Ozone-Induced Dissociation on a Modified Tandem Linear Ion-Trap : Observations of Different Reactivity for Isomeric Lipids

Ozone-induced dissociation (OzID) exploits the gas-phase reaction between mass-selected lipid ions and ozone vapor to determine the position(s) of unsaturation In this contribution, we describe the modification of a tandem linear ion-trap mass spectrometer specifically for OzID analyses wherein ozone vapor is supplied to the collision cell This instrumental configuration provides spatial separation between mass-selection, the ozonolysis reaction, and mass-analysis steps in the OzID process and thus delivers significant enhancements in speed and sensitivity (ca 30-fold) These improvements allow spectra revealing the double-bond position(s) within unsaturated lipids to be acquired within 1 s significantly enhancing the utility of OzID in high-throughput lipidomic protocols The stable ozone concentration afforded by this modified instrument also allows direct comparison of relative reactivity of isomeric lipids and reveals reactivity trends related to (1) double-bond position, (2) substitution position on the glycerol backbone, and (3) stereochemistry For cis- and trans-isomers, differences were also observed in the branching ratio of product ions arising from the gas-phase ozonolysis reaction, suggesting that relative ion abundances could be exploited as markers for double-bond geometry Additional activation energy applied to mass-selected lipid ions during injection into the collision cell (with ozone present) was found to yield spectra containing both OzID and classical-CID fragment ions This combination CID-OzID acquisition on an ostensibly simple monounsaturated phosphatidylcholine within a cow brain lipid extract provided evidence for up to four structurally distinct phospholipids differing in both double-bond position and sn-substitution U Am Soc Mass Spectrom 2010, 21, 1989-1999) (C) 2010 American Society for Mass Spectrometry

The organisation and expression of the genes encoding the mitochondrial glycine decarboxylase complex and serine hydroxymethyltransferase in pea (Pisum sativum)

Restriction fragment length polymorphisms have been used to determine the chromosomal location of the genes encoding the glycine decarboxylase complex (GDC) and serine hydroxymethyltransferase (SHMT) of pea leaf mitochondria. The genes encoding the H subunit of GDC and the genes encoding SHMT both show linkage to the classical group I marker i. In addition, the genes for the P protein of GDC show linkage to the classic group I marker a. The genes for the L and T proteins of GDC are linked to one another and are probably situated on the satellite of chromosome 7. The mRNAs encoding the five polypeptides that make up GDC and SHMT are strongly induced when dark-grown etiolated pea seedlings are placed in the light. Similarly, when mature plants are placed in the dark for 48 h, the levels of both GDC protein and SHMT mRNAs decline dramatically and then are induced strongly when these plants are returned to the light. During both treatments a similar pattern of mRNA induction is observed, with the mRNA encoding the P protein of GDC being the most rapidly induced and the mRNA for the H protein the slowest. Whereas during the greening of etiolated seedlings the polypeptides of GDC and SHMT show patterns of accumulation similar to those of the corresponding mRNAs, very little change in the level of the polypeptides is seen when mature plants are placed in the dark and then re-exposed to the light.

Port-Hamiltonian theory of motion control for marine craft

Port-Hamiltonian Systems (PHS) have a particular form that incorporates explicitly a function of the total energy in the system (energy function) and also other functions that describe structure of the system in terms of energy distribution. For PHS, the product of the input and output variables gives the rate of energy change. This type of systems have the property that under certain conditions on the energy function, the system is passive; and thus, stable. Therefore, if one can design a controller such that the closed-loop system retains - or takes - a PHS form, such closed-loop system will inherit the properties of passivity and stability. In this paper, the classical model of marine craft is put into a PHS form. It is shown that models used for positioning control do not have a PHS form due to a kinematic transformation, but a control design can be done such that the closed-loop system takes a PHS form. It is further shown how integral action can be added and how the PHS-form can be exploited to provide a procedure for control design that ensures passivity and thus stability.

Paracrine interactions between LNCaP prostate cancer cells and bioengineered bone in 3D in vitro culture reflect molecular changes during bone metastasis

As microenvironmental factors such as three-dimensionality and cell–matrix interactions are increasingly being acknowledged by cancer biologists, more complex 3D in vitro models are being developed to study tumorigenesis and cancer progression. To better understand the pathophysiology of bone metastasis, we have established and validated a 3D indirect co-culture model to investigate the paracrine interactions between prostate cancer (PCa) cells and human osteoblasts. Co-culture of the human PCa, LNCaP cells embedded within polyethylene glycol hydrogels with human osteoblasts in the form of a tissue engineered bone construct (TEB), resulted in reduced proliferation of LNCaP cells. LNCaP cells in both monoculture and co-culture were responsive to the androgen analog, R1881, as indicated by an increase in the expression (mRNA and/or protein induction) of androgen-regulated genes including prostate specific antigen and fatty acid synthase. Microarray gene expression analysis further revealed an up-regulation of bone markers and other genes associated with skeletal and vasculature development and a significant activation of transforming growth factor β1 downstream genes in LNCaP cells after co-culture with TEB. LNCaP cells co-cultured with TEB also unexpectedly showed similar changes in classical androgen-responsive genes under androgen-deprived conditions not seen in LNCaP monocultures. The molecular changes of LNCaP cells after co-culturing with TEBs suggest that osteoblasts exert a paracrine effect that may promote osteomimicry and modulate the expression of androgen-responsive genes in LNCaP cells. Taken together, we have presented a novel 3D in vitro model that allows the study of cellular and molecular changes occurring in PCa cells and osteoblasts that are relevant to metastatic colonization of bone. This unique in vitro model could also facilitate cancer biologists to dissect specific biological hypotheses via extensive genomic or proteomic assessments to further our understanding of the PCa-bone crosstalk.

A mass spectrometry study of XCO+, X = Si, Ge : Is SiCO+ a main group carbonyl? Comments on the bonding in ground state SiCO and the Si,C,O (+) potential energy surface

The cation\[Si,C,O](+) has been generated by 1) the electron ionisation (EI) of tetramethoxysilane and 2) chemical ionisation (CI) of a mixture of silane and carbon monoxide. Collisional activation (CA) experiments performed for mass-selected \[Si,C,O](+), generated by using both methods, indicate that the structure is not inserted OSiC+; however, a definitive structural assignment as Si+-CO, Si+-OC or some cyclic variant is impossible based on these results alone. Neutralisation-reionisation (+NR+) experiments for EI-generated \[Si,C,O](+) reveal a small peak corresponding to SiC+, but no detectable SiO+ signal, and thus establishes the existence of the Si+-CO isomer. CCSD(T)//B3LYP calculations employing a triple-zeta basis set have been used to explore the doublet and quartet potential-energy surfaces of the cation, as well as some important neutral states The results suggest that both Si+-CO and Si+ - OC isomers are feasible; however, the global minimum is (2)Pi SiCO+. Isomeric (2)Pi SiOC+ is 12.1 kcal mol(-1) less stable than (2)Pi SiCO+, and all quartet isomers are much higher in energy. The corresponding neutrals Si-CO and Si-OC are also feasible, but the lowest energy Si - OC isomer ((3)A") is bound by only 1.5 kcal mol(-1). We attribute most, if nor all, of the recovery signal in the +NR' experiment to SiCO+ survivor ions. The nature of the bonding in the lowest energy isomers of Si+ -(CO,OC) is interpreted with the aid of natural bond order analyses, and the ground stale bonding of SiCO+ is discussed in relation to classical analogues such as metal carbonyls and ketenes.

Ambiguity Acceptance Testing : A Comparison of the Ratio Test and Difference Test

Integer ambiguity resolution is an indispensable procedure for all high precision GNSS applications. The correctness of the estimated integer ambiguities is the key to achieving highly reliable positioning, but the solution cannot be validated with classical hypothesis testing methods. The integer aperture estimation theory unifies all existing ambiguity validation tests and provides a new prospective to review existing methods, which enables us to have a better understanding on the ambiguity validation problem. This contribution analyses two simple but efficient ambiguity validation test methods, ratio test and difference test, from three aspects: acceptance region, probability basis and numerical results. The major contribution of this paper can be summarized as: (1) The ratio test acceptance region is overlap of ellipsoids while the difference test acceptance region is overlap of half-spaces. (2) The probability basis of these two popular tests is firstly analyzed. The difference test is an approximation to optimal integer aperture, while the ratio test follows an exponential relationship in probability. (3) The limitations of the two tests are firstly identified. The two tests may under-evaluate the failure risk if the model is not strong enough or the float ambiguities fall in particular region. (4) Extensive numerical results are used to compare the performance of these two tests. The simulation results show the ratio test outperforms the difference test in some models while difference test performs better in other models. Particularly in the medium baseline kinematic model, the difference tests outperforms the ratio test, the superiority is independent on frequency number, observation noise, satellite geometry, while it depends on success rate and failure rate tolerance. Smaller failure rate leads to larger performance discrepancy.

Cadherins in the human placenta : epithelial-mesenchymal transition (EMT) and placental development

Colonisation of the maternal uterine wall by the trophoblast involves a series of alterations in the behaviour and morphology of trophoblast cells. Villous cytotrophoblast cells change from a well-organised coherently layered phenotype to one that is extravillous, acquiring a proliferative, migratory and invasive capacity, to facilitate fetal-maternal interaction. These changes are similar to those of other developmental processes falling under the umbrella of an epithelial-mesenchymal transition (EMT). Modulation of cell adhesion and cell polarity occurs through changes in cell-cell junctional molecules, such as the cadherins. The cadherins, particularly the classical cadherins (e.g. Epithelial-(E)-cadherin), and their link to adaptors called catenins at cell-cell contacts, are important for maintaining cell attachment and the layered phenotype of the villous cytotrophoblast. In contrast, reduced expression and re-organization of cadherins from these cell junctional regions promote a loosened connection between cells, coupled with reduced apico-basal polarity. Certain non-classical cadherins play an active role in cell migration processes. In addition to the classical cadherins, two other cadherins which have been reported in placental tissues are vascular endothelial (VE) cadherin and cadherin-11. Cadherin molecules are well placed to be key regulators of trophoblast cell behaviour, analogous to their role in other developmental EMTs. This review addresses cadherin expression and function in normal and diseased human placental tissues, especially in fetal growth restriction and pre-eclampsia where trophoblast invasion is reduced.

Exploring subscription renewal intention of operational cloud enterprise systems-a socio-technical approach

Despite the fact that customer retention is crucial for providers of cloud enterprise systems, only little attention has been directed towards investigating the antecedents of subscription renewal in an organizational context. This is even more surprising, as cloud services are usually offered as subscription-based pricing models with the (theoretical) possibility of immediate service cancellation, strongly opposing classical long-term IT-Outsourcing contracts or license-based payment plans of on premise enterprise systems. To close this research gap an empirical study was undertaken. Firstly, a conceptual model was drawn from theories of social psychology, organizational system continuance and IS success. The model was subsequently tested using survey responses of senior management within companies which adopted cloud enterprise systems. Gathered data was then analysed using PLS. The results indicate that subscription renewal intention is influenced by both – social-related and technology-specific factors – which are able to explain 50.4% of the variance in the dependent variable. Beneath the cloud enterprise systems specific contributions, the work advances knowledge in the area of organizational system continuance, as well as IS success.

Characterisations of extended resiliency and extended immunity of S-boxes

New criteria of extended resiliency and extended immunity of vectorial Boolean functions, such as S-boxes for stream or block ciphers, were recently introduced. They are related to a divide-and-conquer approach to algebraic attacks by conditional or unconditional equations. Classical resiliency turns out to be a special case of extended resiliency and as such requires more conditions to be satisfied. In particular, the algebraic degrees of classically resilient S-boxes are restricted to lower values. In this paper, extended immunity and extended resiliency of S-boxes are studied and many characterisations and properties of such S-boxes are established. The new criteria are shown to be necessary and sufficient for resistance against the divide-and-conquer algebraic attacks by conditional or unconditional equations.

Cryptanalysis of block ciphers with overdefined systems of equations

Several recently proposed ciphers, for example Rijndael and Serpent, are built with layers of small S-boxes interconnected by linear key-dependent layers. Their security relies on the fact, that the classical methods of cryptanalysis (e.g. linear or differential attacks) are based on probabilistic characteristics, which makes their security grow exponentially with the number of rounds N r r. In this paper we study the security of such ciphers under an additional hypothesis: the S-box can be described by an overdefined system of algebraic equations (true with probability 1). We show that this is true for both Serpent (due to a small size of S-boxes) and Rijndael (due to unexpected algebraic properties). We study general methods known for solving overdefined systems of equations, such as XL from Eurocrypt’00, and show their inefficiency. Then we introduce a new method called XSL that uses the sparsity of the equations and their specific structure. The XSL attack uses only relations true with probability 1, and thus the security does not have to grow exponentially in the number of rounds. XSL has a parameter P, and from our estimations is seems that P should be a constant or grow very slowly with the number of rounds. The XSL attack would then be polynomial (or subexponential) in N r> , with a huge constant that is double-exponential in the size of the S-box. The exact complexity of such attacks is not known due to the redundant equations. Though the presented version of the XSL attack always gives always more than the exhaustive search for Rijndael, it seems to (marginally) break 256-bit Serpent. We suggest a new criterion for design of S-boxes in block ciphers: they should not be describable by a system of polynomial equations that is too small or too overdefined.

Efficient extension of standard Schnorr/RSA signatures into Universal Designated-Verifier Signatures

Universal Designated-Verifier Signature (UDVS) schemes are digital signature schemes with additional functionality which allows any holder of a signature to designate the signature to any desired designated-verifier such that the designated-verifier can verify that the message was signed by the signer, but is unable to convince anyone else of this fact. Since UDVS schemes reduce to standard signatures when no verifier designation is performed, it is natural to ask how to extend the classical Schnorr or RSA signature schemes into UDVS schemes, so that the existing key generation and signing implementation infrastructure for these schemes can be used without modification. We show how this can be efficiently achieved, and provide proofs of security for our schemes in the random oracle model.

Magnetic control of breakdown : toward energy-efficient hollow-cathode magnetron discharges

Characteristics of electrical breakdown of a planar magnetron enhanced with an electromagnet and a hollow-cathode structure, are studied experimentally and numerically. At lower pressures the breakdown voltage shows a dependence on the applied magnetic field, and the voltage necessary to achieve the self-sustained discharge regime can be significantly reduced. At higher pressures, the dependence is less sensitive to the magnetic field magnitude and shows a tendency of increased breakdown voltage at the stronger magnetic fields. A model of the magnetron discharge breakdown is developed with the background gas pressure and the magnetic field used as parameters. The model describes the motion of electrons, which gain energy by passing the electric field across the magnetic field and undergo collisions with neutrals, thus generating new bulk electrons. The electrons are in turn accelerated in the electric field and effectively ionize a sufficient amount of neutrals to enable the discharge self-sustainment regime. The model is based on the assumption about the combined classical and near-wall mechanisms of electron conductivity across the magnetic field, and is consistent with the experimental results. The obtained results represent a significant advance toward energy-efficient multipurpose magnetron discharges.

Electron transport across magnetic field in low-temperature plasmas : an alternative approach for obtaining evidence of Bohm mechanism

A comparative study involving both experimental and numerical investigations was made to resolve a long-standing problem of understanding electron conductivity mechanism across magnetic field in low-temperature plasmas. We have calculated the plasma parameters from experimentally obtained electric field distribution, and then made a 'back' comparison with the distributions of electron energy and plasma density obtained in the experiment. This approach significantly reduces an influence of the assumption about particular phenomenology of the electron conductivity in plasma. The results of the experiment and calculations made by this technique have showed that the classical conductivity is not capable of providing realistic total current and electron energy, whereas the phenomenological anomalous Bohm mobility has demonstrated a very good agreement with the experiment. These results provide an evidence in favor of the Bohm conductivity, thus making it possible to clarify this pressing long-living question about the main driving mechanism responsible for the electron transport in low-temperature plasmas.

Discharge parameters and dominant electron conductivity mechanism in a low-pressure planar magnetron discharge

Parameters of a discharge sustained in a planar magnetron configuration with crossed electric and magnetic fields are studied experimentally and numerically. By comparing the data obtained in the experiment with the results of calculations made using the proposed theoretical model, conclusion was made about the leading role of the turbulence-driven Bohm electron conductivity in the low-pressure operation mode (up to 1 Pa) of the discharge in crossed electric and magnetic fields. A strong dependence of the width of the cathode sputter trench, associated with the ionization region of the magnetron discharge, on the discharge parameters was observed in the experiments. The experimental data were used as input parameters in the discharge model that describes the motion of secondary electrons across the magnetic field in the ionization region and takes into account the classical, near-wall, and Bohm mechanisms of electron conductivity.