Comparison of the binding stoichiometries of positively charged DNA-binding drugs using positive and negative ion electrospray ionization mass spectrometry

Positive and negative ion electrospray ionization (ESI) mass spectra of complexes of positively charged small molecules (distamycin, Hoechst 33258, [Ru(phen)2dpq]Cl2 and [Ru(phen)2dpqC]Cl2) have been compared. [Ru(phen)2dpq]Cl2 and [Ru(phen)2dpqC]Cl2 bind to DNA by intercalation. Negative ion ESI mass spectra of mixtures of [Ru(phen)2dpq]Cl2 or [Ru(phen)2dpqC]Cl2 with DNA showed ions from DNA-ligand complexes consistent with solution studies. In contrast, only ions from freeDNAwere present in positive ion ESI mass spectra of mixtures of [Ru(phen)2dpq]Cl2 or [Ru(phen)2dpqC]Cl2 with DNA, highlighting the need for obtaining ESI mass spectra of non-covalent complexes under a range of experimental conditions. Negative ion spectra of mixtures of the minor groove binder Hoechst 33258 with DNA containing a known minor groove binding sequence were dominated by ions from a 1:1 complex. In contrast, in positive ion spectra there were also ions present from a 2:1 (Hoechst 33258: DNA) complex, suggesting an alternative binding mode was possible either in solution or in the gas phase. When Hoechst 33258 was mixed with a DNA sequence lacking a high affinity minor groove binding site, the negative ion ESI mass spectra showed that 1:1 and 2:1 complexes were formed, consistent with existence of binding modes other than minor groove binding. The data presented suggest that comparison of positive and negative ion ESI-MS spectra might provide an insight into various binding modes in both solution and the gas phase.

Challenges in mass spectrometry-based quantification of bioactive peptides: A case study exploring the neuropeptide Y family

The study of biologically active peptides is critical to the understanding of physiological pathways, especially those involved in the development of disease. Historically, the measurement of biologically active endogenous peptides has been undertaken by radioimmunoassay, a highly sensitive and robust technique that permits the detection of physiological concentrations in different biofluid and tissue extracts. Over recent years, a range of mass spectrometric approaches have been applied to peptide quantification with limited degrees of success. Neuropeptide Y (NPY), peptide YY (PYY), and pancreatic polypeptide (PP) belong to the NPY family exhibiting regulatory effects on appetite and feeding behavior. The physiological significance of these peptides depends on their molecular forms and in vivo concentrations systemically and at local sites within tissues. In this report, we describe an approach for quantification of individual peptides within mixtures using high-performance liquid chromatography electrospray ionization tandem mass spectrometry analysis of the NPY family peptides. Aspects of quantification including sample preparation, the use of matrix-matched calibration curves, and internal standards will be discussed. This method for the simultaneous determination of NPY, PYY, and PP was accurate and reproducible but lacks the sensitivity required for measurement of their endogenous concentration in plasma. The advantages of mass spectrometric quantification will be discussed alongside the current obstacles and challenges. © 2012 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 98: 357–366, 2012.

Undrained sediment loading key to long-runout submarine mass movements : evidence from the Caribbean Volcanic Arc

Long undersea debris runout can be facilitated by a boundary layer formed by weak marine sediments under a moving slide mass. Undrained loading of such offshore sediment results in a profound drop of basal shear resistance, compared to subaerial shear resistance, enabling long undersea runout. Thus large long-runout submarine landslides are not truly enigmatic (Voight and Elsworth 1992, 1997), but are understandable in terms of conventional geotechnical principles. A corollary is that remoulded undrained strength, and not friction angle, should be used for basal resistance in numerical simulations. This hypothesis is testable via drilling and examining the structure at the soles of undersea debris avalanches for indications of incorporation of sheared marine sediments, by tests of soil properties, and by simulations. Such considerations of emplacement process are an aim of ongoing research in the Lesser Antilles (Caribbean Sea), where multiple offshore debris avalanche and dome-collapse debris deposits have been identified since 1999 on swath bathymetric surveys collected in five oceanographic cruises. This paper reviews the prehistoric and historic collapses that have occurred offshore of Antilles arc islands and summarizes ongoing research on emplacement processes.

Mass transfer properties (permeability and mass diffusivity) of four australian hardwood species

Characterization of mass transfer properties was achieved in the longitudinal, radial, and tangential directions for four Australian hardwood species: spotted gum, blackbutt, jarrah, and messmate. Measurement of mass transfer properties for these species was necessary to complement current vacuum drying modeling research. Water-vapour diffusivity was determined in steady state using a specific vapometer. Permeability was determined using a specialized device developed to measure over a wide range of permeability values. Permeability values of some species and material directions were extremely low and undetectable by the mass flow meter device. Hence, a custom system based on volume evolution was conceived to determine very low, previously unpublished, wood permeability values. Mass diffusivity and permeability were lowest for spotted gum and highest for messmate. Except for messmate in the radial direction, the four species measured were less permeable in all directions than the lowest published figures, demonstrating the high impermeability of Australian hardwoods and partly accounting for their relatively slow drying rates. Permeability, water-vapour diffusivity, and associated anisotropic ratio data obtained for messmate were extreme or did not follow typical trends and is consequently the most difficult of the four woods to dry in terms of collapse and checking degradation. © The State of Queensland, Department of Agriculture, Fisheries and Forestry, 2012.

The health and cost implications of high body mass index in Australian Defence Force personnel.

BACKGROUND: Frequent illness and injury among workers with high body mass index (BMI) can raise the costs of employee healthcare and reduce workforce maintenance and productivity. These issues are particularly important in vocational settings such as the military, which require good physical health, regular attendance and teamwork to operate efficiently. The purpose of this study was to compare the incidence of injury and illness, absenteeism, productivity, healthcare usage and administrative outcomes among Australian Defence Force personnel with varying BMI. METHODS: Personnel were grouped into cohorts according to the following ranges for (BMI): normal (18.5-24.9 kg/m²; n = 197), overweight (25-29.9 kg/m²; n = 154) and obese (≥30 kg/m²) with restricted body fat (≤28 % for females, ≤24 % for males) (n = 148) and with no restriction on body fat (n = 180). Medical records for each individual were audited retrospectively to record the incidence of injury and illness, absenteeism, productivity, healthcare usage (i.e., consultation with medical specialists, hospital stays, medical investigations, prescriptions) and administrative outcomes (e.g., discharge from service) over one year. These data were then grouped and compared between the cohorts. RESULTS: The prevalence of injury and illness, cost of medical specialist consultations and cost of medical scans were all higher (p <0.05) in both obese cohorts compared with the normal cohort. The estimated productivity losses from restricted work days were also higher (p <0.05) in the obese cohort with no restriction on body fat compared with the normal cohort. Within the obese cohort, the prevalence of injury and illness, healthcare usage and productivity were not significantly greater in the obese cohort with no restriction on body fat compared with the cohort with restricted body fat. The number of restricted work days, the rate of re-classification of Medical Employment Classification and the rate of discharge from service were similar between all four cohorts. CONCLUSIONS: High BMI in the military increases healthcare usage, but does not disrupt workforce maintenance. The greater prevalence of injury and illness, greater healthcare usage and lower productivity in obese Australian Defence Force personnel is not related to higher levels of body fat.

Preliminary results on the characterisation of organic aerosols in urban schools by Aerosol Mass Spectrometry

Vehicle emissions have been linked to detrimental health effects with children thought to be more susceptible (See e.g., Ryan et al 2005). In an urban environment a major source of organic aerosols (OA) are vehicle emissions. The ambient concentration of OA is dynamic in nature and the use of an aerosol mass spectrometer can achieve the necessary temporal resolution to capture the daily variation of OA (Jimenez et al 2009). Currently there is a limited understanding of effects of long term exposure to traffic emissions on children’s health. In the present study, we used an aerosol mass spectrometer to monitor OA and determine children’s potential exposure at school to traffic emissions.In this paper, we present the preliminary results of this investigation. The study is a part of a larger project aimed at gaining a holistic picture of the exposure of children to traffic related pollutants, known as UPTECH (www.ilaqh.qut.edu.au/Misc/ UPTECH%20Home.htm).

Making sense of mass education

Making Sense of Mass Education provides a comprehensive analysis of the field of mass education. The book presents new assessment of traditional issues associated with education – class, race, gender, discrimination and equity –to dispel myths and assumptions about the classroom. It examines the complex relationship between the media, popular culture and schooling, and places the expectations surrounding the modern teacher within ethical, legal and historical contexts. The book blurs some of the disciplinary boundaries within the field of education, drawing upon sociology, cultural studies, history, philosophy, ethics and jurisprudence to provide stronger analyses. The book reframes the sociology of education as a complex mosaic of cultural practices, forces and innovations. Engaging and contemporary, it is an invaluable resource for teacher education students, and anyone interested in a better understanding of mass education.

Comparing measures of fat-free mass in overweight older adults using three different bioelectrical impedance devices and three prediction equations

Objectives: To compare measures of fat-free mass (FFM) by three different bioelectrical impedance analysis (BIA) devices and to assess the agreement between three different equations validated in older adult and/or overweight populations. Design: Cross-sectional study. Setting: Orthopaedics ward of Brisbane public hospital, Australia. Participants: Twenty-two overweight, older Australians (72 yr ± 6.4, BMI 34 kg/m2 ± 5.5) with knee osteoarthritis. Measurements: Body composition was measured using three BIA devices: Tanita 300-GS (foot-to-foot), Impedimed DF50 (hand-to-foot) and Impedimed SFB7 (bioelectrical impedance spectroscopy (BIS)). Three equations for predicting FFM were selected based on their ability to be applied to an older adult and/ or overweight population. Impedance values were extracted from the hand-to-foot BIA device and included in the equations to estimate FFM. Results: The mean FFM measured by BIS (57.6 kg ± 9.1) differed significantly from those measured by foot-to-foot (54.6 kg ± 8.7) and hand-to-foot BIA (53.2 kg ± 10.5) (P < 0.001). The mean ± SD FFM predicted by three equations using raw data from hand-to-foot BIA were 54.7 kg ± 8.9, 54.7 kg ± 7.9 and 52.9 kg ± 11.05 respectively. These results did not differ from the FFM predicted by the hand-to-foot device (F = 2.66, P = 0.118). Conclusions: Our results suggest that foot-to-foot and hand-to-foot BIA may be used interchangeably in overweight older adults at the group level but due to the large limits of agreement may lead to unacceptable error in individuals. There was no difference between the three prediction equations however these results should be confirmed within a larger sample and against a reference standard.

Modeling heat and mass transfer process during convection drying of fruit

Fruit drying is a process of removing moisture to preserve fruits by preventing microbial spoilage. It increases shelf life, reduce weight and volume thus minimize packing, storage, and transportation cost and enable storage of food under ambient environment. But, it is a complex process which involves combination of heat and mass transfer and physical property change and shrinkage of the material. In this background, the aim of this paper to develop a mathematical model to simulate coupled heat and mass transfer during convective drying of fruit. This model can be used predict the temperature and moisture distribution inside the fruits during drying. Two models were developed considering shrinkage dependent and temperature dependent moisture diffusivity and the results were compared. The governing equations of heat and mass transfer are solved and a parametric study has been done with Comsol Multiphysics 4.3. The predicted results were validated with experimental data.

Timing and emplacement dynamics of newly recognised mass flow deposits at ~ 8–12 ka offshore Soufrière Hills volcano, Montserrat : how submarine stratigraphy can complement subaerial eruption histories

This contribution describes two mass movement deposits (total volume ~0.5 km3) identified in seven marine cores located 8 to 15 km offshore southern Montserrat, West Indies. The deposits were emplaced in the last 35 ka and have not previously been recognised in either the subaerial or distal submarine records. Age constraints, provided by radiocarbon dating, show that an explosive volcanic eruption occurred at ca 8–12 ka, emplacing a primary eruption-related deposit that overlies a large (~0.3 km3) reworked bioclastic and volcaniclastic flow deposit, formed from a shelf collapse between 8 and 35 ka. The origin of these deposits has been deduced through the correlation of marine sediment cores, component analysis and geochemical analysis. The 8–12 ka primary volcanic deposit was likely derived from a highly-erosive pyroclastic flow from the Soufrière Hills volcano that entered the ocean and mixed with the water column forming a water-supported density current. Previous investigations of the eruption record suggested that there was a hiatus in activity at the Soufrière Hills volcano between 16 and 6 ka. The ca 8–12 ka eruptive episode identified here shows that this hiatus was shorter than previously hypothesised, and thus highlights the importance of obtaining an accurate and completemarine record of events offshore from volcanic islands and incorporating such data into eruption history reconstructions. Comparisons with the submarine deposit characteristics of the 2003 dome collapse also suggests that the ~8–12 ka eruptive episode was more explosive than eruptions from the current eruptive episode.

Prediction of age at menopause from assessment of ovarian reserve may be improved by using body mass index and smoking status

Objective: Menopause is the consequence of exhaustion of the ovarian follicular pool. AMH, an indirect hormonal marker of ovarian reserve, has been recently proposed as a predictor for age at menopause. Since BMI and smoking status are relevant independent factors associated with age at menopause we evaluated whether a model including all three of these variables could improve AMH-based prediction of age at menopause. Methods: In the present cohort study, participants were 375 eumenorrheic women aged 19–44 years and a sample of 2,635 Italian menopausal women. AMH values were obtained from the eumenorrheic women. Results: Regression analysis of the AMH data showed that a quadratic function of age provided a good description of these data plotted on a logarithmic scale, with a distribution of residual deviates that was not normal but showed significant leftskewness. Under the hypothesis that menopause can be predicted by AMH dropping below a critical threshold, a model predicting menopausal age was constructed from the AMH regression model and applied to the data on menopause. With the AMH threshold dependent on the covariates BMI and smoking status, the effects of these covariates were shown to be highly significant. Conclusions: In the present study we confirmed the good level of conformity between the distributions of observed and AMH-predicted ages at menopause, and showed that using BMI and smoking status as additional variables improves AMH-based prediction of age at menopause.