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).

Construction of interstellar cumulenes and heterocumulenes : Mass spectrometric studies

The last few years have brought an increasing interest in the chemistry of rite interstellar and circumstellar environs. Many of the molecular species discovered in remote galactic regions have been dubbed 'non-terrestrial' because of their unique structures (Thaddeus et al, 1993). These findings have provided a challenge to chemists in many differing fields to attempt to generate these unusual species in the laboratory of particular recent interest have been the unsaturated hydrocarbon families, CnH and CnH2, which have been pursued by a number of diverse methodologies. A wine range of heterocumulenes, including CnO, HCnO, CnN, HCnN, CnS, HCnS, CnSi and HCnSi have also provided intriguing targets for laboratory experiments. Strictly the term cumulene refers to a class of compounds that possess a series of adjacent double bonds, with allene representing the simplest example (H2C=C=CH2). However for many of the non-terrestrial molecules presented here, the carbon chain cannot be described in terms of a single simple valence structure, and so we use the terms cumulene and heterocumulene in a more general sense: to describe molecular species that contain an unsaturated polycarbon chain. Mass spectrometry has proved an invaluable tool in the quest for interstellar cumulenes and heterocumulenes in the laboratory it has the ability in its many forms, to (i) generate charged analogs of these species in the gas phase, (ii) probe their connectivity, ion chemistry, and thermochemistry, and (iii) in some cases, elucidate the neutrals themselves. Here, we will discuss the progress of these studies to this time. (C) 1999 John Wiley & Sons, Inc.

Using ambient ozone for assignment of double bond position in unsaturated lipids

Unsaturated lipids deposited onto a range of materials are observed to react with the low concentrations of ozone present in normal laboratory air. Parent lipids and ozonolysis cleavage products are both detected directly from surfaces by desorption electrospray ionisation mass spectrometry (DESI-MS) with the resulting mass spectra providing clear evidence of the double bond position within these molecules. This serendipitous process has been coupled with thin-layer chromatography (TLC) to provide a simple but powerful approach for the detailed structural elucidation of lipids present in complex biological extracts. Lipid extracts from human lens were deposited onto normal phase TLC plates and then developed to separate components according to lipid class. Exposure of the developed plates to laboratory air for ca. 1 h prior to DESI-MS analysis gave rise to ozonolysis products allowing for the unambiguous identification of double bond positions in even low abundant, unsaturated lipids. In particular, the co-localization of intact unsaturated lactosylceramides (LacCer) with products from their oxidative cleavage provide the first evidence for the presence of three isomeric LacCer (d18:0/24:1) species in the ocular lens lipidome, i.e., variants with double bonds at the n-9, n-7 and n-5 positions.

An assessment of the geographical scale of recurrent gene flow in wild populations of two species of Mekong River carps (Henicorhynchus spp.)

The Mekong is the most productive river fishery in the world, and such as, the Mekong River Basin (MRB) is very important to very large human populations across the region as a source of revenue (through fishing and marketing of aquatic resources products) and as the major source for local animal protein. Threats to biodiversity in the MRB, either to the fishery sector itself or to other sectors are a major concern, even though currently, fisheries across this region are still very productive. If not managed properly however, fish population declines will cause significant economic impact and affect livelihoods of local people and will have a major impact on food security and nutrition. Biodiversity declines will undoubtedly affect food security, income and socio-economic status of people in the MRB that depend on aquatic resources. This is an indicator of unsustainable development and hence should be avoided. Genetic diversity (biodiversity) that can be measured using techniques based on DNA markers; refers to variation within and among populations within the same species or reproductive units. In a population, new genetic variation is generated by sexual recombination contributed by individuals with mutations in genes and chromosomes. Over time, populations of a species that are not reproducing together will diverge as differential impacts of selection and genetic drift change their genetic attributes. For mud carp (Henicorhynchus spp.), understanding the status of breeding units in the MRB will be important for their long term persistence, sustainability and for implementing effective management strategies. Earlier analysis of stock structure in two economically important mud carp species (Henicorhynchus siamensis and H. lobatus) in the MRB completed with mtDNA markers identified a number of populations of both species where gene flow had apparently been interrupted or reduced but applying these data directly to management unit identification is potentially compromised because information was only available about female dispersal patterns. The current study aimed to address this problem and to fully assess the extent of current gene flow (nDNA) and reproductive exchange among selected wild populations of two species of carp (Henicorhynchus spp.) of high economic importance in the MRB using combined mtDNA and nDNA markers. In combination, the data can be used to define effective management units for each species. In general, nDNA diversity for H. lobatus (with average allelic richness (A) 7.56 and average heterozygosity (Ho) 0.61) was very similar to that identified for H. siamensis (A = 6.81 and Ho = 0.75). Both mud carp species show significant but low FST estimates among populations as a result of lower genetic diversity among sampled populations compared with genetic diversity within populations that may potentially mask any 'real' population structure. Overall, population genetic structure patterns from mtDNA and nDNA in both Henicorhynchus species were largely congruent. Different population structures however, were identified for the two Henicorhynchus species across the same geographical area. Apparent co-similarity in morphology and co-distribution of these two relatively closely related species does not apparently imply parallel evolutionary histories. Differences in each species population structure likely reflect historical drainage rearrangement of the Mekong River. The data indicate that H. siamensis is likely to have occupied the Mekong system for much longer than has H. lobatus in the past. Two divergent stocks were identified for H. lobatus in the MRB below the Khone Falls while a single stock had been evident in the earlier mtDNA study. This suggests that the two Henicorhynchus species may possess different life history traits and that different patterns of gene flow has likely influenced modern genetic structure in these close congeners. In combination, results of the earlier mtDNA and the current study have implications for effective management of both Henicorhynchus species across the MRB. Currently, both species are essentially treated as a single management unit in this region. This strategy may be appropriate for H. lobatus as a single stock was evident in the main stream of the MRB, but may not be appropriate for H. siamensis as more than a single stock was identified across the same range for this species. Management strategies should consider this difference to conserve overall biodiversity (local discrete populations) and this will include maintaining natural habitat and migration pathways, provision of fish sanctuaries (refuges) and may also require close monitoring of any stock declines, a signal that may require effective recovery strategies.

Ozonolysis of phospholipid double bonds during electrospray ionization : A new tool for structure determination

Phospholipids are the key structural component of cell membranes, and recent advances in electrospray ionization mass spectrometry provide for the fast and efficient analysis of these compounds in biological extracts.1-3 The application of electrospray ionization tandem mass spectrometry (ESI-MS/MS) to phospholipid analysis has demonstrated several key advantages over the more traditional chromatographic methods, including speed and greater structural information.4 For example, the ESI-MS/MS spectrum of a typical phospholipidsparticularly in negative ion modesreadily identifies the carbon chain length and the degree of unsaturation of each of the fatty acids esterified to the parent molecule.5 A critical limitation of conventional ESI-MS/MS analysis, however, is the inability to uniquely identify the position of double bonds within the fatty acid chains. This is especially problematic given the importance of double bond position in determining the biological function of lipid classes.6 Previous attempts to identify double bond position in intact phospholipids using mass spectrometry employ either MS3 or offline chemical derivatization.7-11 The former method requires specialized instrumentation and is rarely applied, while the latter methods suffer from complications inherent in sample handling prior to analysis. In this communication we outline a novel on-line approach for the identification of double bond position in intact phospholipids. In our method, the double bond(s) present in unsaturated phospholipids are cleaved by ozonolysis within the ion source of a conventional ESI mass spectrometer to give two chemically induced fragment ions that may be used to unambiguously assign the position of the double bond. This is achieved by using oxygen as the electrospray nebulizing gas in combination with high electrospray voltages to initiate the formation of an ozoneproducing.

Similarity solutions for flow and heat transfer of non-Newtonian fluid over a stretching surface

Similarity solutions are carried out for flow of power law non-Newtonian fluid film on unsteady stretching surface subjected to constant heat flux. Free convection heat transfer induces thermal boundary layer within a semi-infinite layer of Boussinesq fluid. The nonlinear coupled partial differential equations (PDE) governing the flow and the boundary conditions are converted to a system of ordinary differential equations (ODE) using two-parameter groups. This technique reduces the number of independent variables by two, and finally the obtained ordinary differential equations are solved numerically for the temperature and velocity using the shooting method. The thermal and velocity boundary layers are studied by the means of Prandtl number and non-Newtonian power index plotted in curves.

Identification of double bond position in lipids : From GC to OzID

Recent developments in mass spectrometry and chromatography provide new possibilities for the identification and in some instances quantification of a wide range of lipids in complex matrices. These advances in analytical technologies have provided a tantalizing glimpse of the true structural diversity of lipids in nature and have reinvigorated interest in the role of lipids in biology. While technological advances have been impressive, difficulties in the ready identification of sites of unsaturation (i.e., double bond position) within these molecules presents a significant impediment to understanding lipid biochemistry. This is of particular importance given the growing body of literature suggesting that the presence of naturally occurring lipid double bond isomers can have a significant influence, both positive and negative, on the development of pathologies such as cancer, cardiovascular disease and type 2 diabetes. This article provides a critical review of the Current suite of analytical approaches to the challenge of identification of the position of carbon-carbon double bonds in intact lipids. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

A natural oil-based emulsion containing allantoin versus aqueous cream for managing radiation-induced skin reactions in patients with cancer : a phase III double-blind randomised controlled trial

Purpose To investigate the effects of a natural oil-based emulsion containing allantoin versus aqueous cream for preventing and managing radiation induced skin reactions (RISR). Methods and Materials A total of 174 patients were randomised and participated in the study. Patients either received Cream 1 (the natural oil-based emulsion containing allantoin) or Cream 2 (aqueous cream). Skin toxicity, pain, itching and skin-related quality of life scores were collected for up to four weeks after radiation treatment. Results Patients who received Cream 1 had a significantly lower average level of Common Toxicity Criteria at week 3 (p<0.05), but had statistically higher average levels of skin toxicity at weeks 7, 8 and 9 (all p<0.001). Similar results were observed when skin toxicity was analysed by grades. With regards to pain, patients in the Cream 2 group had a significantly higher average level of worst pain (p<0.05) and itching (p=0.046) compared to the Cream 1 group at week 3, however these differences were not observed at other weeks. In addition, there was a strong trend for Cream 2 to reduce the incidence of grade 2 or more skin toxicity in comparison to Cream 1 (p=0.056). Overall, more participants in the Cream 1 group were required to use another topical treatment at weeks 8 (p=0.049) and 9 (p=0.01). Conclusion The natural oil-based emulsion containing allantoin appears to have similar effects for managing skin toxicity compared to aqueous cream up to week 5, however, it becomes significantly less effective at later weeks into the radiation treatment and beyond treatment completion (week 6 and beyond). There were no major differences in pain, itching and skin-related quality of life. In light of these results, clinicians and patients can base their decision on costs and preferences. Overall, aqueous cream appears to be a more preferred option.

Double-authentication-preventing signatures

Digital signatures are often used by trusted authorities to make unique bindings between a subject and a digital object; for example, certificate authorities certify a public key belongs to a domain name, and time-stamping authorities certify that a certain piece of information existed at a certain time. Traditional digital signature schemes however impose no uniqueness conditions, so a trusted authority could make multiple certifications for the same subject but different objects, be it intentionally, by accident, or following a (legal or illegal) coercion. We propose the notion of a double-authentication-preventing signature, in which a value to be signed is split into two parts: a subject and a message. If a signer ever signs two different messages for the same subject, enough information is revealed to allow anyone to compute valid signatures on behalf of the signer. This double-signature forgeability property discourages signers from misbehaving---a form of self-enforcement---and would give binding authorities like CAs some cryptographic arguments to resist legal coercion. We give a generic construction using a new type of trapdoor functions with extractability properties, which we show can be instantiated using the group of sign-agnostic quadratic residues modulo a Blum integer.

Chemotherapeutic compounds targeting the DNA double-strand break repair pathways : the good, the bad, and the promising

The repair of DNA double-strand breaks (DSBs) is a critical cellular mechanism that exists to ensure genomic stability. DNA DSBs are the most deleterious type of insult to a cell’s genetic material and can lead to genomic instability, apoptosis, or senescence. Incorrectly repaired DNA DSBs have the potential to produce chromosomal translocations and genomic instability, potentially leading to cancer. The prevalence of DNA DSBs in cancer due to unregulated growth and errors in repair opens up a potential therapeutic window in the treatment of cancers. The cellular response to DNA DSBs is comprised of two pathways to ensure DNA breaks are repaired: homologous recombination and non-homologous end joining. Identifying chemotherapeutic compounds targeting proteins involved in these DNA repair pathways has shown promise as a cancer therapy for patients, either as a monotherapy or in combination with genotoxic drugs. From the beginning, there have been a number of chemotherapeutic compounds that have yielded successful responses in the clinic, a number that have failed (CGK-733 and iniparib), and a number of promising targets for future studies identified. This review looks in detail at how the cell responds to these DNA DSBs and investigates the chemotherapeutic avenues that have been and are currently being explored to target this repair process.

Corner and finger formation in Hele-Shaw flow with kinetic undercooling regularisation

We examine the effect of a kinetic undercooling condition on the evolution of a free boundary in Hele--Shaw flow, in both bubble and channel geometries. We present analytical and numerical evidence that the bubble boundary is unstable and may develop one or more corners in finite time, for both expansion and contraction cases. This loss of regularity is interesting because it occurs regardless of whether the less viscous fluid is displacing the more viscous fluid, or vice versa. We show that small contracting bubbles are described to leading order by a well-studied geometric flow rule. Exact solutions to this asymptotic problem continue past the corner formation until the bubble contracts to a point as a slit in the limit. Lastly, we consider the evolving boundary with kinetic undercooling in a Saffman--Taylor channel geometry. The boundary may either form corners in finite time, or evolve to a single long finger travelling at constant speed, depending on the strength of kinetic undercooling. We demonstrate these two different behaviours numerically. For the travelling finger, we present results of a numerical solution method similar to that used to demonstrate the selection of discrete fingers by surface tension. With kinetic undercooling, a continuum of corner-free travelling fingers exists for any finger width above a critical value, which goes to zero as the kinetic undercooling vanishes. We have not been able to compute the discrete family of analytic solutions, predicted by previous asymptotic analysis, because the numerical scheme cannot distinguish between solutions characterised by analytic fingers and those which are corner-free but non-analytic.

Atmospheric-pressure plasma jets : effect of gas flow, active species, and snake-like bullet propagation

Cold atmospheric-pressure plasma jets have recently attracted enormous interest owing to numerous applications in plasma biology, health care, medicine, and nanotechnology. A dedicated study of the interaction between the upstream and downstream plasma plumes revealed that the active species (electrons, ions, excited OH, metastable Ar, and nitrogen-related species) generated by the upstream plasma plume enhance the propagation of the downstream plasma plume. At gas flows exceeding 2 l/min, the downstream plasma plume is longer than the upstream plasma plume. Detailed plasma diagnostics and discharge species analysis suggest that this effect is due to the electrons and ions that are generated by the upstream plasma and flow into the downstream plume. This in turn leads to the relatively higher electron density in the downstream plasma. Moreover, high-speed photography reveals a highly unusual behavior of the plasma bullets, which propagate in snake-like motions, very differently from the previous reports. This behavior is related to the hydrodynamic instability of the gas flow, which results in non-uniform distributions of long-lifetime active species in the discharge tube and of surface charges on the inner surface of the tube.

CFD convective flow simulation of the varying properties of CO2-H20 mixtures in geothermal systems

Numerical simulation of a geothermal reservoir, modelled as a bottom-heated square box, filled with water-CO2 mixture is presented in this work. Furthermore, results for two limiting cases of a reservoir filled with either pure water or CO2 are presented. Effects of different parameters including CO2 concentration as well as reservoir pressure and temperature on the overall performance of the system are investigated. It has been noted that, with a fixed reservoir pressure and temperature, any increase in CO2concentration leads to better performance, i.e. stronger convection and higher heat transfer rates. With a fixed CO2 concentration, however, the reservoir pressure and temperature can significantly affect the overall heat transfer and flow rate from the reservoir. Details of such variations are documented and discussed in the present paper.

Effect of a floating electrode on a plasma jet

Two kinds of floating electrode, floating dielectric barrier covered electrode (FDBCE) and floating pin electrode (FPE), which can enhance the performance of plasma jet are reported. The intense discharge between the floating electrode and power electrode decreased the voltage to trigger the plasma jet substantially. The transition of plasma bullet from ring shape to disk shape in the high helium concentration region happened when the floating electrode was totally inside the powered ring electrode. The enhanced electric field between propagating plasma bullet and ground electrode is the reason for this transition. The double plasma bullets happened when part of the FDBCE was outside the powered ring electrode, which is attributed to the structure and surface charge of FDBCE. As part of the FPE was outside the powered ring electrode, the return stroke resulted in a single intensified plasma channel between FPE and ground electrode.

CFD simulations of flow and heat transfer through the porous interface of a metal foam heat exchanger

This paper offers numerical modelling of a waste heat recovery system. A thin layer of metal foam is attached to a cold plate to absorb heat from hot gases leaving the system. The heat transferred from the exhaust gas is then transferred to a cold liquid flowing in a secondary loop. Two different foam PPI (Pores Per Inch) values are examined over a range of fluid velocities. Numerical results are then compared to both experimental data and theoretical results available in the literature. Challenges in getting the simulation results to match those of the experiments are addressed and discussed in detail. In particular, interface boundary conditions specified between a porous layer and a fluid layer are investigated. While physically one expects much lower fluid velocity in the pores compared to that of free flow, capturing this sharp gradient at the interface can add to the difficulties of numerical simulation. The existing models in the literature are modified by considering the pressure gradient inside and outside the foam. Comparisons against the numerical modelling are presented. Finally, based on experimentally-validated numerical results, thermo-hydraulic performance of foam heat exchangers as waste heat recovery units is discussed with the main goal of reducing the excess pressure drop and maximising the amount of heat that can be recovered from the hot gas stream.