Hydrous lithium aluminosilicate (L–A–S–H) and lithium aluminate (L–A–H) gels are candidate precursors for glass-ceramics and ceramics with potential advantages over conventional processing routes. However, their structure before calcination remained largely unknown, despite the importance of precursor structure on the properties of the resulting materials. In the present study, it is demonstrated that L–A–S–H and L–A–H gels with Li/Al ≤ 1 can be produced via an organic steric entrapment route, while higher Li/Al ratios lead to crystallization of gibbsite or nordstrandite. The composition and the structure of the gels was studied by thermogravimetric analysis, X-ray diffraction, 27Al and 29Si magic-angle spinning nuclear magnetic resonance, and Raman spectroscopy. Aluminium was found to be almost exclusively in six-fold coordination in both the L–A–H and the L–A–S–H gels. Silicon in the L–A–S–H gels was mainly in Q4 sites and to a lesser extent in Q3 sites (four-fold coordination with no Si–O–Al bonds). The results thus indicate that silica-rich and aluminium-rich domains formed in these gels.

This dissertation explores the innovative integration of optical trapping (OT) with advanced laser spectroscopy techniques to investigate the physicochemical properties of single particles from a variety of atmospheric aerosols, such as bioaerosols, terrestrial dust, and extraterrestrial dust. Each technique offers unique insights, significantly enhancing our understanding of these critical atmospheric components. The first work focuses on employing OT in conjunction with cavity ringdown spectroscopy (OT-CRDS) to measure the single-particle extinction of interplanetary dust particles at ultraviolet wavelengths (~308 nm). This method allows for the stable trapping of individual dust particles in air, facilitating precise characterization with minimal external interference. Our findings illustrate that the integration of OT with cavity ringdown spectroscopy serves as a novel tool for obtaining multimodal information on IDPs, thus providing new avenues for understanding planetary phenomena and their implications for atmospheric science. In the second work of the dissertation, we investigate the capabilities of optical trapping-Raman spectroscopy (OT-RS) for the characterization, identification, and detection of aerosol particles in their native atmospheric states. We constructed a comprehensive library of OT-RS fingerprints from various aerosol categories, including bioaerosols, terrestrial dust, and extraterrestrial dust. This library addresses significant challenges in particle identification and serves as a crucial reference for future atmospheric studies. The advantages of single-particle characterization through OT-RS are highlighted, demonstrating its potential for advancing our understanding of aerosol behavior in the atmosphere. The third study integrates optical trapping with circular intensity differential scattering (OT-CIDS) to analyze single biological particles, highlighting its potential for detecting chiral structures like DNA and RNA. Using a custom-designed elliptical reflector, we achieve optical levitation to measure angle-dependent scattering without interference from surrounding equipment. Our results demonstrate the feasibility of capturing two-dimensional angular optical scattering (TAOS) patterns, revealing distinct angular responses from various levitated particles. In summary, this dissertation presents a groundbreaking interaction between optical trapping and advanced spectroscopic techniques, offering innovative methodologies for studying the intricate properties of single particles in atmospheric science and beyond. The insights gained from this research contribute significantly to our understanding of atmospheric phenomena and open new avenues for particle characterization and environmental monitoring across diverse contexts.

Raman spectroscopy is often used for material identification but may be used for characterization. This document focuses on using Raman measurements to characterize polymers, specifically the curing and aging mechanism for hydroxyl-terminated polybutadiene (HTPB). HTPB is a well-known elastomer used in sealants, non-slip surfaces, rocket repellants and plastic explosives. Raman spectroscopy was used to monitor urethane linkages that form from curing HTPB with a cyanate curing agent to suggest a curing mechanism for HTPB. Since this polymer is highly susceptible to oxidation, the methods used to characterize curing were also used for the aging process to see if urethane breakages could be observed. Raman measurements were compared to elongation-at-break measurements to assess the short-term aging process. Results showed that oxidation of the urethane linkage seemed to be the primary source of degradation during early thermal aging. Patterns seen in Raman data may be studied to suggest an oxidation mechanism at the urethane site as a starting point to unravel the network of aging mechanisms for HTPB. Additionally, a recently published mount design is discussed for sustained tensile strain. The mount setup was used to mechanically extend samples while taking real-time spectroscopic data. Testing for the mount was done on HTPB and high-density polyethylene, but the design may accommodate a large variety of materials and is compatible with many spectroscopic methods including Raman spectroscopy.

Geochemistry plays a vital role in our understanding mechanisms behind major geological systems such as the Earth's crust and its oceans (Albarède, F. 2003). More recently, geo-chemistry has played a vital role in the field of forensic investigation and in period dating. Forensic soil samples have been traditionally analysed via examinations of colour, texture and mineral content by physical or chemical methods. However, these methods leave any organic or water-soluble fractions unexamined. Tephrochronology (the dating of sedimentary sequences using volcanic ash layers) is an important tool for the dating and correlation of sedimentary sequences containing archives and proxies of past environmental change. Its importance in this area has increased since the increased free carbon in out atmosphere has made radio-carbon dating unreliable. Tephrochronology requires successful geo-chemical identification of the tephras, a method reliant on electron probe micro-analysis (EPMA) to analyse major element composition. However, it is often impossible to differentiate key tephra layers using EPMA alone. Raman spectroscopy is commonly used in chemistry, since vibrational information is specific to the chemical bonds and symmetry of molecules, and can provide a fingerprint by which these can be identified. Here, we demonstrate how Raman spectroscopy can be used for the successful discrimination of mineral species in tephra through the analysis of individual glass shards. We further demonstrate how, with the use of oxidative preparation methods, Raman spectroscopy can be used to successfully discriminate between soil types using mineralogy as well as the organic and water-soluble fractions of soils.

The regulations of many food products in the United States have been made and followed very well but unfortunately some products are not put under such rigorous standards as others. This leads to products being sold, that are thought to be healthy, but in reality contain unknown ingredients that may be hazardous to the consumers. With the use of several instrumentations and techniques the detection, characterization and identification of these unknown contaminates can be determined. Both the AZ-100 and the TE2000 inverted microscope were used for visual characterizations, image collection and to help guide the extraction. Direct analyte-probed nanoextraction (DAPNe) technique and nanospray ionization mass spectrometry (NSI-MS) was the technique used for examination and identification of all adulterants. A Raman imaging technique was than introduced and has proven to be a rapid, non-destructive and distinctive way to localize a specific adulterant. By compiling these techniques then applying them to the FDA supplied test samples three major adulterants were detected and identified.

Graphene is one of the most important low dimensional materials. Ever since the inception of graphene, attempts to scale up production of graphene have never stopped. Chemical vapor deposition synthesis of graphene on copper is one of the most promising pathways. However, the poor quality of CVD-derived graphene has hindered synthetic graphene for large scale basic science and commercial applications. The lack of reproducibility of CVD graphene research, and the inferior quality of CVD graphene points to potential hidden variables and misunderstanding of the graphene CVD process. In this thesis, it is identified that trace oxygen is a key factor in determining the quality and growth trajectory for graphene grown by low-pressure CVD. By innovative design in the CVD system layout and meticulous control over the substrate quality, it is demonstrated that by eliminating oxygen below µTorr level in the growth chamber, high quality graphene comparable to exfoliated graphene can be obtained. The ultrahigh graphene quality is showcased by a combination of Raman spectroscopy, electrical transport measurement and various scanning probe techniques including scanning tunneling microscopy (STM) and atomic force microscopy (AFM). Moreover, a graphite-gated device encapsulated by hexagonal boron nitride (h-BN) shows well developed fractional quantum hall effect. Using the oxygen free CVD (OF-CVD) system as a platform, the effect of oxygen is revealed to be inducing etching effect at the µTorr limit. Addition of hydrogen delays the etching effect with reduced graphene growth rate. At high hydrogen concentrations, µTorr-level of oxygen is found to be inducing amorphous carbon contaminations to the graphene surface, at the same time, the quality of the resulting graphene deteriorates with increasing level of oxygen, as characterized by AFM, XPS, Raman spectroscopy and electrical transport measurements. OF-CVD enables unprecedented tunability of the graphene growth behavior in terms of growth rate and nucleation density. Controlled experiments reveal the individual effect of all experimental parameters such as temperature, and partial pressure of methane and hydrogen are studied. Their effect on the initial growth rate of graphene can be modeled by a compact model based on competitive adsorption of methane and hydrogen onto the copper surface. The mechanism of overall coverage-time evolution is further revealed by phase-field modeling. Collectively, the theoretical insights of the CVD process of graphene pave way for graphene synthesis by design. The underlying mechanism and principles provide insights for understanding and optimizing other 2D materials growth mediated by catalytic substrates.

<p>Chromatography is a powerful technique, essential in chemical analyses and preparative separation in industry and research. Many different kinds of chromatographic material are needed, due to the large variety of applications. Detailed methods of characterisation are needed to design new chromatographic materials and understand their properties. In this thesis, confocal Raman spectroscopy and surface enhanced Raman spectroscopy (SERS) have been applied to micrometer-size chromatographic beads, for which these techniques have not been used earlier. New methodology, optimized for use with the chromatographic beads, has been developed and evaluated. </p><p>Confocal spectroscopy has been used to determine distributions of functional groups within single chromatographic beads. This distribution is of great importance in determining the chromatographic properties, since the material is porous and the solute molecules can diffuse inside the beads. Most of the confocal experiments have been performed with Raman spectroscopy; fluorescence spectroscopy, using Nd³⁺ ions or dye-labelled proteins as fluorescence probes, has been used for comparison. </p><p>The concentration of adsorbed analytes is very low within the beads. SERS was therefore used to enhance the Raman signal. SERS-active surfaces were prepared by incorporating gold nano-particles into the interior of the bead. TEM measurements showed that the gold nano-particles could be observed throughout, and it was possible to record analyte spectra from different positions within the bead. Enhanced spectra could be obtained both for small test molecules and for larger bio-molecules, although the spectra for the smaller analytes were much more intense.</p>

Chromatography is a powerful technique, essential in chemical analyses and preparative separation in industry and research. Many different kinds of chromatographic material are needed, due to the large variety of applications. Detailed methods of characterisation are needed to design new chromatographic materials and understand their properties. In this thesis, confocal Raman spectroscopy and surface enhanced Raman spectroscopy (SERS) have been applied to micrometer-size chromatographic beads, for which these techniques have not been used earlier. New methodology, optimized for use with the chromatographic beads, has been developed and evaluated. Confocal spectroscopy has been used to determine distributions of functional groups within single chromatographic beads. This distribution is of great importance in determining the chromatographic properties, since the material is porous and the solute molecules can diffuse inside the beads. Most of the confocal experiments have been performed with Raman spectroscopy; fluorescence spectroscopy, using Nd3+ ions or dye-labelled proteins as fluorescence probes, has been used for comparison. The concentration of adsorbed analytes is very low within the beads. SERS was therefore used to enhance the Raman signal. SERS-active surfaces were prepared by incorporating gold nano-particles into the interior of the bead. TEM measurements showed that the gold nano-particles could be observed throughout, and it was possible to record analyte spectra from different positions within the bead. Enhanced spectra could be obtained both for small test molecules and for larger bio-molecules, although the spectra for the smaller analytes were much more intense.

Polycrystalline Zn1-xCrxO (0.01 ≤ x ≤ 0.09) samples synthesized by solid state reaction technique were sintered at different temperatures following slow step sintering schedule. Structural, micro-structural, optical, magnetic properties and homogeneity were investigated using suitable characterisation techniques. Cr2O3 and CrO2 phases have been detected in the XRD patterns and Raman spectra of Zn1-xCrxO samples with x ≥ 0.05. Photoluminescence study has indicated improved optical property of the samples compared to undoped ZnO. While low percentage Cr doped samples showed diamagnetic behaviour, higher percentage doped samples (≥ 5%) exhibited ferromagnetic, paramagnetic and anti-ferromagnetic behaviours depending upon the sintering temperatures. The magnetic properties have been analysed through Electron Spin Resonance study. A g-value of 1.97 indicates Cr in +3 valence state in doped ZnO system. Presence of Cr3+ and Cr4+ in ZnO is understood to facilitate super exchange interactions to promote ferromagnetism at room temperature. ESR study shows improved magnetic homogeneity achieved by slow step sintering process. / Physics / M. Sc. (Physics)

Over the last century, despite enormous advancements in biomedical research and the development of sophisticated analytical instruments many diseases continue to be a burden on humankind particularly on the aged. This is because of a lack of complete understanding of the pathogenesis and specific therapies. Due to the complexity involved, we need to explore all facets of diagnosis and therapies. Therefore, there is a requirement for different strategies to combat these diseases. A quick diagnosis is the primary step towards improving treatment and increasing the chance of survival. To realize this goal we entail to monitor multiple biomarkers which will also help us to understand the progression of disease. Mid-Infrared (MIR) and Raman spectroscopic techniques are well established analytical methods to understand the molecular structure and chemical composition of heterogeneous systems. These techniques are rapid, non-destructive and offer multiple component analysis (global/multiplex) in a single measurement without any labels. Importantly, biological materials like proteins, carbohydrates, lipids, nucleic acids etc. have unique structures and therefore we can obtain unique spectral fingerprints of these molecules in different physiological and pathological conditions. This will provide a potential route to obtain diagnostic markers for diseases. Also, to improve the ability to diagnose and treat human diseases much more efficiently, understanding the mechanisms involved in the progression of disease is necessary. It would be time consuming and often unethical to perform these studies directly on humans. Therefore, there is a need for model organisms to explore the complexity of various diseases. A model organism is an animal, plant or microbe that is being studied to understand a range of biological phenomena. They should meet certain criteria such as short life cycles, easy to breed and maintain in large numbers under laboratory conditions, and the data generated through use of the model should be applicable to other higher organisms like humans. The microbial system, mouse, rat, Drosophila (fruitfly), C Elegans (nematode worm) and zebrafish are being used extensively for this purpose. The most adaptable organisms to study diseases in humans are the mice as they share almost 99% of their genes with humans. Mice are similar to humans in most physiological and pathological features such as nervous, cardiovascular, immune, liver etc. In addition to mice, Drosophila melanogaster (fruitfly) has been used for years as an attractive model organism to understand the mechanisms of underlying human diseases. This is because 75% of human disease genes have counterparts in Drosophila and it meets the above mentioned criteria to be a model organism. It also plays an important role for studying genetics and development biology. The average life span of Drosophila is 60-80 days; therefore it is a suitable model to study age related diseases. In the present thesis, the ability to probe low-micrometer domains using Raman and Fourier Transform Infrared (FTIR) microspectroscopy was utilized to monitor the chemical changes during various biomedical conditions using model systems. Chapter 1 of the thesis discusses about the origin of Raman and FTIR microspectroscopy along with instrumentation and applications. Various data analysis methods (both univariate & multivariate) and the validation criterion are described in chapter 2. Depending on the objective of the study and based on the technique (Raman or FTIR) used, one (or more) of these methods can be applied for effective interpretation of the data. Further, the thesis includes four different investigations; a) the FTIR spectroscopic study of hepatotoxicity due to acetaminophen using mice as model, b) the Raman spectroscopic studies of muscle-related disorders using Drosophila as a model, c) Vibrational spectroscopic study of septic shock using mice as model, d) Surface Enhanced Raman Spectroscopy (SERS) study of serum components using Lab-on-a-chip (LOC). The first part comprises mainly the FTIR microspectroscopy study of hepatotoxicity in mice post oral dosing of acetaminophen (paracetamol), which is extensively used worldwide as an analgesic and antipyretic drug (chapter 3). The infrared spectra of acetaminophen treated livers in BALB/c mice show a decrease in glycogen and an increase in amounts of cholesteryl esters and DNA. Importantly, analysis of sera identified the lowering of glycogen and increase in DNA and chlolesteryl esters earlier than the increase in alanine aminotransferase, which is routinely used to diagnose liver damage. Similar changes are also observed in C57BL/6 and Nos2−/− mice. Revert experiments using an antidote (L-methionine) demonstrate that depletion in glycogen and increase in DNA are abrogated with pre-treatment, but not post-treatment, with L-methionine. In the second study Raman spectroscopy is applied to discriminate between various muscle defects in Drosophila, since it can provide a unique molecular fingerprint of tissues on the basis of their biochemical composition (chapter 4). Raman spectra were collected from Indirect Flight Muscles (IFM) of mutants upheld1 (up1), heldup2 (hdp2), Myosin heavy chain7 (Mhc7), Actin88FKM88 (Act88FKM88), upheld101 (up101) and Canton-S (CS) for both 2 and 12-days old flies. The difference spectra (mutant minus CS) of all mutants have shown an increase in nucleic acids (DNA/RNA) content along with an increase in β-sheet and/or random coil content at the expense of α-helix. Interestingly, 12th day sample of up1 & Act88FKM88 exhibit significantly higher levels of glycogen and carotenoids than CS. A Principal Components based Linear Discriminant Analysis (PC-LDA) classification model was developed, which classifies the mutants according to their pathophysiology and yielded overall accuracy (OA) of 97% and 93% for 2 and 12-days old flies respectively. up1 & Act88FKM88 (nemaline myopathy phenotypes) form a group which is clearly separated in a Linear Discriminant (LD) Plane from up101 & hdp2 (cardiomyopathy phenotypes). In the third part we investigated septic shock, a life threatening condition associated with multiple organ dysfunctions, in mice (chapter 5). Salmonella typhimurium were given to BALB/c and 129/SvJ mice via the intraperitoneal route to induce infection. Liver, spleen and sera samples were studied using FTIR microspectroscopy. The infrared spectra of liver, spleen and serum samples in BALB/c (Nramp1-deficient) mice show significant spectral changes as early as 1 hour post infection but spleen shows changes only after 6 hour. Interestingly, 129/SvJ (Nramp1-sufficient) mice were resistant to sepsis and show significant spectral changes only at 12 hour post infection. This study demonstrates that suppression of Nramp-1, a renowned gene known to control susceptibility to infections by intracellular bacteria can be an effective cure for sepsis. The final study presented in this thesis demonstrates the use and benefits of lab-on-a-chip (LOC) devices in surface enhanced Raman spectroscopy (SERS) which is used to enhance the weak Raman signals (chapter 6). Most of the diseases have related proteins or analytes present in serum although in early stages their concentration in blood are low. The idea is to detect at low concentration using SERS the serum components which are related to progression of disease. Here, we have compared the effect of different aggregating agents on silver colloids and the resulting enhancement in Raman signals for tryptophan and Bovine Serum Albumin (BSA). Reproducibility issues, the key concern of static phase SERS, can be overcome by performing SERS spectroscopic measurements in automated flow cells. Further, pyridine and tryptophan were used to demonstrate SERS in a segmented flow system. The spectra from different drops were compared and demonstrate the high reproducibility in comparision to static SERS. Lastly, chapter 7 summarizes the entire work of the present thesis with future prospects of Raman and FTIR microspectroscopy to study the progression mechanism of various diseases like neurodegenerative diseases which is easy to follow in drosophila due to their short life span. Also, technological developments in the field of nanotechnology and micro-fluidics will enable the detection of early biochemical changes in bodily fluids such as urine, cerebral spinal fluid, tears etc. Building on the results demonstrated in this thesis, hopefully label-free vibrational (Raman and FTIR) microspectroscopic studies using model organisms would help in understanding the underlying mechanisms of progression of various other diseases which in turn would facilitate the development of effective therapies.