Headspace analysis of smokeless powders: Development of mass calibration methods using microdrop printing for chromatographic and ion mobility spectrometric detection

Smokeless powder additives are usually detected by their extraction from post-blast residues or unburned powder particles followed by analysis using chromatographic techniques. This work presents the first comprehensive study of the detection of the volatile and semi-volatile additives of smokeless powders using solid phase microextraction (SPME) as a sampling and pre-concentration technique. Seventy smokeless powders were studied using laboratory based chromatography techniques and a field deployable ion mobility spectrometer (IMS). The detection of diphenylamine, ethyl and methyl centralite, 2,4-dinitrotoluene, diethyl and dibutyl phthalate by IMS to associate the presence of these compounds to smokeless powders is also reported for the first time. A previously reported SPME-IMS analytical approach facilitates rapid sub-nanogram detection of the vapor phase components of smokeless powders. A mass calibration procedure for the analytical techniques used in this study was developed. Precise and accurate mass delivery of analytes in picoliter volumes was achieved using a drop-on-demand inkjet printing method. Absolute mass detection limits determined using this method for the various analytes of interest ranged between 0.03–0.8 ng for the GC-MS and between 0.03–2 ng for the IMS. Mass response graphs generated for different detection techniques help in the determination of mass extracted from the headspace of each smokeless powder. The analyte mass present in the vapor phase was sufficient for a SPME fiber to extract most analytes at amounts above the detection limits of both chromatographic techniques and the ion mobility spectrometer. Analysis of the large number of smokeless powders revealed that diphenylamine was present in the headspace of 96% of the powders. Ethyl centralite was detected in 47% of the powders and 8% of the powders had methyl centralite available for detection from the headspace sampling of the powders by SPME. Nitroglycerin was the dominant peak present in the headspace of the double-based powders. 2,4-dinitrotoluene which is another important headspace component was detected in 44% of the powders. The powders therefore have more than one headspace component and the detection of a combination of these compounds is achievable by SPME-IMS leading to an association to the presence of smokeless powders.

The development of direct ultra-fast PCR for forensic genotyping using short channel microfluidic systems with enhanced sieving matrices

There are situations in which it is very important to quickly and positively identify an individual. Examples include suspects detained in the neighborhood of a bombing or terrorist incident, individuals detained attempting to enter or leave the country, and victims of mass disasters. Systems utilized for these purposes must be fast, portable, and easy to maintain. The goal of this project was to develop an ultra fast, direct PCR method for forensic genotyping of oral swabs. The procedure developed eliminates the need for cellular digestion and extraction of the sample by performing those steps in the PCR tube itself. Then, special high-speed polymerases are added which are capable of amplifying a newly developed 7 loci multiplex in under 16 minutes. Following the amplification, a postage stamp sized microfluidic device equipped with specially designed entangled polymer separation matrix, yields a complete genotype in 80 seconds. The entire process is rapid and reliable, reducing the time from sample to genotype from 1-2 days to under 20 minutes. Operation requires minimal equipment and can be easily performed with a small high-speed thermal-cycler, reagents, and a microfluidic device with a laptop. The system was optimized and validated using a number of test parameters and a small test population. The overall precision was better than 0.17 bp and provided a power of discrimination greater than 1 in 106. The small footprint, and ease of use will permit this system to be an effective tool to quickly screen and identify individuals detained at ports of entry, police stations and remote locations. The system is robust, portable and demonstrates to the forensic community a simple solution to the problem of rapid determination of genetic identity.

Context -aware data caching for mobile computing environments

The deployment of wireless communications coupled with the popularity of portable devices has led to significant research in the area of mobile data caching. Prior research has focused on the development of solutions that allow applications to run in wireless environments using proxy based techniques. Most of these approaches are semantic based and do not provide adequate support for representing the context of a user (i.e., the interpreted human intention.). Although the context may be treated implicitly it is still crucial to data management. In order to address this challenge this dissertation focuses on two characteristics: how to predict (i) the future location of the user and (ii) locations of the fetched data where the queried data item has valid answers. Using this approach, more complete information about the dynamics of an application environment is maintained. ^ The contribution of this dissertation is a novel data caching mechanism for pervasive computing environments that can adapt dynamically to a mobile user's context. In this dissertation, we design and develop a conceptual model and context aware protocols for wireless data caching management. Our replacement policy uses the validity of the data fetched from the server and the neighboring locations to decide which of the cache entries is less likely to be needed in the future, and therefore a good candidate for eviction when cache space is needed. The context aware driven prefetching algorithm exploits the query context to effectively guide the prefetching process. The query context is defined using a mobile user's movement pattern and requested information context. Numerical results and simulations show that the proposed prefetching and replacement policies significantly outperform conventional ones. ^ Anticipated applications of these solutions include biomedical engineering, tele-health, medical information systems and business. ^

Contribution of lipophilic secondary metabolites to the toxicity of strains of freshwater cyanobacterial harmful algal blooms, identified using the zebrafish (Danio rerio) embryo as a model for vertebrate development

Cyanobacteria ("blue-green algae") are known to produce a diverse repertoire of biologically active secondary metabolites. When associated with so-called "harmful algal blooms", particularly in freshwater systems, a number of these metabolites have been associated—as "toxins", or commonly "cyanotoxins"—with human and animal health concerns. In addition to the known water-soluble toxins from these genera (i.e. microcystins, cylindrospermopsin, and saxitoxins), our studies have shown that there are metabolites within the lipophilic extracts of these strains that inhibit vertebrate development in zebrafish embryos. Following these studies, the zebrafish embryo model was implemented in the bioassay-guided purification of four isolates of cyanobacterial harmful algal blooms, namely Aphanizomenon, two isolates of Cylindrospermopsis, and Microcystis, in order to identify and chemically characterize the bioactive lipophilic metabolites in these isolates. ^ We have recently isolated a group of polymethoxy-1-alkenes (PMAs), as potential toxins, based on the bioactivity observed in the zebrafish embryos. Although PMAs have been previously isolated from diverse cyanobacteria, they have not previously been associated with relevant toxicity. These compounds seem to be widespread across the different genera of cyanobacteria, and, according to our studies, suggested to be derived from the polyketide biosynthetic pathway which is a common synthetic route for cyanobacterial and other algal toxins. Thus, it can be argued that these metabolites are perhaps important contributors to the toxicity of cyanobacterial blooms. In addition to the PMAs, a set of bioactive glycosidic carotenoids were also isolated because of their inhibition of zebrafish embryonic development. These pigmented organic molecules are found in many photosynthetic organisms, including cyanobacteria, and they have been largely associated with the prevention of photooxidative damage. This is the first indication of these compounds as toxic metabolites and the hypothesized mode of action is via their biotransformation to retinoids, some of which are known to be teratogenic. Additional fractions within all four isolates have been shown to contain other uncharacterized lipophilic toxic metabolites. This apparent repertoire of lipophilic compounds may contribute to the toxicity of these cyanobacterial harmful algal blooms, which were previously attributed primarily to the presence of the known water-soluble toxins.^

Headspace Analysis of Smokeless Powders: Development of Mass Calibration Methods using Microdrop Printing for Chromatographic and Ion Mobility Spectrometric Detection

Smokeless powder additives are usually detected by their extraction from post-blast residues or unburned powder particles followed by analysis using chromatographic techniques. This work presents the first comprehensive study of the detection of the volatile and semi-volatile additives of smokeless powders using solid phase microextraction (SPME) as a sampling and pre-concentration technique. Seventy smokeless powders were studied using laboratory based chromatography techniques and a field deployable ion mobility spectrometer (IMS). The detection of diphenylamine, ethyl and methyl centralite, 2,4-dinitrotoluene, diethyl and dibutyl phthalate by IMS to associate the presence of these compounds to smokeless powders is also reported for the first time. A previously reported SPME-IMS analytical approach facilitates rapid sub-nanogram detection of the vapor phase components of smokeless powders. A mass calibration procedure for the analytical techniques used in this study was developed. Precise and accurate mass delivery of analytes in picoliter volumes was achieved using a drop-on-demand inkjet printing method. Absolute mass detection limits determined using this method for the various analytes of interest ranged between 0.03 - 0.8 ng for the GC-MS and between 0.03 - 2 ng for the IMS. Mass response graphs generated for different detection techniques help in the determination of mass extracted from the headspace of each smokeless powder. The analyte mass present in the vapor phase was sufficient for a SPME fiber to extract most analytes at amounts above the detection limits of both chromatographic techniques and the ion mobility spectrometer. Analysis of the large number of smokeless powders revealed that diphenylamine was present in the headspace of 96% of the powders. Ethyl centralite was detected in 47% of the powders and 8% of the powders had methyl centralite available for detection from the headspace sampling of the powders by SPME. Nitroglycerin was the dominant peak present in the headspace of the double-based powders. 2,4-dinitrotoluene which is another important headspace component was detected in 44% of the powders. The powders therefore have more than one headspace component and the detection of a combination of these compounds is achievable by SPME-IMS leading to an association to the presence of smokeless powders.

Development of a binary positive and negative protein fragment complementation assay using yeast cytosine deaminase

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

High accuracy mobile robot positioning using an external large volume metrology instrument

A method of accurately controlling the position of a mobile robot using an external Large Volume Metrology (LVM) instrument is presented in this paper. Utilizing a LVM instrument such as the laser tracker in mobile robot navigation, many of the most difficult problems in mobile robot navigation can be simplified or avoided. Using the real- Time position information from the laser tracker, a very simple navigation algorithm, and a low cost robot, 5mm repeatability was achieved over a volume of 30m radius. A surface digitization scan of a wind turbine blade section was also demonstrated, illustrating possible applications of the method for manufacturing processes. © Springer-Verlag Berlin Heidelberg 2010.

Enterprise management and ERP development:case study of Zoomlion using dynamic enterprise reference grid

The enterprise management approach provides a holistic view of organizations and their related information systems. In order to cope with the globalization, virtualization, and volatile competitive environment, traditional firms are seeking to reconstruct their organizational structures and establish new IS architectures to transform from single autonomous entities into more open enterprises supported by new Enterprise Resource Planning (ERP) systems. This paper reports on ERP engage-abilities within three different enterprise management patterns based on the theoretical foundations of the "Dynamic Enterprise Reference Grid". An exploratory inductive study in Zoomlion using the narrative research approach has been conducted. Also, this research delivers a conceptual framework to demonstrate the adoption of ERP in the three enterprise management structures and points to a new architectural type (ERPIII) for operating in the virtual enterprise paradigm. © 2010 Springer-Verlag.

The Genetics of Success: How Single-Nucleotide Polymorphisms Associated With Educational Attainment Relate to Life-Course Development.

A previous genome-wide association study (GWAS) of more than 100,000 individuals identified molecular-genetic predictors of educational attainment. We undertook in-depth life-course investigation of the polygenic score derived from this GWAS using the four-decade Dunedin Study (N = 918). There were five main findings. First, polygenic scores predicted adult economic outcomes even after accounting for educational attainments. Second, genes and environments were correlated: Children with higher polygenic scores were born into better-off homes. Third, children's polygenic scores predicted their adult outcomes even when analyses accounted for their social-class origins; social-mobility analysis showed that children with higher polygenic scores were more upwardly mobile than children with lower scores. Fourth, polygenic scores predicted behavior across the life course, from early acquisition of speech and reading skills through geographic mobility and mate choice and on to financial planning for retirement. Fifth, polygenic-score associations were mediated by psychological characteristics, including intelligence, self-control, and interpersonal skill. Effect sizes were small. Factors connecting DNA sequence with life outcomes may provide targets for interventions to promote population-wide positive development.

Development and reliability of a direct access sensor using flip chip on flex technology with anisotropic conductive adhesive

Technological developments in biomedical microsystems are opening up new opportunities to improve healthcare procedures. Swallowable diagnostic sensing capsules are an example of these. In none of the diagnostic sensing capsules, is the sensor’s first level packaging achieved via Flip Chip Over Hole (FCOH) method using Anisotropic Conductive Adhesive (ACA). In a capsule application with direct access sensor (DAS), ACA not only provides the electrical interconnection but simultaneously seals the interconnect area and the underlying electronics. The development showed that the ACA FCOH was a viable option for the DAS interconnection. Adequate adhesive formed a strong joint that withstood a shear stress of 120N/mm2 and a compressive stress of 6N required to secure the final sensor assembly in place before encapsulation. Electrical characterization of the ACA joint in a fluid environment showed that the ACA was saturated with moisture and that the ions in the solution actively contributed to the leakage current, characterized by the varying rate of change of conductance. Long term hygrothermal aging of the ACA joint showed that a thermal strain of 0.004 and a hygroscopic strain of 0.0052 were present and resulted in a fatigue like process. In-vitro tests showed that high temperature and acidity had a deleterious effect of the ACA and its joint. It also showed that the ACA contact joints positioned at around or over 1mm would survive the gastrointestinal (GI) fluids and would be able to provide a reliable contact during the entire 72hr of the GI transit time. A final capsule demonstrator was achieved by successfully integrating the DAS, the battery and the final foldable circuitry into a glycerine capsule. Final capsule soak tests suggested that the silicone encapsulated system could survive the 72hr gut transition.

Development of a binary positive and negative protein fragment complementation assay using yeast cytosine deaminase

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

A Framework to Capture and Share Knowledge Using Storytelling and Video Sharing in Global Product Development

In global engineering enterprises, information and knowledge sharing are critical factors that can determine a project’s success. This statement is widely acknowledged in published literature. However, according to some academics, tacit knowledge is derived from a person’s lifetime of experience, practice, perception and learning, which makes it hard to capture and document in order to be shared. This project investigates if social media tools can be used to improve and enable tacit knowledge sharing within a global engineering enterprise. This paper first provides a brief background of the subject area, followed by an explanation of the industrial investigation, from which the proposed knowledge framework to improve tacit knowledge sharing is presented. This project’s main focus is on the improvement of collaboration and knowledge sharing amongst product development engineers in order to improve the whole product development cycle.

IF-MANET: Interoperable framework for heterogeneous mobile ad hoc networks

The advances in low power micro-processors, wireless networks and embedded systems have raised the need to utilize the significant resources of mobile devices. These devices for example, smart phones, tablets, laptops, wearables, and sensors are gaining enormous processing power, storage capacity and wireless bandwidth. In addition, the advancement in wireless mobile technology has created a new communication paradigm via which a wireless network can be created without any priori infrastructure called mobile ad hoc network (MANET). While progress is being made towards improving the efficiencies of mobile devices and reliability of wireless mobile networks, the mobile technology is continuously facing the challenges of un-predictable disconnections, dynamic mobility and the heterogeneity of routing protocols. Hence, the traditional wired, wireless routing protocols are not suitable for MANET due to its unique dynamic ad hoc nature. Due to the reason, the research community has developed and is busy developing protocols for routing in MANET to cope with the challenges of MANET. However, there are no single generic ad hoc routing protocols available so far, which can address all the basic challenges of MANET as mentioned before. Thus this diverse range of ever growing routing protocols has created barriers for mobile nodes of different MANET taxonomies to intercommunicate and hence wasting a huge amount of valuable resources. To provide interaction between heterogeneous MANETs, the routing protocols require conversion of packets, meta-model and their behavioural capabilities. Here, the fundamental challenge is to understand the packet level message format, meta-model and behaviour of different routing protocols, which are significantly different for different MANET Taxonomies. To overcome the above mentioned issues, this thesis proposes an Interoperable Framework for heterogeneous MANETs called IF-MANET. The framework hides the complexities of heterogeneous routing protocols and provides a homogeneous layer for seamless communication between these routing protocols. The framework creates a unique Ontology for MANET routing protocols and a Message Translator to semantically compare the packets and generates the missing fields using the rules defined in the Ontology. Hence, the translation between an existing as well as newly arriving routing protocols will be achieved dynamically and on-the-fly. To discover a route for the delivery of packets across heterogeneous MANET taxonomies, the IF-MANET creates a special Gateway node to provide cluster based inter-domain routing. The IF-MANET framework can be used to develop different middleware applications. For example: Mobile grid computing that could potentially utilise huge amounts of aggregated data collected from heterogeneous mobile devices. Disaster & crises management applications can be created to provide on-the-fly infrastructure-less emergency communication across organisations by utilising different MANET taxonomies.

PIPc study: development of indicators of potentially inappropriate prescribing in children (PIPc) in primary care using a modified Delphi technique

Objective There is limited evidence regarding the quality of prescribing for children in primary care. Several prescribing criteria (indicators) have been developed to assess the appropriateness of prescribing in older and middle-aged adults but few are relevant to children. The objective of this study was to develop a set of prescribing indicators that can be applied to prescribing or dispensing data sets to determine the prevalence of potentially inappropriate prescribing in children (PIPc) in primary care settings.


Design Two-round modified Delphi consensus method.


Setting Irish and UK general practice.


Participants A project steering group consisting of academic and clinical general practitioners (GPs) and pharmacists was formed to develop a list of indicators from literature review and clinical expertise. 15 experts consisting of GPs, pharmacists and paediatricians from the Republic of Ireland and the UK formed the Delphi panel.


Results 47 indicators were reviewed by the project steering group and 16 were presented to the Delphi panel. In the first round of this exercise, consensus was achieved on nine of these indicators. Of the remaining seven indicators, two were removed following review of expert panel comments and discussion of the project steering group. The second round of the Delphi process focused on the remaining five indicators, which were amended based on first round feedback. Three indicators were accepted following the second round of the Delphi process and the remaining two indicators were removed. The final list consisted of 12 indicators categorised by respiratory system (n=6), gastrointestinal system (n=2), neurological system (n=2) and dermatological system (n=2).


Conclusions The PIPc indicators are a set of prescribing criteria developed for use in children in primary care in the absence of clinical information. The utility of these criteria will be tested in further studies using prescribing databases.