IODP Expedition 339 in the Gulf of Cadiz and off West Iberia : decoding the environmental significance of the Mediterranean outflow water and its global influence

IODP Expedition 339 drilled five sites in the Gulf of Cadiz and two off the west Iberian margin (November 2011 to January 2012), and recovered 5.5 km of sediment cores with an average recovery of 86.4%. The Gulf of Cadiz was targeted for drilling as a key location for the investigation of Mediterranean outflow water (MOW) through the Gibraltar Gateway and its influence on global circulation and climate. It is also a prime area for understanding the effects of tectonic activity on evolution of the Gibraltar Gateway and on margin sedimentation. We penetrated into the Miocene at two different sites and established a strong signal of MOW in the sedimentary record of the Gulf of Cadiz, following the opening of the Gibraltar Gateway. Preliminary results show the initiation of contourite deposition at 4.2–4.5 Ma, although subsequent research will establish whether this dates the onset of MOW. The Pliocene succession, penetrated at four sites, shows low bottom current activity linked with a weak MOW. Significant widespread unconformities, present in all sites but with hiatuses of variable duration, are interpreted as a signal of intensified MOW, coupled with flow confinement. The Quaternary succession shows a much more pronounced phase of contourite drift development, with two periods of MOW intensification separated by a widespread unconformity. Following this, the final phase of drift evolution established the contourite depositional system (CDS) architecture we see today. There is a significant climate control on this evolution of MOW and bottom-current activity. However, from the closure of the Atlantic–Mediterranean gateways in Spain and Morocco just over 6 Ma and the opening of the Gibraltar Gateway at 5.3 Ma, there has been an even stronger tectonic control on margin development, downslope sediment transport and contourite drift evolution. The Gulf of Cadiz is the world's premier contourite laboratory and thus presents an ideal testing ground for the contourite paradigm. Further study of these contourites will allow us to resolve outstanding issues related to depositional processes, drift budgets, and recognition of fossil contourites in the ancient record on shore. The expedition also verified an enormous quantity and extensive distribution of contourite sands that are clean and well sorted. These represent a relatively untapped and important exploration target for potential oil and gas reservoirs.

Elucidation of double bond position in unsaturated lipids by ozone electrospray ionization mass spectrometry

The position(s) of carbon-carbon double bonds within lipids can dramatically affect their structure and reactivity and thus has a direct bearing on biological function. Commonly employed mass spectrometric approaches to the characterization of complex lipids, however, fail to localize sites of unsaturation within the molecular structure and thus cannot distinguish naturally occurring regioisomers. In a recent communication \[Thomas, M. C.; Mitchell, T. W.; Blanksby, S. J. J. Am. Chem. Soc. 2006, 128, 58-59], we have presented a new technique for the elucidation of double bond position in glycerophospholipids using ozone-induced fragmentation within the source of a conventional electrospray ionization mass spectrometer. Here we report the on-line analysis, using ozone electrospray mass spectrometry (OzESI-MS), of a broad range of common unsaturated lipids including acidic and neutral glycerophospholipids, sphingomyelins, and triacylglycerols. All lipids analyzed are found to form a pair of chemically induced fragment ions diagnostic of the position of each double bond(s) regardless of the polarity, the number of charges, or the adduction (e.g., \[M - H](-), \[M - 2H](2-), \[M + H](+), \[M + Na](+), \[M + NH4](+)). The ability of OzESI-MS to distinguish lipids that differ only in the position of the double bonds is demonstrated using the glycerophosphocholine standards, GPCho(9Z-18:1/9Z-18:1) and GPCho(6Z-18:1/6Z-18:1). While these regioisomers cannot be differentiated by their conventional tandem mass spectra, the OzESI-MS spectra reveal abundant fragment ions of distinctive mass-to-charge ratio (m/z). The approach is found to be sufficiently robust to be used in conjunction with the m/z 184 precursor ion scans commonly employed for the identification of phosphocholine-containing lipids in shotgun lipidomic analyses. This tandem OzESI-MS approach was used, in conjunction with conventional tandem mass spectral analysis, for the structural characterization of an unknown sphingolipid in a crude lipid extract obtained from a human lens. The OzESI-MS data confirm the presence of two regioisomers, namely, SM(d18:0/15Z-24:1) and SM(d18:0/17Z-24:1), and suggest the possible presence of a third isomer, SM(d18:0/19Z-24:1), in lower abundance. The data presented herein demonstrate that OzESI-MS is a broadly applicable, on-line approach for structure determination and, when used in conjunction with established tandem mass spectrometric methods, can provide near complete structural characterization of a range of important lipid classes. As such, OzESI-MS may provide important new insight into the molecular diversity of naturally occurring lipids.

Anionic migration reactions in aromatic systems effected by collisional activation : Deprotonated anilides containing methoxycarbonyl substituents

Long-range cross-ring reactions are of minor importance in the collision-induced mass spectra (MS/MS) of [M - H]- ions of CH2OCO-C6H4-NHCOR systems: e.g. the loss of 'CD3CO2CH3' from CH3OCO-C6H4-(N) over bar COCD3. Major processes involve (i) losses of radicals to form stable radical anions, e.g. loss of a ring hydrogen atom and losses from the ester (CH3 ., CH3O . and . CO2CH3), (ii) losses of neutral molecules from the amide moiety [e.g. CO (R = H) and CH2CO (R = CH3), and proximity effects when the two substituents are ortho [e.g. loss of (CH3OD+CO2) from o-CH3OCO-C6H4 (N) over bar COCD3].

Breaking time-inversion invariance through decoherence : energetic consequences for attosecond neutron scattering

Nuclei and electrons in condensed matter and/or molecules are usually entangled, due to the prevailing (mainly electromagnetic) interactions. However, the "environment" of a microscopic scattering system (e.g. a proton) causes ultrafast decoherence, thus making atomic and/or nuclear entanglement e®ects not directly accessible to experiments. However, our neutron Compton scattering experiments from protons (H-atoms) in condensed systems and molecules have a characteristic collisional time about 100|1000 attoseconds. The quantum dynamics of an atom in this ultrashort, but ¯nite, time window is governed by non-unitary time evolution due to the aforementioned decoherence. Unexpectedly, recent theoretical investigations have shown that decoherence can also have the following energetic consequences. Disentangling two subsystems A and B of a quantum system AB is tantamount to erasure of quantum phase relations between A and B. This erasure is widely believed to be an innocuous process, which e.g. does not a®ect the energies of A and B. However, two independent groups proved recently that disentangling two systems, within a su±ciently short time interval, causes increase of their energies. This is also derivable by the simplest Lindblad-type master equation of one particle being subject to pure decoherence. Our neutron-proton scattering experiments with H2 molecules provide for the first time experimental evidence of this e®ect. Our results reveal that the neutron-proton collision, leading to the cleavage of the H-H bond in the attosecond timescale, is accompanied by larger energy transfer (by about 2|3%) than conventional theory predicts. Preliminary results from current investigations show qualitatively the same e®ect in the neutron-deuteron Compton scattering from D2 molecules. We interpret the experimental findings by treating the neutron-proton (or neutron-deuteron) collisional system as an entangled open quantum system being subject to fast decoherence caused by its "environment" (i.e., two electrons plus second nucleus of H2 or D2). The presented results seem to be of generic nature, and may have considerable consequences for various processes in condensed matter and molecules, e.g. in elementary chemical reactions.

Stepwise engineering of a Pichia pastoris D-amino acid oxidase whole cell catalyst

Trigonopsis variabilis D-amino acid oxidase (TvDAO) is a well characterized enzyme used for cephalosporin C conversion on industrial scale. However, the demands on the enzyme with respect to activity, operational stability and costs also vary with the field of application. Processes that use the soluble enzyme suffer from fast inactivation of TvDAO while immobilized oxidase preparations raise issues related to expensive carriers and catalyst efficiency. Therefore, oxidase preparations that are more robust and active than those currently available would enable a much broader range of economically viable applications of this enzyme in fine chemical syntheses. A multi-step engineering approach was chosen here to develop a robust and highly active Pichia pastoris TvDAO whole-cell biocatalyst. As compared to the native T. variabilis host, a more than seven-fold enhancement of the intracellular level of oxidase activity was achieved in P. pastoris through expression optimization by codon redesign as well as efficient subcellular targeting of the enzyme to peroxisomes. Multi copy integration further doubled expression and the specific activity of the whole cell catalyst. From a multicopy production strain, about 1.3 x 103 U/g wet cell weight (wcw) were derived by standard induction conditions feeding pure methanol. A fed-batch cultivation protocol using a mixture of methanol and glycerol in the induction phase attenuated the apparent toxicity of the recombinant oxidase to yield final biomass concentrations in the bioreactor of >or= 200 g/L compared to only 117 g/L using the standard methanol feed. Permeabilization of P. pastoris using 10% isopropanol yielded a whole-cell enzyme preparation that showed 49% of the total available intracellular oxidase activity and was notably stabilized (by three times compared to a widely used TvDAO expressing Escherichia coli strain) under conditions of D-methionine conversion using vigorous aeration. Stepwise optimization using a multi-level engineering approach has delivered a new P. pastoris whole cell TvDAO biocatalyst showing substantially enhanced specific activity and stability under operational conditions as compared to previously reported preparations of the enzyme. The production of the oxidase through fed-batch bioreactor culture and subsequent cell permeabilization is high-yielding and efficient. Therefore this P. pastoris catalyst has been evaluated for industrial purposes.

Making YAWL and SmartPM interoperate : managing highly dynamic processes by exploiting automatic adaptation features

In the last years, the trade-o between exibility and sup- port has become a leading issue in work ow technology. In this paper we show how an imperative modeling approach used to de ne stable and well-understood processes can be complemented by a modeling ap- proach that enables automatic process adaptation and exploits planning techniques to deal with environmental changes and exceptions that may occur during process execution. To this end, we designed and imple- mented a Custom Service that allows the Yawl execution environment to delegate the execution of subprocesses and activities to the SmartPM execution environment, which is able to automatically adapt a process to deal with emerging changes and exceptions. We demonstrate the fea- sibility and validity of the approach by showing the design and execution of an emergency management process de ned for train derailments.

Superoxide does react with peroxides : direct observation of the haber-weiss reaction in the gas phase

The fact that nature provides specific enzymes to selectively remove superoxide (O2.−) from aerobic organisms, namely, the superoxide dismutase enzymes,1 has led to the suggestion that this radical ion may cause the oxidative damage associated with degradative disease and aging.2 Intriguingly, however, superoxide itself is relatively unreactive toward most cellular components, which suggests that dismutase enzymes may ultimately protect the cell against more pernicious oxidants formed from superoxide. As such, there is increasing interest in the endogenous chemistry of superoxide and the pathways by which it might beget more reactive oxygen species. Protonation of superoxide to form the hydroperoxyl radical (HOO.) and dismutation of the same species to hydrogen peroxide (HOOH), with subsequent metal-catalyzed reduction to the hydroxyl radical (HO.), are well-characterized processes in which both the HOO. and HO. radicals are significantly more reactive than their common progenitor.2 Recent examples, however, have also linked superoxide to the putative production of singlet oxygen3 and ozone,4, 5 although the definitive characterization of these chemistries in the cellular milieu has proved challenging

Hypergraph-based modeling of ad-hoc business processes

Process models are usually depicted as directed graphs, with nodes representing activities and directed edges control flow. While structured processes with pre-defined control flow have been studied in detail, flexible processes including ad-hoc activities need further investigation. This paper presents flexible process graph, a novel approach to model processes in the context of dynamic environment and adaptive process participants’ behavior. The approach allows defining execution constraints, which are more restrictive than traditional ad-hoc processes and less restrictive than traditional control flow, thereby balancing structured control flow with unstructured ad-hoc activities. Flexible process graph focuses on what can be done to perform a process. Process participants’ routing decisions are based on the current process state. As a formal grounding, the approach uses hypergraphs, where each edge can associate any number of nodes. Hypergraphs are used to define execution semantics of processes formally. We provide a process scenario to motivate and illustrate the approach.

Prospects for the development of sugarcane biorefineries

Sugarcane biorefineries co-producing fuels, green chemicals and bio-products offer great potential for improving the profitability and sustainability of sugarcane industries around the world. Sugarcane bagasse is widely regarded as one of the best biomass feedstocks for early adoption and commercialisation of biorefining technologies because of the large scale of the resource and its availability at sugar factories. Biomass biorefineries aim to convert bagasse through biochemical and thermochemical processes to produce low cost fermentable sugars which are a platform for value-adding. Through subsequent fermentation technologies or chemical synthesis, the sugars can be converted to fuels including ethanol and butanol, oils, organic acids such as succinic and levulinic and polymer precursors. Other biorefinery products can include food and animal feeds, plastics, fibre products and resins. Recent advances in biorefinery production technologies are being demonstrated in a unique research facility at the Queensland University of Technology’s Mackay Renewable Biocommodities Pilot Plant in Mackay, Australia. This pilot scale production facility located at Mackay Sugar Ltd’s Racecourse Mill is demonstrating the production of a range of fuels and other products from sugarcane bagasse. This paper will address the opportunities available for sugarcane biorefineries to contribute to future profitability and sustainability of the sugarcane industry.

When should private property rights give way to the public interest?

Since Queensland Wire Industries Pty Ltd v Broken Hill Pty Co Ltd (1989) 167 CLR 177 it has been recognised that corporations with substantial market power are subject to special responsibilities and restraints that corporations without market power are not. In NT Power Generation Pty Ltd v Power and Water Authority (2004) 219 CLR 90 McHugh A-CJ, Gummow, Callinan and Heydon JJ in their joint reasons stated (at [76]), that s 46 of the Competition and Consumer Act 2010 (Cth) (CCA) can operate not only to prevent firms with substantial market power from doing prohibited things, but also compel them positively to do things they do not want to do. Their Honours also stated (at [126]) that the proposition that a private property owner who declines to permit competitors to use the property is immune from s 46 is “intrinsically unsound”. However, the circumstances in which a firm with substantial power must accommodate competitors, and private property rights give way to the public interest are uncertain. The purpose of this Note is to consider recent developments in two areas of the CCA where the law requires private property rights to give way to the public interest. The first part of the Note considers two recent cases which clarify the circumstances in which s 46 of the CCA can be used to compel a firm with substantial market power to accommodate a competitor and allow the competitor to make use of private property rights in the public interest. Secondly, on 12 February 2014 the Minister for Small Business, the Hon Bruce Billson,released the Productivity Commission’s Final Report, on the National Access Regime in Pt IIIA of the CCA (National Access Regime, Inquiry Report No 66, Canberra). Pt IIIA provides for the processes by which third parties may obtain access to infrastructure owned by others in the public interest. The Report recommends that Pt IIIA be retained but makes a number of suggestions for its reform, some of which will be briefly considered.

Raising levels of awareness of rights and obligations in the provision of financial product advice to retail clients

In September-December 2012, 548 financial planning retail clients and 77 financial advisers responded to online surveys addressing consumer satisfaction with financial planning services and the provision of information concerning regulatory and rights issues. Retail clients commented on areas related to the best interests duty in s 961B of the Corporations Act 2001 (Cth), in particular the extent to which advisers considered their clients’ financial objectives and lifestyle situations, and the client-centredness of the financial advice they received. Retail clients also indicated their level of awareness of their substantive rights in relation to receiving advice, the legal obligations imposed on advisers, and whether they would access internal and external complaints processes if warranted. Advisers reported on the extent to which they provide clients with information relating to their substantive rights, and complaints processes available to them. Responses were analysed in relation to client demographics (e.g., age, gender, education), and experience of financial advice. This article reports on the findings of the surveys and their implications for financial planners.

Dietary flavonoids from modified apple reduce inflammation markers and modulate gut microbiota in mice

Apples are rich in polyphenols, which provide antioxidant properties, mediation of cellular processes such as inflammation, and modulation of gut microbiota. In this study we compared genetically engineered apples with increased flavonoids [myeloblastis transcription factor 10 (MYB10)] with nontransformed apples from the same genotype, "Royal Gala" (RG), and a control diet with no apple. Compared with the RG diet, the MYB10 diet contained elevated concentrations of the flavonoid subclasses anthocyanins, flavanol monomers (epicatechin) and oligomers (procyanidin B2), and flavonols (quercetin glycosides), but other plant secondary metabolites were largely unaltered. We used these apples to investigate the effects of dietary flavonoids on inflammation and gut microbiota in 2 mouse feeding trials. In trial 1, male mice were fed a control diet or diets supplemented with 20% MYB10 apple flesh and peel (MYB-FP) or RG apple flesh and peel (RG-FP) for 7 d. In trial 2, male mice were fed MYB-FP or RG-FP diets or diets supplemented with 20% MYB10 apple flesh or RG apple flesh for 7 or 21 d. In trial 1, the transcription levels of inflammation-linked genes in mice showed decreases of >2-fold for interleukin-2 receptor (Il2rb), chemokine receptor 2 (Ccr2), chemokine ligand 10 (Cxcl10), and chemokine receptor 10 (Ccr10) at 7 d for the MYB-FP diet compared with the RG-FP diet (P <0.05). In trial 2, the inflammation marker prostaglandin E2 (PGE2) in the plasma of mice fed the MYB-FP diet at 21 d was reduced by 10-fold (P < 0.01) compared with the RG-FP diet. In colonic microbiota, the number of total bacteria for mice fed the MYB-FP diet was 6% higher than for mice fed the control diet at 21 d (P = 0.01). In summary, high-flavonoid apple was associated with decreases in some inflammation markers and changes in gut microbiota when fed to healthy mice.

Actinidia DRM1 : an intrinsically disordered protein whose mRNA expression is inversely correlated with spring budbreak in Kiwifruit

Intrinsically disordered proteins (IDPs) are a relatively recently defined class of proteins which, under native conditions, lack a unique tertiary structure whilst maintaining essential biological functions. Functional classification of IDPs have implicated such proteins as being involved in various physiological processes including transcription and translation regulation, signal transduction and protein modification. Actinidia DRM1 (Ade DORMANCY ASSOCIATED GENE 1), represents a robust dormancy marker whose mRNA transcript expression exhibits a strong inverse correlation with the onset of growth following periods of physiological dormancy. Bioinformatic analyses suggest that DRM1 is plant specific and highly conserved at both the nucleotide and protein levels. It is predicted to be an intrinsically disordered protein with two distinct highly conserved domains. Several Actinidia DRM1 homologues, which align into two distinct Actinidia-specific families, Type I and Type II, have been identified. No candidates for the Arabidopsis DRM1-Homologue (AtDRM2) an additional family member, has been identified in Actinidia.

Review : "Genetic Privacy: A challenge to Medico-Legal Norms" by Laurie, G

The discovery by Watson and Crick of the structure of DNA is one of the great scientific discoveries. In the period since that discovery new areas of genetic research have opened up which hold out the hope of developing treatments or cures for many illnesses and diseases. Yet with these discoveries have also come an array of ethical and legal dilemmas about the use of genetic information and concerns about the potential for those with genetic diseases or conditions to be stigmatised and discriminated against. The discussion about the developments in genetic science has become increasingly, a debate about the use of genetic information within our society. Graeme Laurie’s book, Genetic Privacy: A Challenge to Medico-Legal Norms, guides the reader through the complexities of these debates by considering what we mean by privacy and asking whether our existing concepts are adequate to meet the challenges posed by the new genetics.

Framework of a process laboratory for the operational control of service processes

Service processes such as financial advice, booking a business trip or conducting a consulting project have emerged as units of analysis of high interest for the business process and service management communities in practice and academia. While the transactional nature of production processes is relatively well understood and deployed, the less predictable and highly interactive nature of service processes still lacks in many areas appropriate methodological grounding. This paper proposes a framework of a process laboratory as a new IT artefact in order to facilitate the holistic analysis and simulation of such service processes. Using financial services as an example, it will be shown how such a process laboratory can be used to reduce the complexity of service process analysis and facilitate operational service process control.