Identification of abundant alkyl ether glycerophospholipids in the human lens by tandem mass spectrometry techniques

Previous studies have shown that the human lens contains glycerophospholipids with ether linkages. These lipids differ from conventional glycerophospholipids in that the sn-1 substituent is attached to the glycerol backbone via an 1-O-alkyl or an 1-O-alk-1'-enyl ether rather than an ester bond. The present investigation employed a combination of collision-induced dissociation (CID) and ozone-induced dissociation (OzID) to unambiguously distinguish such 1-O-alkyl and 1-O-alk-1'-enyl ethers. Using these methodologies the human lens was found to contain several abundant 1-O-alkyl glycerophos-phoethanolamines, including GPEtn(16:0e/9Z-18:1), GPEtn(11Z-18:1e/9Z-18:1), and GPEtn(18:0e/9Z-18:1), as well as a related series of unusual 1-O-alkyl glycerophosphoserines, including GPSer(16:0e/9Z-18:1), GPSer(11Z-18:1e/9Z-18:1), GPSer(18:0e/9Z-18:1) that to our knowledge have not previously been observed in human tissue. Isomeric 1-O-alk-1'-enyl ethers were absent or in low abundance. Examination of the double bond position within the phospholipids using OzID revealed that several positional isomers were present, including sites of unsaturation at the n-9, n-7, and even n-5 positions. Tandem CID/OzID experiments revealed a preference for double bonds in the n-7 position of 1-O-ether linked chains, while n-9 double bonds predominated in the ester-linked fatty acids [e.g., GPEtn(11Z-18:1e/9Z-18:1) and GPSer(11Z-18:1e/9Z-18:1)]. Different combinations of these double bond positional isomers within chains at the sn-1 and sn-2 positions point to a remarkable molecular diversity of ether-lipids within the human lens.

The fragmentation pathways of protonated Amiton in the gas phase : towards the structural characterisation of organophosphorus chemical warfare agents by electrospray ionisation tandem mass spectrometry

Amiton (O,O-diethyl-S-[2-(diethylamino)ethyl]phosphorothiolate), otherwise known as VG, is listed in schedule 2 of the Chemical Weapons Convention (CWC) and has a structure closely related to VX (O-ethyl-S-(2-diisopropylamino)ethylmethylphosphonothiolate). Fragmentation of protonated VG in the gas phase was performed using electrospray ionisation ion trap mass spectrometry (ESI-ITMS) and revealed several characteristic product ions. Quantum chemical calculations provide the most probable structures for these ions as well as the likely unimolecular mechanisms by which they are formed. The decomposition pathways predicted by computation are consistent with deuterium-labeling studies. The combination of experimental and theoretical data suggests that the fragmentation pathways of VG and analogous organophosphorus nerve agents, such as VX and Russian VX, are predictable and thus ESI tandem mass spectrometry is a powerful tool for the verification of unknown compounds listed in the CWC. Copyright (c) 2006 Commonwealth of Australia. Published by John Wiley & Sons, Ltd.

Mass spectrometric study of the dissociation of Group XI metal complexes with fatty acids and glycerolipids : Ag2H+ and Cu2H+ ion formation in the presence of a double bond

Results of mass spectrometric studies are reported for the collisional dissociation of Group XI (Cu, Ag, Au) metal ion complexes with fatty acids (palmitic, oleic, linoleic and a-linolenic) and glycerolipids. Remarkably, the formation of M2H+ ions (M = Cu, Ag) is observed as a dissociation product of the ion complexes containing more than one metal cation and only if the lipid in the complex contains a double bond. Ag2H+ is formed as the main dissociation channel for all three of the fatty acids containing double bonds that were investigated while Cu2H+ is formed with one of the fatty acids and, although abundant, is not the dominant dissociation channel. Also. Cu(I) and Ag(I) ion complexes were observed with glycerolipids (including triacylglycerols and glycerophospholipids) containing either saturated or unsaturated fatty acid substituents. Interestingly. Ag2H+ ion is formed in a major fragmentation channel with the lipids that are able to form the complex with two metal cations (triacylglycerols and glycerophosphoglycerols), while lipids containing a fixed positive charge (glycerophospocholines) complex only with a single metal cation. The formation of Ag2H+ ion is a significant dissociation channel from the complex ion Ag-2(L-H)(+) where L = Glycerophospholipid (GP) (18:1/18:1). Cu(I) also forms complexes of two metal cations with glycerophospholipids but these do not produce Cu2H+ upon dissociation. Rather organic fragments, not containing Cu(I), are formed, perhaps due to different interactions of these metal cations with lipids resulting from the much smaller ionic radius of Cu(I) compared to Ag(I) (C).

Work and family : the perception of balance among female teachers in northern Malaysia

Women’s participation in paid employment has become a common scenario even in non-western developing countries. For example in Malaysia, the trend is growing although the traditional gender role remains strong in Malaysian society. Even though working, women are still expected to assume major responsibilities at home. Thus, as opposed to men, women in this society face the challenge to satisfactorily balance work and family. This study was carried out to explore how Malaysian women perceive the meaning of a balanced work-family life. Sampling women teachers, the interview findings revealed that work-family balance was mainly perceived in terms of an individual’s ‘ability to fulfill role obligation’ appropriately in both the work and family domains. A few participants also viewed balance in the context of role satisfaction and role interference. Overall, the results support the assumption in the literature that perceptions of work-family experience are not universal, rather, the construct of work-family balance is culture-specific.

Kiwi Forego Vision in the Guidance of Their Nocturnal Activities

Background In vision, there is a trade-off between sensitivity and resolution, and any eye which maximises information gain at low light levels needs to be large. This imposes exacting constraints upon vision in nocturnal flying birds. Eyes are essentially heavy, fluid-filled chambers, and in flying birds their increased size is countered by selection for both reduced body mass and the distribution of mass towards the body core. Freed from these mass constraints, it would be predicted that in flightless birds nocturnality should favour the evolution of large eyes and reliance upon visual cues for the guidance of activity. Methodology/Principal Findings We show that in Kiwi (Apterygidae), flightlessness and nocturnality have, in fact, resulted in the opposite outcome. Kiwi show minimal reliance upon vision indicated by eye structure, visual field topography, and brain structures, and increased reliance upon tactile and olfactory information. Conclusions/Significance This lack of reliance upon vision and increased reliance upon tactile and olfactory information in Kiwi is markedly similar to the situation in nocturnal mammals that exploit the forest floor. That Kiwi and mammals evolved to exploit these habitats quite independently provides evidence for convergent evolution in their sensory capacities that are tuned to a common set of perceptual challenges found in forest floor habitats at night and which cannot be met by the vertebrate visual system. We propose that the Kiwi visual system has undergone adaptive regressive evolution driven by the trade-off between the relatively low rate of gain of visual information that is possible at low light levels, and the metabolic costs of extracting that information.

A new period of volcanogenic massive sulfide formation in the Yilgarn: A volcanological study of the ca 2.76 Ga Hollandaire VMS deposit, Yilgarn Craton, Western Australia

The Archean Hollandaire volcanogenic massive sulfide deposit is a felsic–siliciclastic VMS deposit located in the Murchison Domain of the Youanmi Terrane, Yilgarn Craton, Western Australia. It is hosted in a succession of turbidites, mudstones and coherent rhyodacite sills and has been metamorphosed to upper greenschist/lower amphibolite facies and includes a pervasive S1 deformational fabric. The coherent rhyodacitic sills are interpreted as syndepositional based on geochemical similarities with well-known VMS-associated felsic rocks and similar foliations to the metasediments. We offer several explanations for the absence of textural evidence (e.g. breccias) for syn-depositional origins: 1) the subaqueous sediments were dehydrated by long-lived magmatism such that no pore-water remained to drive quench fragmentation; 2) pore-space occlusion by burial and/or, 3) alteration overprinting and obscuring of primary breccias at contact margins. Mineralisation occurs by sub-seafloor replacement of original host rocks in two ore bodies, Hollandaire Main (~125 x >500 m and ~8 m thick) and Hollandaire West (~100 x 470 m and ~5 m thick), and occurs in three main textural styles, massive sulfides, which are exclusively hosted in turbidites and mudstones, and stringer and disseminated sulfides, which are also hosted in coherent rhyodacite. Most sulfides have textures consistent with remobilisation and recrystallisation. Hydrothermal metamorphism has altered the hangingwall and footwall to similar degrees, with significant gains in Mg, Mn and K and losses in Na, Ca and Sr. Garnet and staurolite porphyryoblasts also exhibit a footprint around mineralisation, extending up to 30 m both above and below the ore zone. High precision thermal ionisation mass spectrometry of zircons extracted from the coherent rhyodacite yield an age of 2759.5 ± 0.9 Ma, which along with geochemical comparisons, places the succession within the 2760–2735 Ma Greensleeves Formation of the Polelle Group of the Murchison Supergroup. Geochemical and geochronological evidence link the coherent rhyodacite sills to the Peter Well Granodiorite pluton ~2 km to the W, which acted as the heat engine driving hydrothermal circulation during VMS mineralisation. This study highlights the importance of both: detailed physical volcanological studies from which an accurate assessment of timing relationships, particularly the possibility of intrusions dismembering ore horizons, can be made; and identifying synvolcanic plutons and other similar suites, for VMS exploration targets in the Youanmi Terrane and worldwide.

The origin of cyclical high- and low-Cr basalts with continental crust trace element signatures in the Kalkarindji Large Igneous Province

The 510 million year old Kalkarindji Large Igneous Province correlates in time with the first major extinction event after the Cambrian explosion of life. Large igneous provinces correlate with all major mass extinction events in the last 500 million years. The genetic link between large igneous provinces and mass extinction remains unclear. My work is a contribution towards understanding magmatic processes involved in the generation of Large Igneous Provinces. I concentrate on the origin of variation in Cr in magmas and have developed a model in which high temperature melts intrude into and assimilate large amounts of upper continental crust.

Submarine record of volcanic island construction and collapse in the Lesser Antilles arc: First scientific drilling of submarine volcanic island landslides by IODP Expedition 340

IODP Expedition 340 successfully drilled a series of sites offshore Montserrat, Martinique and Dominica in the Lesser Antilles from March to April 2012. These are among the few drill sites gathered around volcanic islands, and the first scientific drilling of large and likely tsunamigenic volcanic island-arc landslide deposits. These cores provide evidence and tests of previous hypotheses for the composition and origin of those deposits. Sites U1394, U1399, and U1400 that penetrated landslide deposits recovered exclusively seafloor sediment, comprising mainly turbidites and hemipelagic deposits, and lacked debris avalanche deposits. This supports the concepts that i/ volcanic debris avalanches tend to stop at the slope break, and ii/ widespread and voluminous failures of preexisting low-gradient seafloor sediment can be triggered by initial emplacement of material from the volcano. Offshore Martinique (U1399 and 1400), the landslide deposits comprised blocks of parallel strata that were tilted or microfaulted, sometimes separated by intervals of homogenized sediment (intense shearing), while Site U1394 offshore Montserrat penetrated a flat-lying block of intact strata. The most likely mechanism for generating these large-scale seafloor sediment failures appears to be propagation of a decollement from proximal areas loaded and incised by a volcanic debris avalanche. These results have implications for the magnitude of tsunami generation. Under some conditions, volcanic island landslide deposits composed of mainly seafloor sediment will tend to form smaller magnitude tsunamis than equivalent volumes of subaerial block-rich mass flows rapidly entering water. Expedition 340 also successfully drilled sites to access the undisturbed record of eruption fallout layers intercalated with marine sediment which provide an outstanding high-resolution data set to analyze eruption and landslides cycles, improve understanding of magmatic evolution as well as offshore sedimentation processes.

Analysis, characterisation and expression of gill-expressed carbonic anhydrase genes in the freshwater crayfish Cherax quadricarinatus

Changes in water quality parameters such as pH and salinity can have a significant effect on productivity of aquaculture species. Similarly, relative osmotic pressure influences various physiological processes and regulates expression of a number of osmoregulatory genes. Among those, carbonic anhydrase (CA) plays a key role in systemic acid–base balance and ion regulation. Redclaw crayfish (Cherax quadricarinatus) are unique in their ability to thrive in environments with naturally varied pH levels, suggesting unique adaptation to pH stress. To date, however, no studies have focused on identification and characterisation of CA or other osmoregulatory genes in C. quadricarinatus. Here, we analysed the redclaw gill transcriptome and characterized CA genes along with a number of other key osmoregulatory genes that were identified in the transcriptome. We also examined patterns of gene expression of these CA genes when exposed to three pH treatments. In total, 72,382,710 paired end Illumina reads were assembled into 36,128 contigs with an average length of 800 bp. Approximately 37% of contigs received significant BLAST hits and 22% were assigned gene ontology terms. Three full length CA isoforms; cytoplasmic CA (ChqCAc), glycosyl-phosphatidylinositol-linked CA (ChqCAg), and β-CA (ChqCA-beta) as well as two partial CA gene sequences were identified. Both partial CA genes showed high similarity to ChqCAg and appeared to be duplicated from the ChqCAg. Full length coding sequences of Na+/K+-ATPase, V-type H+-ATPase, sarcoplasmic Ca+-ATPase, arginine kinase, calreticulin and Cl− channel protein 2 were also identified. Only the ChqCAc gene showed significant differences in expression across the three pH treatments. These data provide valuable information on the gill expressed CA genes and their expression patterns in freshwater crayfish. Overall our data suggest an important role for the ChqCAc gene in response to changes in pH and in systemic acid–base balance in freshwater crayfish.

Investigating sea level rise due to global warming in the teaching laboratory using Archimedes’ principle

A teaching laboratory experiment is described that uses Archimedes’ principle to precisely investigate the effect of global warming on the oceans. A large component of sea level rise is due to the increase in the volume of water due to the decrease in water density with increasing temperature. Water close to 0 °C is placed in a beaker and a glass marble hung from an electronic balance immersed in the water. As the water warms, the weight of the marble increases as the water is less buoyant due to the decrease in density. In the experiment performed in this paper a balance with a precision of 0.1 mg was used with a marble 40.0 cm3 and mass of 99.3 g, yielding water density measurements with an average error of -0.008 ± 0.011%.

Maternal pregravid body mass index and child hospital admissions in the first 5 years of life: results from an Australian birth cohort

Objectives: To examine the association of maternal pregravid body mass index (BMI) and child offspring, all-cause hospitalisations in the first 5 years of life. Methods: Prospective birth cohort study. From 2006 to 2011, 2779 pregnant women (2807 children) were enrolled in the Environments for Healthy Living: Griffith birth cohort study in South-East Queensland, Australia. Hospital delivery record and self-report baseline survey of maternal, household and demographic factors during pregnancy were linked to the Queensland Hospital Admitted Patients Data Collection from 1 November 2006 to 30 June 2012, for child admissions. Maternal pregravid BMI was classified as underweight (<18.5 kg m−2), normal weight (18.5–24.9 kg m−2), overweight (25.0–29.9 kg m−2) or obese (30 kg m−2). Main outcomes were the total number of child hospital admissions and ICD-10-AM diagnostic groupings in the first 5 years of life. Negative binomial regression models were calculated, adjusting for follow-up duration, demographic and health factors. The cohort comprised 8397.9 person years (PYs) follow-up. Results: Children of mothers who were classified as obese had an increased risk of all-cause hospital admissions in the first 5 years of life than the children of mothers with a normal BMI (adjusted rate ratio (RR) =1.48, 95% confidence interval 1.10–1.98). Conditions of the nervous system, infections, metabolic conditions, perinatal conditions, injuries and respiratory conditions were excessive, in both absolute and relative terms, for children of obese mothers, with RRs ranging from 1.3–4.0 (PYs adjusted). Children of mothers who were underweight were 1.8 times more likely to sustain an injury or poisoning than children of normal-weight mothers (PYs adjusted). Conclusion: Results suggest that if the intergenerational impact of maternal obesity (and similarly issues related to underweight) could be addressed, a significant reduction in child health care use, costs and public health burden would be likely.

In the red shadow of the Earth

A technique is described for calculating the brightness of the atmosphere of the Earth that shines into the Earth’s umbra during a total lunar eclipse making the Moon red. This ‘Rim of Fire’ is due to refracted un scattered light from all the sunrises and sunsets rimming the Earth. In this article, a photograph of the totally eclipsed Moon was compared with the Full Moon and the difference in brightness calculated taking into account the exposure time and ISO setting. The results show that the Full Moon is over 14 000 times brighter than the totally eclipsed Moon. The relative brightness of the eclipsed Moon can be used to estimate that the luminance of Rim of Fire is over 12 trillion watts. The experiment described in this paper would be suitable as a high school or university exercise.

Pivotal principles for digital earth development in the 21st century

Reductionist thinking will no longer suffice to address contemporary, complex challenges that defy sectoral, national, or disciplinary boundaries. Furthermore, lessons learned from the past cannot be confidently used to predict outcomes or help guide future actions. The authors propose that the confluence of a number of technology and social disruptors presents a pivotal moment in history to enable real-time, accelerated and integrated action that can adequately support a ‘future earth’ through transformational solutions. Building on more than a decade of dialogues hosted by the International Society for Digital Earth (ISDE), and evolving a briefing note presented to delegates of Pivotal2015, the paper presents an emergent context for collectively addressing spatial information, sustainable development and good governance through three guiding principles for enabling prosperous living in the 21st Century. These are: (1) open data, (2) real world context and (3) informed visualization for decision support. The paper synthesizes an interdisciplinary dialogue to create a credible and positive future vision of collaborative and transparent action for the betterment of humanity and planet. It is intended that the three Pivotal Principles can be used as an elegant framework for action towards the Digital Earth vision, across local, regional, and international communities and organizations.

Comment on “Whole-genome analyses resolve early branches in the tree of life of modern birds”

Jarvis et al. (Research Articles, 12 December 2014, p. 1320) presented molecular clock analyses that suggested that most modern bird orders diverged just after the mass extinction event at the Cretaceous-Paleogene boundary (about 66 million years ago). We demonstrate that this conclusion results from the use of a single inappropriate maximum bound, which effectively precludes the Cretaceous diversification overwhelmingly supported by previous molecular studies.