Structural characterization of glycerophospholipids by combinations of ozone- and collision-induced dissociation mass spectrometry: The next step towards "top-down" lipidomics

The complete structural elucidation of complex lipids, including glycerophospholipids, using only mass spectrometry represents a major challenge to contemporary analytical technologies. Here, we demonstrate that product ions arising from the collision-induced dissociation (CID) of the [M + Na] + adduct ions of phospholipids can be isolated and subjected to subsequent gas-phase ozonolysis-known as ozone-induced dissociation (OzID)-in a linear ion-trap mass spectrometer. The resulting CID/OzID experiment yields abundant product ions that are characteristic of the acyl substitution on the glycerol backbone (i.e., sn-position). This approach is shown to differentiate sn-positional isomers, such as the regioisomeric phosphatidylcholine pair of PC 16:0/18:1 and PC 18:1/16:0. Importantly, CID/OzID provides a sensitive diagnostic for the existence of an isomeric mixture in a given sample. This is of very high value for the analysis of tissue extracts since CID/OzID analyses can reveal changes in the relative abundance of isomeric constituents even within different tissues from the same animal. Finally, we demonstrate the ability to assign carbon-carbon double bond positions to individual acyl chains at specific backbone positions by adding subsequent CID and/or OzID steps to the workflow and that this can be achieved in a single step using a hybrid triple quadrupole-linear ion trap mass spectrometer. This unique approach represents the most complete and specific structural analysis of lipids by mass spectrometry demonstrated to date and is a significant step towards comprehensive top-down lipidomics. This journal is © The Royal Society of Chemistry 2014. Grant Number ARC/DP0986628, ARC/FT110100249, ARC/LP110200648

Multi-party computation with conversion of secret sharing

Classical results in unconditionally secure multi-party computation (MPC) protocols with a passive adversary indicate that every n-variate function can be computed by n participants, such that no set of size t < n/2 participants learns any additional information other than what they could derive from their private inputs and the output of the protocol. We study unconditionally secure MPC protocols in the presence of a passive adversary in the trusted setup (‘semi-ideal’) model, in which the participants are supplied with some auxiliary information (which is random and independent from the participant inputs) ahead of the protocol execution (such information can be purchased as a “commodity” well before a run of the protocol). We present a new MPC protocol in the trusted setup model, which allows the adversary to corrupt an arbitrary number t < n of participants. Our protocol makes use of a novel subprotocol for converting an additive secret sharing over a field to a multiplicative secret sharing, and can be used to securely evaluate any n-variate polynomial G over a field F, with inputs restricted to non-zero elements of F. The communication complexity of our protocol is O(ℓ · n 2) field elements, where ℓ is the number of non-linear monomials in G. Previous protocols in the trusted setup model require communication proportional to the number of multiplications in an arithmetic circuit for G; thus, our protocol may offer savings over previous protocols for functions with a small number of monomials but a large number of multiplications.

The relationship between BCOM1 gene variants and macular pigment optical density in persons with and without age-related macular degeneration

Background: Recent evidence indicates that gene variants related to carotenoid metabolism play a role in the uptake of macular pigments lutein (L) and zeaxanthine (Z). Moreover, these pigments are proposed to reduce the risk for advanced age-related macular degeneration (AMD). This study provides the initial examination of the relationship between the gene variants related to carotenoid metabolism, macular pigment optical density (MPOD) and their combined expression in healthy humans and patients with AMD. Participants and Methods: Forty-four participants were enrolled from a general population and a private practice including 20 healthy participants and 24 patients with advanced (neovascular) AMD. Participants were genotyped for the three single nucleotide polymorphisms (SNPs) upstream from BCMO1, rs11645428, rs6420424 and rs6564851 that have been shown to either up or down regulate beta-carotene conversion efficiency in the plasma. MPOD was determined by heterochromatic flicker photometry. Results: Healthy participants with the rs11645428 GG genotype, rs6420424 AA genotype and rs6564851 GG genotype all had on average significantly lower MPOD compared to those with the other genotypes (p < 0.01 for all three comparisons). When combining BCMO1 genotypes reported to have “high” (rs11645428 AA/rs6420424 GG/rs6564851 TT) and “low” (rs11645428 GG/rs6420424 AA/rs6564851 GG) beta-carotene conversion efficiency, we demonstrate clear differences in MPOD values (p<0.01). In patients with AMD there were no significant differences in MPOD for any of the three BCMO1 gene variants. Conclusion: In healthy participants MPOD levels can be related to high and low beta-carotene conversion BCMO1 genotypes. Such relationships were not found in patients with advanced neovascular AMD, indicative of additional processes influencing carotenoid uptake, possibly related to other AMD susceptibility genes. Our findings indicate that specific BCMO1 SNPs should be determined when assessing the effects of carotenoid supplementation on macular pigment and that their expression may be influenced by retinal disease.

Interstellar molecules : Conversion or C3O-. to C3O in the gas phase

Neutral C3O has been prepared by collision induced neutralisation of the precursor radical anion formed by the reaction C-=C-CO-OEt --> C3O-. +EtO. . The similar neutralisaaion reionisation (-NR+) and charge reversal (CR) spectra of C3O-. indicate that the potential surfaces of C3O and C3O+. show favourable vertical Franck-Condon overlap, This suggests that the bond connectivities of anion, neutral and cation C3O are the same. Copyright (C) 1999 John Wiley & Sons, Ltd.

Interstellar molecules. Conversion or C3O-. to C3O in the gas phase

Neutral C3O has been prepared by collision induced neutralisation of the precursor radical anion formed by the reaction C-=C-CO-OEt --> C3O-. +EtO. The similar neutralisaaion reionisation (-NR+) and charge reversal (CR) spectra of C3O-. indicate that the potential surfaces of C3O and C3O+. show favourable vertical Franck-Condon overlap, This suggests that the bond connectivities of anion, neutral and cation C3O are the same. Copyright (C) 1999 John Wiley & Sons, Ltd.

Conversion of neutral C2COC2 to C4CO. potential interstellar molecules

Both [C4CO]−· and [C2COC2]−· are formed in the ion source of a VG ZAB 2HF mass spectrometer by the respective processes HO− + Me3Si–CC–CC–CO–CMe3 → [C4CO]−· + Me3SiOH + Me3C·, and Me3Si–CC–CO–CC–SiMe3 + SF6 + e → [C2COC2]−· + 2Me3SiF + SF4. The second synthetic pathway involves a double desilylation reaction similar to that first reported by Squires. The two radical anion isomers produce different and characteristic charge reversal spectra upon collisional activation. In contrast, following collision induced charge stripping, both radical anions produce neutral C4CO as evidenced by the identical neutralisation reionisation (−NR+) spectra. The exclusive rearrangement of C213COC2 to C413CO indicates that 12C–O bond formation is not involved in the reaction. Ab initio calculations (at the RCCSD(T)/aug-cc-pVDZ//B3LYP/6-31G∗ level of theory) have been used to investigate the reaction coordinates on the potential surfaces for both singlet and triplet rearrangements of neutral C2COC2. Singlet C2COC2 is less stable than singlet C4CO by 78.8 kcal mol−1 and requires only 8.5 kcal mol−1 of additional energy to effect conversion to C4CO by a rearrangement sequence involving three C–C ring opening/cyclisation steps.

Methanesulfonic acid-catalyzed conversion of glucose and xylose mixtures to levulinic acid and furfural

Methanesulfonic acid (MSA) was compared with sulfuric acid for the conversion of glucose and xylose mixtures to produce levulinic acid and furfural. The interactions of glucose and xylose, the predominant sugars found in biomass, were found to influence product yields with furfural degradation reactions enhanced under higher reactant loadings. Fast heating rates allowed maximal yields (>60 mol%) of levulinic acid and furfural to be achieved under short reaction times. Under the range of conditions examined, sulfuric acid produced a slight increase in levulinic acid yield by 6% (P = 0.02), although there was no significant difference (P = 0.11) between MSA and sulfuric acid in levulinic acid formed from glucose alone. The amount and type of the solid residue is similar between MSA and sulfuric acid. As such, MSA is a suitable alternative because its use minimizes corrosion and disposal issues associated with mineral acid catalysts. The heating value of the residue was 22 MJ/kg implying that it is a suitable source of fuel. On the basis of these results, a two-stage processing strategy is proposed to target high levulinic acid and furfural yields, and other chemical products (e.g., lactic acid, xylitol, acetic acid and formic acid). This will result in full utilization of bagasse components.

Why 'down under' is a cut above: a comparison of rates of and reasons for caesarean section in England and Australia

Background Most studies examining determinants of rising rates of caesarean section have examined patterns in documented reasons for caesarean over time in a single location. Further insights could be gleaned from cross-cultural research that examines practice patterns in locations with disparate rates of caesarean section at a single time point. Methods We compared both rates of and main reason for pre-labour and intrapartum caesarean between England and Queensland, Australia, using data from retrospective cross-sectional surveys of women who had recently given birth in England (n = 5,250) and Queensland (n = 3,467). Results Women in Queensland were more likely to have had a caesarean birth (36.2%) than women in England (25.1% of births; OR = 1.44, 95% CI = 1.28-1.61), after adjustment for obstetric characteristics. Between-country differences were found for rates of pre-labour caesarean (21.2% vs. 12.2%) but not for intrapartum caesarean or assisted vaginal birth. Compared to women in England, women in Queensland with a history of caesarean were more likely to have had a pre-labour caesarean and more likely to have had an intrapartum caesarean, due only to a previous caesarean. Among women with no previous caesarean, Queensland women were more likely than women in England to have had a caesarean due to suspected disproportion and failure to progress in labour. Conclusions The higher rates of caesarean birth in Queensland are largely attributable to higher rates of caesarean for women with a previous caesarean, and for the main reason of having had a previous caesarean. Variation between countries may be accounted for by the absence of a single, comprehensive clinical guideline for caesarean section in Queensland. Keywords: Caesarean section; Childbirth; Pregnancy; Cross-cultural comparison; Vaginal birth after caesarean; Previous caesarean section; Patient-reported data; Quality improvement

The Credit Act Advisory System (CAAS) : conversion from an expert system prototype to a C++ commercial system

CAAS is a rule-based expert system, which provides advice on the Victorial Credit Act 1984. It is currently in commercial use, and has been developed in conjunction with a law firm. It uses an object-oriented hybrid reasoning approach. The system was initially prototyped using the expert system shell NExpert Object, and was then converted into the C++ language. In this paper we describe the advantages that this methodology has, for both commercial and research development.

Conversion of linear to rhombic C-4 in the gas phase: A joint experimental and theoretical study

Charge reversal (CR) and neutralization reionization (NR) experiments carried out on a 4-sector mass spectrometer demonstrate that isotopically labeled, linear C-4 anion rearranges upon collisional oxidation. The cations and neutrals formed in these experiments exhibit differing degrees of isotopic scrambling in their fragmentation patterns, indicative of (at least) partial isomerization of both states. Theoretical studies, employing the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory, favor conversion to the rhombic C-4 isomer on both cationic and neutral potential-energy surfaces with the rhombic structures predicted to be slightly more stable than the linear forms in each case. The combination of experiment with theory indicates that the elusive rhombic C-4 is formed as a cation and as a neutral following charge stripping of linear C-4(-)

The epithelial to mesenchymal transition and metastatic progression in carcinoma

Many data have emerged in support of the concept that the promotion of a migratory phenotype in epithelial cells is the result of an EMT, which leads to the loss of differentiation and to the acquisition of several mesenchymal features. Such an event is likely to occur during the metastatic conversion enabling the metastatic cell to invade the connective tissue and disseminate. Even though it cannot be excluded that some cancer cells might constitutively express a metastatic phenotype, the EMT implicated in the tumor progression process would rather be transient, induced in certain cells of the primary tumor by different factors, and reversed when the cells settle down in secondary organs (as schematically represented in Figure 1). However, it is clear that the phenotype that would emerge from the EMT occurring during tumor progression would also be modulated by the genetic background of the cells and must be to some extent different than the ones observed in normal physiological processes, and must also vary from one tumor to another.

A dual inverter-based supercapacitor direct integration scheme for wind energy conversion systems

Interfacing converters used in connecting energy storage systems like supercapacitors and battery banks to wind power systems introduce additional cost and power losses. This paper therefore presents a direct integration scheme for supercapacitors used in mitigating short-term power fluctuations in wind power systems. This scheme uses a dual inverter topology for both grid connection and interfacing a supercapacitor bank. The main inverter of the dual inverter system is powered by the rectified output of a wind turbine-coupled permanent-magnet synchronous generator. The auxiliary inverter is directly connected to the supercapacitor bank. With this approach, an interfacing converter is not required, and there are no associated costs and power losses incurred. The operation of the proposed system is discussed in detail. Simulation and experimental results are presented to verify the efficacy of the proposed system in suppressing short-term wind power fluctuations.

Five-level Z-source diode-clamped inverter

This study proposes a five-level Z-source diode-clamped inverter designed with two intermediate Z-source networks connected between the dc input sources and rear-end inverter circuitry. By partially shorting the Z-source networks, new operating states not previously reported for two-level Z-source inverter are introduced here for operating the proposed inverter with voltage buck-boost energy conversion ability and five-level phase voltage switching. These characteristic features are in fact always ensured at the inverter terminal output by simply adopting a properly designed carrier modulation scheme, which always inserts two partial shoot-through states per half carrier cycle for smooth balanced operation. Theoretical findings and practical issues identified are eventually verified by constructing a scaled down laboratory prototype for testing.

The experiences of teachers teaching children with Down syndrome in the early years of schooling

This innovative collective case study research documented teachers' experiences of teaching children with Down syndrome in the early years of schooling in Australia. Results indicated differences in teachers' conceptualisation of children with Down syndrome as learners and how these variations impacted the way the child was included within the class. Unique to this research was the utilisation of a mind-mapping technique of data collection which effectively captured the individual nature of teachers' experiences, making implicit knowledge explicit through description and interpretation of these experiences. Overall findings indicated that teachers were more likely to include children with Down syndrome into general education classrooms if they operated within a contemporary understanding of disability, had positive support from key stakeholders such as school principals and parents/caregivers, and had access to current information on Down syndrome from professional bodies.