes this micro-flow cytometer a promising candidate for low concentration applications. Counting of E. coli DH5α cell suspensions in phosphate buffered saline is performed using the micro-flow cytometer. Side-scattered light signals are used to count the E. coli cells. A detection efficiency of 92% is achieved when compared with the expected count from a haemocytometer. It is demonstrated that E. coli can be easily distinguished from beads of similar sizes (2-4µm) as their scattering intensities are different. / Thesis / Doctor of Philosophy (PhD)

The increase in antibacterial resistance has placed the issue of microbial multi-drug resistance on a global stage (Gurunathan, 2019). This issue poses a threat to human and animal health as well as to the environment (Aslam et al., 2018). It affects not only the efficacy of treatment but also how those treatments are conducted (Friedman, Temkin, & Carmeli, 2016). As a result of this ongoing threat, new treatments that have potent effects on bacteria are necessary. One scientific response to this issue has been the development of multifunctional nanoparticles (NPs)(H. Wang et al., 2018). NPs have the ability to be utilized by its varying modes of action and compatibility with other forms of treatments (Alavi & Rai, 2019). This advantage, when successful, would allow for the lowering of dosage and frequency of treatments required to achieve bacteria-killing (Alavi & Rai, 2019). Despite a plethora of proposed designs for the improvement of antibacterial treatment, questions remain concerning the mode of action of these new agents. The aim of this study is to develop a protocol facilitating the identification of modes of action of newly formulated antibacterial agents. Our hypothesis is that different modes of action will have distinct effects on the morphology and composition of the cells. To test this, we characterized the structural, physical and molecular changes of a model system, E. coli., before and after treatments using antibiotics with known modes of action. We selected two bactericidal antibiotics: colistin which is a membrane disrupting antibiotic, and streptomycin which is a protein inhibiting antibiotic (Santo-Domingo, Chareyron, Broenimann, Lassueur, & Wiederkehr, 2017; Sun et al., 2019; Thummeepak, Kitti, Kunthalert, & Sitthisak, 2016). We discuss the protocol development and the significant differences observed in the bacterial responses as well as the limitations of the envisioned approach. We conclude by providing a perspective of the impact our findings are expected to have on evaluating new engineers NP treatments.