Multivariate spectroscopic methods for the analysis of solutions

In this thesis some multivariate spectroscopic methods for the analysis of solutions are proposed. Spectroscopy and multivariate data analysis form a powerful combination for obtaining both quantitative and qualitative information and it is shown how spectroscopic techniques in combination with chemometric data evaluation can be used to obtain rapid, simple and efficient analytical methods. These spectroscopic methods consisting of spectroscopic analysis, a high level of automation and chemometric data evaluation can lead to analytical methods with a high analytical capacity, and for these methods, the term high-capacity analysis (HCA) is suggested. It is further shown how chemometric evaluation of the multivariate data in chromatographic analyses decreases the need for baseline separation. The thesis is based on six papers and the chemometric tools used are experimental design, principal component analysis (PCA), soft independent modelling of class analogy (SIMCA), partial least squares regression (PLS) and parallel factor analysis (PARAFAC). The analytical techniques utilised are scanning ultraviolet-visible (UV-Vis) spectroscopy, diode array detection (DAD) used in non-column chromatographic diode array UV spectroscopy, high-performance liquid chromatography with diode array detection (HPLC-DAD) and fluorescence spectroscopy. The methods proposed are exemplified in the analysis of pharmaceutical solutions and serum proteins. In Paper I a method is proposed for the determination of the content and identity of the active compound in pharmaceutical solutions by means of UV-Vis spectroscopy, orthogonal signal correction and multivariate calibration with PLS and SIMCA classification. Paper II proposes a new method for the rapid determination of pharmaceutical solutions by the use of non-column chromatographic diode array UV spectroscopy, i.e. a conventional HPLC-DAD system without any chromatographic column connected. In Paper III an investigation is made of the ability of a control sample, of known content and identity to diagnose and correct errors in multivariate predictions something that together with use of multivariate residuals can make it possible to use the same calibration model over time. In Paper IV a method is proposed for simultaneous determination of serum proteins with fluorescence spectroscopy and multivariate calibration. Paper V proposes a method for the determination of chromatographic peak purity by means of PCA of HPLC-DAD data. In Paper VI PARAFAC is applied for the decomposition of DAD data of some partially separated peaks into the pure chromatographic, spectral and concentration profiles.

Towards Automation in Digital Investigations : Seeking Efficiency in Digital Forensics in Mobile and Cloud Environments

Cybercrime and related malicious activity in our increasingly digital world has become more prevalent and sophisticated, evading traditional security mechanisms. Digital forensics has been proposed to help investigate, understand and eventually mitigate such attacks. The practice of digital forensics, however, is still fraught with various challenges. Some of the most prominent of these challenges include the increasing amounts of data and the diversity of digital evidence sources appearing in digital investigations. Mobile devices and cloud infrastructures are an interesting specimen, as they inherently exhibit these challenging circumstances and are becoming more prevalent in digital investigations today. Additionally they embody further characteristics such as large volumes of data from multiple sources, dynamic sharing of resources, limited individual device capabilities and the presence of sensitive data. These combined set of circumstances make digital investigations in mobile and cloud environments particularly challenging. This is not aided by the fact that digital forensics today still involves manual, time consuming tasks within the processes of identifying evidence, performing evidence acquisition and correlating multiple diverse sources of evidence in the analysis phase. Furthermore, industry standard tools developed are largely evidence-oriented, have limited support for evidence integration and only automate certain precursory tasks, such as indexing and text searching. In this study, efficiency, in the form of reducing the time and human labour effort expended, is sought after in digital investigations in highly networked environments through the automation of certain activities in the digital forensic process. To this end requirements are outlined and an architecture designed for an automated system that performs digital forensics in highly networked mobile and cloud environments. Part of the remote evidence acquisition activity of this architecture is built and tested on several mobile devices in terms of speed and reliability. A method for integrating multiple diverse evidence sources in an automated manner, supporting correlation and automated reasoning is developed and tested. Finally the proposed architecture is reviewed and enhancements proposed in order to further automate the architecture by introducing decentralization particularly within the storage and processing functionality. This decentralization also improves machine to machine communication supporting several digital investigation processes enabled by the architecture through harnessing the properties of various peer-to-peer overlays. Remote evidence acquisition helps to improve the efficiency (time and effort involved) in digital investigations by removing the need for proximity to the evidence. Experiments show that a single TCP connection client-server paradigm does not offer the required scalability and reliability for remote evidence acquisition and that a multi-TCP connection paradigm is required. The automated integration, correlation and reasoning on multiple diverse evidence sources demonstrated in the experiments improves speed and reduces the human effort needed in the analysis phase by removing the need for time-consuming manual correlation. Finally, informed by published scientific literature, the proposed enhancements for further decentralizing the Live Evidence Information Aggregator (LEIA) architecture offer a platform for increased machine-to-machine communication thereby enabling automation and reducing the need for manual human intervention.