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(1 - 8 of 8)
- Title
- Forensic Application of Chemometric Analysis to Visible Absorption Spectra Collected from Dyed Textile Fibers.
- Creator
-
Flores, Alejandra, Sigman, Michael, Yestrebsky, Cherie, Campiglia, Andres, Chumbimuni Torres, Karin, Ni, Liqiang, University of Central Florida
- Abstract / Description
-
Forensic analysis of evidence consists of the comparison of physical, spectroscopic, or chemical characteristics of a questioned sample to a set of knowns. Currently, decisions as to whether or not the questioned sample can be associated or grouped with the knowns are left up to the discretion of the forensic analyst. The implications of these outcomes are presented as evidence to a jury in a court of law to determine if a defendant is guilty of committing a crime or not. Leading up to, and...
Show moreForensic analysis of evidence consists of the comparison of physical, spectroscopic, or chemical characteristics of a questioned sample to a set of knowns. Currently, decisions as to whether or not the questioned sample can be associated or grouped with the knowns are left up to the discretion of the forensic analyst. The implications of these outcomes are presented as evidence to a jury in a court of law to determine if a defendant is guilty of committing a crime or not. Leading up to, and since, the publication of the National Academy of Sciences (NAS) report entitled (")Strengthening Forensic Science in the United States: A Path Forward,(") the inadequacies of allowing potentially biased forensic opinion to carry such weight in the courtroom have been unmasked. This report exposed numerous shortcomings in many areas of forensic science, but also made recommendations on how to fortify the discipline. The main suggestions directed towards disciplines that analyze trace evidence include developing error rates for commonly employed practices and evaluating method reliability and validity.This research focuses on developing a statistical method of analysis for comparing visible absorption profiles collected from highly similarly colored textile fibers via microspectrophotometry (MSP). Several chemometric techniques were applied to spectral data and utilized to help discriminate fibers beyond the point where traditional methods of microscopical examination may fail. Because a dye's chemical structure dictates the shape of the absorption profile, two fibers dyed with chemically similar dyes can be very difficult to distinguish from one another using traditional fiber examination techniques. The application of chemometrics to multivariate spectral data may help elicit latent characteristics that may aid in fiber discrimination.The three sample sets analyzed include dyed fabric swatches (three pairs of fabrics were dyed with chemically similar dye pairs), commercially available blue yarns (100% acrylic), and denims fabrics (100% cotton). Custom dyed swatches were each dyed uniformly with a single dye whereas the dye formulation for both the yarns and denims is unknown. As a point for study, spectral comparisons were performed according to the guidelines published by the Standard Working Group for Materials Analysis (SWGMAT) Fiber Subgroup based on visual analysis only. In the next set of tests, principal components analysis (PCA) was utilized to reduce the dimensionality of the large multivariate data sets and to visualize the natural groupings of samples. Comparisons were performed using the resulting PCA scores where group membership of the questioned object was evaluated against the known objects using the score value as the distance metric. Score value is calculated using the score and orthogonal distances, the respective cutoff values based on a quantile percentage, and an optimization parameter, ?. Lastly, likelihood ratios (LR) were generated from density functions modelled from similarity values assessing comparisons between sample population data. R code was written in-house to execute all method of fiber comparisons described here. The SWGMAT method performed with 62.7% accuracy, the optimal accuracy rate for the score value method was 75.9%, and the accuracy rates for swatch-yarn and denim comparisons, respectively, are 97.7% and 67.1% when the LR method was applied.
Show less - Date Issued
- 2015
- Identifier
- CFE0005613, ucf:50212
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005613
- Title
- ANALYTICAL POTENTIAL OF POLYMERIZED LIPOSOMES BOUND TO LANTHANIDE IONS FOR QUALITATIVE AND QUANTITATIVE ANALYSIS OF PROTEINS.
- Creator
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Santos, Marina, Campiglia, Andres, University of Central Florida
- Abstract / Description
-
One of the intriguing features of biological systems is the prevalence of highly selective and often very strong interactions among different cellular components. Such interactions play a variety of organizational, mechanical, and physiological roles at the cellular and organism levels. Antigen-antibody complexes are representative examples of highly selective and potent interactions involving proteins. The marked specificity of protein-antibody complexes have led to a wide range of...
Show moreOne of the intriguing features of biological systems is the prevalence of highly selective and often very strong interactions among different cellular components. Such interactions play a variety of organizational, mechanical, and physiological roles at the cellular and organism levels. Antigen-antibody complexes are representative examples of highly selective and potent interactions involving proteins. The marked specificity of protein-antibody complexes have led to a wide range of applications in cellular and molecular biology related research. They have become an integral research tool in the present genomic and proteomic era. Unfortunately, the production of selective tools based on antigen-antibody interactions requires cumbersome protocols. The long term goal of this project explores the possibility of manipulating liposomes to serve as the chemical receptors ("artificial antibodies") against selected proteins. Cellular lipids (e.g., lipid rafts) are known to facilitate highly selective binding of proteins on cell membranes. The binding of proteins to cell membranes can be envisaged to be modulated via interactions between polar (charged) and non-polar head groups of lipids and the complementary amino acid residues of proteins. Their interaction is facilitated by a combination of van der Waals, electrostatic, hydrogen bonding and hydrophobic forces. A further interesting aspect of the above interaction is the "fluidity" of the membrane resident lipids, which can migrate from other regions to further enhance the complementary interactions of proteins on the initially "docked" membrane surface. With these features in mind, the end goal of this project is expected to deliver lipid-based chemical receptors "synthetically" designed against proteins to function as "artificial antibodies". Protein sensing will be accomplished with lipid receptors assembled in templated polymerized liposomes. The research presented here specifically focus on the analytical aspects of protein sensing via polymerized liposome vesicles. Lanthanide ions (Eu3+ and Tb3+) are incorporated into polymerized liposome with the expectation to "report" quantitative and qualitative information on the interacting protein. Our proposition is to extract quantitative and qualitative information from the luminescence intensity and the luminescence lifetime of the lanthanide ion, respectively. A thorough investigation is presented regarding the analytical potential of these two parameters for protein sensing. Two chemometic approaches - namely partial least squares (PLS-1) and artificial neural networks (ANN) - are compared towards quantitative and qualitative analysis of proteins in binary mixtures.
Show less - Date Issued
- 2007
- Identifier
- CFE0001373, ucf:46999
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001373
- Title
- The Application of Chemometrics to the Detection and Classification of Ignitable Liquids in Fire Debris Using the Total Ion Spectrum.
- Creator
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Lewis, Jennifer, Sigman, Michael, Campiglia, Andres, Clausen, Christian, University of Central Florida
- Abstract / Description
-
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...
Show moreCurrent 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. 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.
Show less - Date Issued
- 2011
- Identifier
- CFE0004477, ucf:49301
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004477
- Title
- Solid Phase Extraction Room Temperature Fluorescence Spectroscopy for the Direct Quantification of Monohydroxy Metabolites of Polycyclic Aromatic Hydrocarbons in Urine Samples.
- Creator
-
Calimag, Korina Jesusa, Campiglia, Andres, Belfield, Kevin, Yestrebsky, Cherie, Chumbimuni Torres, Karin, Schulte, Alfons, University of Central Florida
- Abstract / Description
-
Polycyclic aromatic hydrocarbons (PAH) are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. Because many of them are highly suspect as etiological agents in human cancer, chemical analysis of PAH is of great environmental and toxicological importance. Current methodology for PAH follows the classical pattern of sample preparation and chromatographic analysis. Sample preparation pre-concentrates PAH, simplifies matrix composition, and...
Show morePolycyclic aromatic hydrocarbons (PAH) are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. Because many of them are highly suspect as etiological agents in human cancer, chemical analysis of PAH is of great environmental and toxicological importance. Current methodology for PAH follows the classical pattern of sample preparation and chromatographic analysis. Sample preparation pre-concentrates PAH, simplifies matrix composition, and facilitates analytical resolution in the chromatographic column. Among the several approaches that exist to pre-concentrate PAH from water samples, the Environmental Protection Agency (EPA) recommends the use of solid-phase extraction (SPE). High-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS) are the basis for standard PAH identification and determination. Ultraviolet (UV) absorption and room temperature fluorescence detection are both widely used in HPLC, but the specificity of these detectors is modest. Since PAH identifi(&)#172;cation is solely based on retention times, unambiguous PAH identification requires complete chromatographic resolution of sample components. When HPLC is applied to (")unfamiliar(") samples, the EPA recommends that a supporting analytical technique such as GC-MS be applied to verify compound identification and to check peak-purity HPLC fractions. Independent of the volume of extracted water, the approximate time required to separate and determine the sixteen (")priority pollutants(") (EPA-PAH) via HPLC is approximately 60min. If additional GC-MS analysis is required for unambiguous PAH determination, the total analysis time will reach 2-3 hours per sample. If the concentrations of target species are found to lie outside the detector's response range, the sample must be diluted and the process repeated. These are important considerations when routine analysis of numerous samples is contemplated. Parent PAH are relatively inert and need metabolic activation to express their carcinogenicity. By virtue of the rich heterogeneous distribution of metabolic products they produce, PAH provide a full spectrum of the complexity associated with understanding the initial phase of carcinogenesis. PAH metabolites include a variety of products such as expoxides, hydroxyl aromatics, quinines, dihydrodiols, dioepoxides, tetrols and water soluble conjugates. During the past decades tremendous efforts have been made to develop bio-analytical techniques that possess the selectivity and sensitivity for the problem at hand. Depending on the complexity of the sample and the relative concentrations of the targeted metabolites, a combination of sample preparation techniques is often necessary to reach the limits of detection of the instrumental method of analysis. The numerous preparation steps open ample opportunity to metabolite loss and collection of inaccurate data. Separation of metabolites has been accomplished via HPLC, capillary electrophoresis (CE) and GC-MS. Unfortunately, the existence of chemically related metabolic products with virtually identical fragmentation patterns often challenges the specificity of these techniques. This dissertation presents significant improvements in various fronts. Its first original component (-) which we have named solid-phase nano-extraction (SPNE) - deals with the use of gold nanoparticles (Au NPs) as extracting material for PAH. The advantages of SPNE are demonstrated for the analysis of PAH in water samples via both HPLC1 and Laser-Excited Time-Resolved Shpol'skii Spectroscopy (LETRSS).2 The same concept is then extended to the analysis of monohydroxy-PAH in urine samples via SPE- HPLC3 and In-Capillary SPNE-CE.4 The second original component of this dissertation describes the application of Shpol'skii Spectroscopy to the analysis of polar PAH metabolites. The outstanding selectivity and sensitivity for the direct analysis of PAH at trace concentration levels has made Shpol'skii spectroscopy a leading technique in environmental analysis.5 Unfortunately, the requirement of a specific guest-host combination - typically a non-polar PAH dissolved in an n-alkane - has hindered its widespread application to the field of analytical chemistry. This dissertation takes the first steps in removing this limitation demonstrating its feasibility for the analysis of polar benzo[a]pyrene metabolites in alcohol matrixes.
Show less - Date Issued
- 2013
- Identifier
- CFE0005141, ucf:50693
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005141
- Title
- The Characterization of Condom Lubricants and Personal Hygiene Products using DART-TOFMS and GC- MS and The Investigation of Gold Nanoparticle Behavior in Water and the Interaction with Blood Serum Proteins.
- Creator
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Moustafa, Yasmine, Huo, Qun, Bridge, Candice, Sigman, Michael, Baudelet, Matthieu, Popolan-Vaida, Denisia, Ni, Liqiang, University of Central Florida
- Abstract / Description
-
This dissertation is divided into two independent research projects. First, condom lubricants, sexual lubricants, and personal hygiene products (PHPs) were studied using direct analysis in real time-time-of-flight-mass spectrometry (DART-TOFMS) and gas chromatography-mass spectrometry (GC-MS). The purpose addressed the concern of perpetrators resorting to new tactics, i.e. using condoms to remove seminal fluid that could provide a DNA link to a suspect, leading to the need of the...
Show moreThis dissertation is divided into two independent research projects. First, condom lubricants, sexual lubricants, and personal hygiene products (PHPs) were studied using direct analysis in real time-time-of-flight-mass spectrometry (DART-TOFMS) and gas chromatography-mass spectrometry (GC-MS). The purpose addressed the concern of perpetrators resorting to new tactics, i.e. using condoms to remove seminal fluid that could provide a DNA link to a suspect, leading to the need of the consideration of condom lubricants as pieces of sexual assault evidence. Due to condom lubricants having a chemical composition resembling PHPs, the investigation of both sample groups was analyzed to prevent false positives. Although past research has focused on the identification of major lubricant groups and additives, the discernment between such samples is insufficient. The discriminatory capability and rapid analysis of samples using DART-TOFMS was illustrated through resolution among the sample groups and higher classification rates. Here, lubricant analysis was introduced as a viable source of evidence, with a scheme detailing their discrimination from common hygiene products using DART-TOFMS as a robust tool for the analysis of sexual assault evidence. Second, gold nanoparticles (AuNPs) were characterized using dynamic light scattering (DLS), Ultraviolet-Visible spectroscopy (UV-VIS), dark field Imaging (DFM), and Transmission electron microscopy (TEM). Following characterization, AuNPs were used in protein adsorption study from blood serum concentration and to observe how the differences in their characterization affected their interactions with blood serum proteins. AuNPs are an interest in the bioanalytical sector due to their optical properties, scattering of light, and high surface-to-volume ratio. A common issue plagues the field: the difficulty of inter/intra laboratory reproducibility from one characterization technique. This further affects the understanding of how AuNPs may react for diagnostic and other applications. The importance of a comprehensive characterization protocol for AuNP products and the need for manufacturers to include product specifications is demonstrated in this study.
Show less - Date Issued
- 2019
- Identifier
- CFE0007842, ucf:52814
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007842
- Title
- LASER INDUCED BREAKDOWN SPECTROSCOPY FOR DETECTION OF ORGANIC RESIDUES: IMPACT OF AMBIENT ATMOSPHERE AND LASER PARAMETERS.
- Creator
-
Brown, Christopher, Richardson, Martin, University of Central Florida
- Abstract / Description
-
Laser Induced Breakdown Spectroscopy (LIBS) is showing great potential as an atomic analytical technique. With its ability to rapidly analyze all forms of matter, with little-to-no sample preparation, LIBS has many advantages over conventional atomic emission spectroscopy techniques. With the maturation of the technologies that make LIBS possible, there has been a growing movement to implement LIBS in portable analyzers for field applications. In particular, LIBS has long been considered the...
Show moreLaser Induced Breakdown Spectroscopy (LIBS) is showing great potential as an atomic analytical technique. With its ability to rapidly analyze all forms of matter, with little-to-no sample preparation, LIBS has many advantages over conventional atomic emission spectroscopy techniques. With the maturation of the technologies that make LIBS possible, there has been a growing movement to implement LIBS in portable analyzers for field applications. In particular, LIBS has long been considered the front-runner in the drive for stand-off detection of trace deposits of explosives. Thus there is a need for a better understanding of the relevant processes that are responsible for the LIBS signature and their relationships to the different system parameters that are helping to improve LIBS as a sensing technology. This study explores the use of LIBS as a method to detect random trace amounts of specific organic materials deposited on organic or non-metallic surfaces. This requirement forces the limitation of single-shot signal analysis. This study is both experimental and theoretical, with a sizeable component addressing data analysis using principal components analysis to reduce the dimensionality of the data, and quadratic discriminant analysis to classify the data. In addition, the alternative approach of 'target factor analysis' was employed to improve detection of organic residues on organic substrates. Finally, a new method of characterizing the laser-induced plasma of organics, which should lead to improved data collection and analysis, is introduced. The comparison between modeled and experimental measurements of plasma temperatures and electronic density is discussed in order to improve the present models of low-temperature laser induced plasmas.
Show less - Date Issued
- 2011
- Identifier
- CFE0003708, ucf:48843
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0003708
- Title
- Chemometric Applications to a Complex Classification Problem: Forensic Fire Debris Analysis.
- Creator
-
Waddell, Erin, Sigman, Michael, Belfield, Kevin, Campiglia, Andres, Yestrebsky, Cherie, Ni, Liqiang, University of Central Florida
- Abstract / Description
-
Fire debris analysis currently relies on visual pattern recognition of the total ion chromatograms, extracted ion profiles, and target compound chromatograms to identify the presence of an ignitable liquid according to the ASTM International E1618-10 standard method. For large data sets, this methodology can be time consuming and is a subjective method, the accuracy of which is dependent upon the skill and experience of the analyst. This research aimed to develop an automated classification...
Show moreFire debris analysis currently relies on visual pattern recognition of the total ion chromatograms, extracted ion profiles, and target compound chromatograms to identify the presence of an ignitable liquid according to the ASTM International E1618-10 standard method. For large data sets, this methodology can be time consuming and is a subjective method, the accuracy of which is dependent upon the skill and experience of the analyst. This research aimed to develop an automated classification method for large data sets and investigated the use of the total ion spectrum (TIS). The TIS is calculated by taking an average mass spectrum across the entire chromatographic range and has been shown to contain sufficient information content for the identification of ignitable liquids. The TIS of ignitable liquids and substrates, defined as common building materials and household furnishings, were compiled into model data sets. Cross-validation (CV) and fire debris samples, obtained from laboratory-scale and large-scale burns, were used to test the models. An automated classification method was developed using computational software, written in-house, that considers a multi-step classification scheme to detect ignitable liquid residues in fire debris samples and assign these to the classes defined in ASTM E1618-10. Classifications were made using linear discriminant analysis, quadratic discriminant analysis (QDA), and soft independent modeling of class analogy (SIMCA). Overall, the highest correct classification rates were achieved using QDA for the first step of the scheme and SIMCA for the remaining steps. In the first step of the classification scheme, correct classification rates of 95.3% and 89.2% were obtained for the CV test set and fire debris samples, respectively. Correct classifications rates of 100% were achieved for both data sets in the majority of the remaining steps which used SIMCA for classification. In this research, the first statistically valid error rates for fire debris analysis have been developed through cross-validation of large data sets. The error rates reduce the subjectivity associated with the current methods and provide a level of confidence in sample classification that does not currently exist in forensic fire debris analysis.
Show less - Date Issued
- 2013
- Identifier
- CFE0004954, ucf:49586
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004954
- Title
- Improvements on Instrumentation to Explore the Multidimensionality of Luminescence Spectroscopy.
- Creator
-
Moore, Anthony, Campiglia, Andres, Chumbimuni Torres, Karin, Harper, James, Rex, Matthew, Lee, Woo Hyoung, University of Central Florida
- Abstract / Description
-
This dissertation presents experimental and instrumentation developments that take full advantage of the multidimensional nature of line narrowing spectroscopy at liquid nitrogen (77 K) and liquid helium (4.2 K) temperatures. The inconvenience of sample freezing procedures is eliminated with the aid of cryogenic fiber optic probes. Rapid collection of multidimensional data formats such as wavelength time matrices, excitation emission matrices, time-resolved excitation emission matrices and...
Show moreThis dissertation presents experimental and instrumentation developments that take full advantage of the multidimensional nature of line narrowing spectroscopy at liquid nitrogen (77 K) and liquid helium (4.2 K) temperatures. The inconvenience of sample freezing procedures is eliminated with the aid of cryogenic fiber optic probes. Rapid collection of multidimensional data formats such as wavelength time matrices, excitation emission matrices, time-resolved excitation emission matrices and time resolved excitation emission cubes is made possible with the combination of a pulsed tunable dye laser, a spectrograph and an intensifier-charged coupled device. These data formats provide unique opportunities for processing vibrational luminescence data with second order multivariate calibration algorithms. The use of cryogenic fiber optic probes is extended to commercial instrumentation. An attractive feature of spectrofluorimeters with excitation and emission monochromators is the possibility to record synchronous spectra. The advantages of this approach, which include narrowing of spectral bandwidth and simplification of emission spectra, were demonstrated with the direct analysis of highly toxic dibenzopyrene isomers. The same is true for the collection of steady-state fluorescence excitation-emission matrices. These approaches provide a general solution to unpredictable spectral interference, a ubiquitous problem for the analysis of organic pollutants in environmental samples of unknown composition. Since commercial spectrofluorimeters are readily available in most academic institutions, industrial settings and research institutes, the developments presented here should facilitate the widespread application of line-narrowing spectroscopic techniques to the direct determination, no chromatographic separation, of highly toxic compounds in complex environmental matrixes of unknown composition.
Show less - Date Issued
- 2015
- Identifier
- CFE0005847, ucf:50934
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005847
