Fragmentation pathways of 2,3-dimethyl-2,3-dinitrobutane cations in the gas phase

2,3-Dimethyl-2,3-dinitrobutane (DMNB) is an explosive taggant added to plastic explosives during manufacture making them more susceptible to vapour-phase detection systems. In this study, the formation and detection of gas-phase \[M+H](+), \[M+Li](+), \[M+NH(4)](+) and \[M+Na](+) adducts of DMNB was achieved using electrospray ionisation on a triple quadrupole mass spectrometer. The \[M+H](+) ion abundance was found to have a strong dependence on ion source temperature, decreasing markedly at source temperatures above 50 degrees C. In contrast, the \[M+Na](+) ion demonstrated increasing ion abundance at source temperatures up to 105 degrees C. The relative susceptibility of DMNB adduct ions toward dissociation was investigated by collision-induced dissociation. Probable structures of product ions and mechanisms for unimolecular dissociation have been inferred based on fragmentation patterns from tandem mass (MS/MS) spectra of source-formed ions of normal and isotopically labelled DMNB, and quantum chemical calculations. Both thermal and collisional activation studies suggest that the \[M+Na](+) adduct ions are significantly more stable toward dissociation than their protonated analogues and, as a consequence, the former provide attractive targets for detection by contemporary rapid screening methods such as desorption electrospray ionisation mass spectrometry. Copyright (C) 2009 Commonwealth of Australia. Published by John Wiley & Sons, Ltd.

Adaptive instantaneous frequency estimation: Techniques and algorithms

This thesis deals with the problem of the instantaneous frequency (IF) estimation of sinusoidal signals. This topic plays significant role in signal processing and communications. Depending on the type of the signal, two major approaches are considered. For IF estimation of single-tone or digitally-modulated sinusoidal signals (like frequency shift keying signals) the approach of digital phase-locked loops (DPLLs) is considered, and this is Part-I of this thesis. For FM signals the approach of time-frequency analysis is considered, and this is Part-II of the thesis. In part-I we have utilized sinusoidal DPLLs with non-uniform sampling scheme as this type is widely used in communication systems. The digital tanlock loop (DTL) has introduced significant advantages over other existing DPLLs. In the last 10 years many efforts have been made to improve DTL performance. However, this loop and all of its modifications utilizes Hilbert transformer (HT) to produce a signal-independent 90-degree phase-shifted version of the input signal. Hilbert transformer can be realized approximately using a finite impulse response (FIR) digital filter. This realization introduces further complexity in the loop in addition to approximations and frequency limitations on the input signal. We have tried to avoid practical difficulties associated with the conventional tanlock scheme while keeping its advantages. A time-delay is utilized in the tanlock scheme of DTL to produce a signal-dependent phase shift. This gave rise to the time-delay digital tanlock loop (TDTL). Fixed point theorems are used to analyze the behavior of the new loop. As such TDTL combines the two major approaches in DPLLs: the non-linear approach of sinusoidal DPLL based on fixed point analysis, and the linear tanlock approach based on the arctan phase detection. TDTL preserves the main advantages of the DTL despite its reduced structure. An application of TDTL in FSK demodulation is also considered. This idea of replacing HT by a time-delay may be of interest in other signal processing systems. Hence we have analyzed and compared the behaviors of the HT and the time-delay in the presence of additive Gaussian noise. Based on the above analysis, the behavior of the first and second-order TDTLs has been analyzed in additive Gaussian noise. Since DPLLs need time for locking, they are normally not efficient in tracking the continuously changing frequencies of non-stationary signals, i.e. signals with time-varying spectra. Nonstationary signals are of importance in synthetic and real life applications. An example is the frequency-modulated (FM) signals widely used in communication systems. Part-II of this thesis is dedicated for the IF estimation of non-stationary signals. For such signals the classical spectral techniques break down, due to the time-varying nature of their spectra, and more advanced techniques should be utilized. For the purpose of instantaneous frequency estimation of non-stationary signals there are two major approaches: parametric and non-parametric. We chose the non-parametric approach which is based on time-frequency analysis. This approach is computationally less expensive and more effective in dealing with multicomponent signals, which are the main aim of this part of the thesis. A time-frequency distribution (TFD) of a signal is a two-dimensional transformation of the signal to the time-frequency domain. Multicomponent signals can be identified by multiple energy peaks in the time-frequency domain. Many real life and synthetic signals are of multicomponent nature and there is little in the literature concerning IF estimation of such signals. This is why we have concentrated on multicomponent signals in Part-H. An adaptive algorithm for IF estimation using the quadratic time-frequency distributions has been analyzed. A class of time-frequency distributions that are more suitable for this purpose has been proposed. The kernels of this class are time-only or one-dimensional, rather than the time-lag (two-dimensional) kernels. Hence this class has been named as the T -class. If the parameters of these TFDs are properly chosen, they are more efficient than the existing fixed-kernel TFDs in terms of resolution (energy concentration around the IF) and artifacts reduction. The T-distributions has been used in the IF adaptive algorithm and proved to be efficient in tracking rapidly changing frequencies. They also enables direct amplitude estimation for the components of a multicomponent

The delta-phase spectrum with application to voice activity detection and speaker recognition

For several reasons, the Fourier phase domain is less favored than the magnitude domain in signal processing and modeling of speech. To correctly analyze the phase, several factors must be considered and compensated, including the effect of the step size, windowing function and other processing parameters. Building on a review of these factors, this paper investigates a spectral representation based on the Instantaneous Frequency Deviation, but in which the step size between processing frames is used in calculating phase changes, rather than the traditional single sample interval. Reflecting these longer intervals, the term delta-phase spectrum is used to distinguish this from instantaneous derivatives. Experiments show that mel-frequency cepstral coefficients features derived from the delta-phase spectrum (termed Mel-Frequency delta-phase features) can produce broadly similar performance to equivalent magnitude domain features for both voice activity detection and speaker recognition tasks. Further, it is shown that the fusion of the magnitude and phase representations yields performance benefits over either in isolation.

A plasmonic 'ac Wheatstone bridge' circuit for high-sensitivity phase measurement and single-molecule detection

In this paper, a plasmonic “ac Wheatstone bridge” circuit is proposed and theoretically modeled for the first time. The bridge circuit consists of three metallic nanoparticles, shaped as rectangular prisms, with two nanoparticles acting as parallel arms of a resonant circuit and the third bridging nanoparticle acting as an optical antenna providing an output signal. Polarized light excites localized surface plasmon resonances in the two arms of the circuit, which generate an optical signal dependent on the phase-sensitive excitations of surface plasmons in the antenna. The circuit is analyzed using a plasmonic coupling theory and numerical simulations. The analyses show that the plasmonic circuit is sensitive to phase shifts between the arms of the bridge and has the potential to detect the presence of single molecules.

Direct Detection of a Persistent Carbonyloxyl Radical in the Gas Phase

Long lived: Carbonyloxyl radicals (RCO2 .) are reactive intermediates that play key roles in initiating polymerization reactions. This reactivity also makes their direct observation difficult. For the first time a persistent organic RCO2 . radical is detected in the gas phase, its extraordinary longevity is attributed to the high barrier towards fragmentation owing to the endothermicity of the decarboxylation products. Grant Numbers ARC/DP0986738, ARC/DP120102922, ARC/DE120100467

Early detection : a strategy to reduce risk and severity?

Despite changes in surgical techniques, radiotherapy targeting and the apparent earlier detection of cancers, secondary lymphoedema is still a significant problem for about 20–30% of those who receive treatment for cancer, although the incidence and prevalence does seem to be falling. The figures above generally relate to detection of an enlarged limb or other area, but it seems that about 60% of all patients also suffer other problems with how the limb feels, what can or cannot be done with it and a range of social or psychological issues. Often these ‘subjective’ changes occur before the objective ones, such as a change in arm volume or circumference. For most of those treated for cancer lymphoedema does not develop immediately, and, while about 60–70% develop it in the first few years, some do not develop lymphoedema for up to 15 or 20 years. Those who will develop clinically manifest lymphoedema in the future are, for some time, in a latent or hidden phase of lymphoedema. There also seems to be some risk factors which are indicators for a higher likelihood of lymphoedema post treatment, including oedema at the surgical site, arm dominance, age, skin conditions, and body mass index (BMI).

Detection and Estimation of Nonstationary Power Transients

This chapter looks at issues of non-stationarity in determining when a transient has occurred and when it is possible to fit a linear model to a non-linear response. The first issue is associated with the detection of loss of damping of power system modes. When some control device such as an SVC fails, the operator needs to know whether the damping of key power system oscillation modes has deteriorated significantly. This question is posed here as an alarm detection problem rather than an identification problem to get a fast detection of a change. The second issue concerns when a significant disturbance has occurred and the operator is seeking to characterize the system oscillation. The disturbance initially is large giving a nonlinear response; this then decays and can then be smaller than the noise level ofnormal customer load changes. The difficulty is one of determining when a linear response can be reliably identified between the non-linear phase and the large noise phase of thesignal. The solution proposed in this chapter uses “Time-Frequency” analysis tools to assistthe extraction of the linear model.

Development of a high-speed sensing and detection system for automatic removal of packages with leaky seals from a high-speed food processing and packaging line

Contamination of packaged foods due to micro-organisms entering through air leaks can cause serious public health issues and cost companies large amounts of money due to product recalls, consumer impact and subsequent loss of market share. The main source of contamination is leaks in packaging which allow air, moisture and microorganisms to enter the package. In the food processing and packaging industry worldwide, there is an increasing demand for cost effective state of the art inspection technologies that are capable of reliably detecting leaky seals and delivering products at six-sigma. The new technology will develop non-destructive testing technology using digital imaging and sensing combined with a differential vacuum technique to assess seal integrity of food packages on a high-speed production line. The cost of leaky packages in Australian food industries is estimated close to AUD $35 Million per year. Contamination of packaged foods due to micro-organisms entering through air leaks can cause serious public health issues and cost companies large sums of money due to product recalls, compensation claims and loss of market share. The main source of contamination is leaks in packaging which allow air, moisture and micro-organisms to enter the package. Flexible plastic packages are widely used, and are the least expensive form of retaining the quality of the product. These packets can be used to seal, and therefore maximise, the shelf life of both dry and moist products. The seals of food packages need to be airtight so that the food content is not contaminated due to contact with microorganisms that enter as a result of air leakage. Airtight seals also extend the shelf life of packaged foods, and manufacturers attempt to prevent food products with leaky seals being sold to consumers. There are many current NDT (non-destructive testing) methods of testing the seal of flexible packages best suited to random sampling, and for laboratory purposes. The three most commonly used methods are vacuum/pressure decay, bubble test, and helium leak detection. Although these methods can detect very fine leaks, they are limited by their high processing time and are not viable in a production line. Two nondestructive in-line packaging inspection machines are currently available and are discussed in the literature review. The detailed design and development of the High-Speed Sensing and Detection System (HSDS) is the fundamental requirement of this project and the future prototype and production unit. Successful laboratory testing was completed and a methodical design procedure was needed for a successful concept. The Mechanical tests confirmed the vacuum hypothesis and seal integrity with good consistent results. Electrically, the testing also provided solid results to enable the researcher to move the project forward with a certain amount of confidence. The laboratory design testing allowed the researcher to confirm theoretical assumptions before moving into the detailed design phase. Discussion on the development of the alternative concepts in both mechanical and electrical disciplines enables the researcher to make an informed decision. Each major mechanical and electrical component is detailed through the research and design process. The design procedure methodically works through the various major functions both from a mechanical and electrical perspective. It opens up alternative ideas for the major components that although are sometimes not practical in this application, show that the researcher has exhausted all engineering and functionality thoughts. Further concepts were then designed and developed for the entire HSDS unit based on previous practice and theory. In the future, it would be envisaged that both the Prototype and Production version of the HSDS would utilise standard industry available components, manufactured and distributed locally. Future research and testing of the prototype unit could result in a successful trial unit being incorporated in a working food processing production environment. Recommendations and future works are discussed, along with options in other food processing and packaging disciplines, and other areas in the non-food processing industry.

Automatic region-of-interest detection and prioritisation for visually optimised coding of low bit rate videos

The increasing popularity of video consumption from mobile devices requires an effective video coding strategy. To overcome diverse communication networks, video services often need to maintain sustainable quality when the available bandwidth is limited. One of the strategy for a visually-optimised video adaptation is by implementing a region-of-interest (ROI) based scalability, whereby important regions can be encoded at a higher quality while maintaining sufficient quality for the rest of the frame. The result is an improved perceived quality at the same bit rate as normal encoding, which is particularly obvious at the range of lower bit rate. However, because of the difficulties of predicting region-of-interest (ROI) accurately, there is a limited research and development of ROI-based video coding for general videos. In this paper, the phase spectrum quaternion of Fourier Transform (PQFT) method is adopted to determine the ROI. To improve the results of ROI detection, the saliency map from the PQFT is augmented with maps created from high level knowledge of factors that are known to attract human attention. Hence, maps that locate faces and emphasise the centre of the screen are used in combination with the saliency map to determine the ROI. The contribution of this paper lies on the automatic ROI detection technique for coding a low bit rate videos which include the ROI prioritisation technique to give different level of encoding qualities for multiple ROIs, and the evaluation of the proposed automatic ROI detection that is shown to have a close performance to human ROI, based on the eye fixation data.

Experimental and computer simulation validation of ultrasound phase interference created by lateral inhomogeneity of transit time in replica bone marrow composite models

Purpose: The measurement of broadband ultrasonic attenuation (BUA) in cancellous bone for the assessment of osteoporosis follows a parabolic-type dependence with bone volume fraction; having minima values corresponding to both entire bone and entire marrow. Langton has recently proposed that the primary BUA mechanism may be significant phase interference due to variations in propagation transit time through the test sample as detected over the phase-sensitive surface of the receive ultrasound transducer. This fundamentally simple concept assumes that the propagation of ultrasound through a complex solid : liquid composite sample such as cancellous bone may be considered by an array of parallel ‘sonic rays’. The transit time of each ray is defined by the proportion of bone and marrow propagated, being a minimum (tmin) solely through bone and a maximum (tmax) solely through marrow. A Transit Time Spectrum (TTS), ranging from tmin to tmax, may be defined describing the proportion of sonic rays having a particular transit time, effectively describing lateral inhomogeneity of transit time over the surface of the receive ultrasound transducer. Phase interference may result from interaction of ‘sonic rays’ of differing transit times. The aim of this study was to test the hypothesis that there is a dependence of phase interference upon the lateral inhomogenity of transit time by comparing experimental measurements and computer simulation predictions of ultrasound propagation through a range of relatively simplistic solid:liquid models exhibiting a range of lateral inhomogeneities. Methods: A range of test models was manufactured using acrylic and water as surrogates for bone and marrow respectively. The models varied in thickness in one dimension normal to the direction of propagation, hence exhibiting a range of transit time lateral inhomogeneities, ranging from minimal (single transit time) to maximal (wedge; ultimately the limiting case where each sonic ray has a unique transit time). For the experimental component of the study, two unfocused 1 MHz ¾” broadband diameter transducers were utilized in transmission mode; ultrasound signals were recorded for each of the models. The computer simulation was performed with Matlab, where the transit time and relative amplitude of each sonic ray was calculated. The transit time for each sonic ray was defined as the sum of transit times through acrylic and water components. The relative amplitude considered the reception area for each sonic ray along with absorption in the acrylic. To replicate phase-sensitive detection, all sonic rays were summed and the output signal plotted in comparison with the experimentally derived output signal. Results: From qualtitative and quantitative comparison of the experimental and computer simulation results, there is an extremely high degree of agreement of 94.2% to 99.0% between the two approaches, supporting the concept that propagation of an ultrasound wave, for the models considered, may be approximated by a parallel sonic ray model where the transit time of each ray is defined by the proportion of ‘bone’ and ‘marrow’. Conclusions: This combined experimental and computer simulation study has successfully demonstrated that lateral inhomogeneity of transit time has significant potential for phase interference to occur if a phase-sensitive ultrasound receive transducer is implemented as in most commercial ultrasound bone analysis devices.

Breast cancer detection from thermal images using bispectral invariant features

Highly sensitive infrared (IR) cameras provide high-resolution diagnostic images of the temperature and vascular changes of breasts. These images can be processed to emphasize hot spots that exhibit early and subtle changes owing to pathology. The resulting images show clusters that appear random in shape and spatial distribution but carry class dependent information in shape and texture. Automated pattern recognition techniques are challenged because of changes in location, size and orientation of these clusters. Higher order spectral invariant features provide robustness to such transformations and are suited for texture and shape dependent information extraction from noisy images. In this work, the effectiveness of bispectral invariant features in diagnostic classification of breast thermal images into malignant, benign and normal classes is evaluated and a phase-only variant of these features is proposed. High resolution IR images of breasts, captured with measuring accuracy of ±0.4% (full scale) and temperature resolution of 0.1 °C black body, depicting malignant, benign and normal pathologies are used in this study. Breast images are registered using their lower boundaries, automatically extracted using landmark points whose locations are learned during training. Boundaries are extracted using Canny edge detection and elimination of inner edges. Breast images are then segmented using fuzzy c-means clustering and the hottest regions are selected for feature extraction. Bispectral invariant features are extracted from Radon projections of these images. An Adaboost classifier is used to select and fuse the best features during training and then classify unseen test images into malignant, benign and normal classes. A data set comprising 9 malignant, 12 benign and 11 normal cases is used for evaluation of performance. Malignant cases are detected with 95% accuracy. A variant of the features using the normalized bispectrum, which discards all magnitude information, is shown to perform better for classification between benign and normal cases, with 83% accuracy compared to 66% for the original.

Pharmacokinetics of isofraxidin in rat plasma after oral administration of the extract of acanthopanax senticosus using HPLC with solid phase extraction method

High-performance liquid chromatography coupled with solid phase extraction method was developed for determination of isofraxidin in rat plasma after oral administration of Acanthopanax senticosus extract (ASE), and pharmacokinetic parameters of isofraxidin either in ASE or pure compound were measured. The HPLC analysis was performed on a Dikma Diamonsil RP(18) column (4.6 mm x 150 mm, 5 microm) with the isocratic elution of solvent A (acetonitrile) and solvent B (0.1% aqueous phosphoric acid, v/v) (A : B = 22 : 78) and the detection wavelength was set at 343 nm. The calibration curve was linear over the range of 0.156-15.625 microg/ml. The limit of detection was 60 ng/ml. The intra-day precision was 5.8%, and the inter-day precision was 6.0%. The recovery was 87.30+/-1.73%. When the dosage of ASE is equal to pure compound caculated by the amount of isofraxidin, it has been found to have two maximum concentrations in plasma while the pure compound only showed one peak in the plasma concentration-time curve. The determined content of isofraxidin in plasma after oral administration of ASE is the total contents of free isofraxidin and its precursors in ASE in vitro. The pharmacokinetic characteristics of ASE showed the priority of the extract and the properities of traditional Chinese medicine.

Pharmacokinetics of cimifugin in rat plasma after oral administration of the extract of Saposhnikovia divaricatae root : Determination of cimifugin by high performance liquid chromatography coupled with solid phase extraction

High performance liquid chromatography (HPLC) coupled with the solid phase extraction method was developed for determining cimifugin (a coumarin derivative; one of Saposhnikovia divaricatae's constituents) in rat plasma after oral administration of Saposhnikovia divaricatae extract (SDE), and the pharmacokinetics of cimifugin either in SDE or as a single compound was investigated. The HPLC analysis was performed on a commercially available column (4.6 mm x 200 mm, 5 pm) with the isocratic elution of solvent A (Methanol) and solvent B (Water) (A:B=60:40) and the detection wavelength was set at 250 nm. The calibration curve was linear over the range of 0.100-10.040 microg/mL. The limit of detection was 30 ng/mL. At the rat plasma concentrations of 0.402, 4.016, 10.040 microg/mL, the intra-day precision was 6.21%, 3.98%, and 2.23%; the inter-day precision was 7.59%, 4.26%, and 2.09%, respectively. The absolute recovery was 76.58%, 76.61%, and 77.67%, respectively. When the dosage of SDE was equal to the pure compound calculated by the amount of cimifugin, it was found to have two maximum peaks while the pure compound only showed one peak in the plasma concentration-time curve. The pharmacokinetic characteristics of SDE showed the superiority of the extract and the properties of traditional Chinese medicine.

Analysis of acute-phase proteins, AHSG, C3, CLI, HP and SAA, reveals distinctive expression patterns associated with breast, colorectal and lung cancer

Early detection, clinical management and disease recurrence monitoring are critical areas in cancer treatment in which specific biomarker panels are likely to be very important in each of these key areas. We have previously demonstrated that levels of alpha-2-heremans-schmid-glycoprotein (AHSG), complement component C3 (C3), clusterin (CLI), haptoglobin (HP) and serum amyloid A (SAA) are significantly altered in serum from patients with squamous cell carcinoma of the lung. Here, we report the abundance levels for these proteins in serum samples from patients with advanced breast cancer, colorectal cancer (CRC) and lung cancer compared to healthy controls (age and gender matched) using commercially available enzyme-linked immunosorbent assay kits. Logistic regression (LR) models were fitted to the resulting data, and the classification ability of the proteins was evaluated using receiver-operating characteristic curve and leave-one-out cross-validation (LOOCV). The most accurate individual candidate biomarkers were C3 for breast cancer [area under the curve (AUC) = 0.89, LOOCV = 73%], CLI for CRC (AUC = 0.98, LOOCV = 90%), HP for small cell lung carcinoma (AUC = 0.97, LOOCV = 88%), C3 for lung adenocarcinoma (AUC = 0.94, LOOCV = 89%) and HP for squamous cell carcinoma of the lung (AUC = 0.94, LOOCV = 87%). The best dual combination of biomarkers using LR analysis were found to be AHSG + C3 (AUC = 0.91, LOOCV = 83%) for breast cancer, CLI + HP (AUC = 0.98, LOOCV = 92%) for CRC, C3 + SAA (AUC = 0.97, LOOCV = 91%) for small cell lung carcinoma and HP + SAA for both adenocarcinoma (AUC = 0.98, LOOCV = 96%) and squamous cell carcinoma of the lung (AUC = 0.98, LOOCV = 84%). The high AUC values reported here indicated that these candidate biomarkers have the potential to discriminate accurately between control and cancer groups both individually and in combination with other proteins. Copyright © 2011 UICC.