High Excess Research Articles

Formation of Hg(II) Tetrathiolate Complexes with Cysteine at Neutral pH.

Mercury(II) ions precipitate from aqueous cysteine (H2Cys) solutions containing H2Cys/Hg(II) mole ratio ≥ 2.0 as Hg(S-HCys)2. In absence of additional cysteine, the precipitate dissolves at pH ~12 with the [Hg(S,N-Cys)2]2- complex dominating. With excess cysteine (H2Cys/Hg(II) mole ratio ≥ 4.0), higher complexes form and the precipitate dissolves at lower pH values. Previously, we found that tetrathiolate [Hg(S-Cys)4]6- complexes form at pH = 11.0; in this work we extend the investigation to pH values of physiological interest. We examined two series of Hg(II)-cysteine solutions in which CHg(II) varied between 8 - 9 mM and 80 - 100 mM, respectively, with H2Cys/Hg(II) mole ratios from 4 to ~20. The solutions were prepared in the pH range 7.1 - 8.8, at the pH at which the initial Hg(S-HCys)2 precipitate dissolved. The variations in the Hg(II) speciation were followed by 199Hg NMR, X-ray absorption and Raman spectroscopic techniques. Our results show that in the dilute solutions (CHg(II) = 8 - 9 mM), mixtures of di-, tri- (major) and tetrathiolate complexes exist at moderate cysteine excess (CH2Cys ~ 0.16 M) at pH 7.1. In the more concentrated solutions (CHg(II) = 80 - 100 mM) with high cysteine excess (CH2Cys > 0.9 M), tetrathiolate [Hg(S-cysteinate)4] m-6 (m = 0 - 4) complexes dominate in the pH range 7.3 - 7.8, with lower charge than for the [Hg(S-Cys)4]6- complex due to protonation of some (m) of the amino groups of the coordinated cysteine ligands. The results of this investigation could provide a key to the mechanism of biosorption and accumulation of Hg(II) ions in biological / environmental systems.

ANTARES and Baikal: Recent results from underwater neutrino telescopes

Two Northern hemisphere neutrino telescopes are currently searching for astrophysical neutrinos in the TeV/PeV range: ANTARES and Baikal. Both observatories utilize various signatures like a high energy excess over the atmospheric neutrino flux, searches for localized neutrino sources of various extensions and multi-messenger analyses based on time and/or space coincidences with other cosmic probes. We here review the status of both experiments and discuss a selection of recent results.

Partitioning of Laponite Clay Platelets in Pickering Emulsion Polymerization.

Partitioning of laponite disklike clay platelets between polymer particles and bulk aqueous phase was investigated in Pickering surfactant-free emulsion polymerization of styrene. Adsorption of laponite clay platelets plays an important role in the stabilization of this system, influencing the particle size and the number of particles, and, hence, the reaction rate. Adsorption isotherms show that, while the laponite clay platelets are almost fully exfoliated in water, they form multilayers on the surface of the polymer particles by the end of polymerization, as confirmed by transmission electron microscopy (TEM). This observation is supported by quartz crystal microbalance, conductivity, and TEM measurements, which reveal interactions between the clay and polystyrene, as a function of the ionic strength. The strong adsorption of clay platelets leaves a low residual concentration in the aqueous phase that cannot cause further nucleation of polymer particles, as demonstrated during seeded emulsion polymerization experiments in the presence of a high excess of clay. A Brunauer-Emmett-Teller (BET)-type model for laponite adsorption on polystyrene particles matches the adsorption isotherms.

Gram scale synthesis of specialized pro-resolving mediator 17(S)-HDHA using lipoxygenase enhanced by water-soluble reducing agent TCEP

17(S)-Hydroxy docosahexaenoic acid (17(S)-HDHA) is a specialized pro-resolving mediator. The oxidation of docosahexaenoic acid (DHA) to 17(S)-HDHA using soybean lipoxygenase was accomplished in the presence of the reducing agent TCEP in high yield and high enantio excess. We demonstrated application of this strategy to the synthesis of other fatty acids and to gram scale synthesis of 17(S)-HDHA.

Enhancement of Transistor-to-Transistor Variability Due to Total Dose Effects in 65-nm MOSFETs

We studied device-to-device variations as a function of total dose in MOSFETs, using specially designed test structures and procedures aimed at maximizing matching between transistors. Degradation in nMOSFETs is less severe than in pMOSFETs and does not show any clear increase in sample-to-sample variability due to the exposure. At doses smaller than 1 Mrad( SiO 2 ) variability in pMOSFETs is also practically unaffected, whereas at very high doses-in excess of tens of Mrad( SiO 2 )-variability in the on-current is enhanced in a way not correlated to pre-rad variability. The phenomenon is likely due to the impact of random dopant fluctuations on total ionizing dose effects.

Two competing reactions of tetrabutylammonium alginate in organic solvents: Amidation versus γ-lactone synthesis

Biocompatibility and thickening properties predetermine alginates as ingredients in food, cosmetic and pharmaceutical products. Further chemical modifications are often desired for a product optimization. The introduction of hydrophobic groups can be realized by employing organic tetrabutylammonium alginate (TBA-Alg) solutions. The synthesis of alginic acid alkyl amides from TBA-Alg with 2-chloro-1-methylpyridinium iodide (CMPI) as a coupling agent, however, has so far not resulted in a high degree of amidation. The analysis of the coupling reaction revealed the formation of mannuronic acid γ-lactone structures, which required a conformation change from 1C4 to 4C1. The opening of the γ-lactone required a high excess of butylamine. In the case of CMPI, triethylamine had to be added prior to the coupling agent in order to suppress the assumed alginic acid formation. The degrees of amidation achieved were up to 0.8, and for propylphosphonic anhydride as the coupling agent up to 1. The molecular weights of the alginic acid butyl amide were ≥35kDa.

Herschel-PACS observations of discs in theηChamaeleontis association

Context. Protoplanetary discs are the birthplace of planets. Studying protoplanetary discs is the key to constraining theories of planet formation. By observing dust and gas in associations at different ages we can study the evolution of these discs, their clearing timescales, and their physical and geometrical properties.The stellar association η Cha is peculiar; some members still retain detectable amounts of gas in their discs at the late age of ~7 Myr, making it one of the most interesting young stellar associations in the solar neighbourhood. Aims: We characterise the properties of dust and gas in protoplanetary and transitional discs in the η Cha young cluster, with special emphasis on explaining the peculiarities that lead to the observed high disc detection fraction and prominent IR excesses at an age of ~7 Myr. Methods: We observed 17 members of the η Cha association with Herschel-PACS in photometric mode and line spectroscopic mode. A subset of members were also observed in range spectroscopic mode. The observations trace [OI] and H2O emissions at 63.18 and 63.32 μm, respectively, as well as CO, OH, CH+, and [CII] at different wavelengths for those systems observed in range mode. The photometric observations were used to build complete spectral energy distributions (SEDs) from the optical to the far-IR. High-resolution multi-epoch optical spectra with high signal-to-noise ratios were also analysed to study the multiplicity of the sources and look for further gas (accreting) and outflow indicators. Results: We detect four out of fifteen sources observed at 70 μm, four out of six at 100 μm, and six out of sixteen at 160 μm. Only one system shows [OI] emission at 63 μm, namely RECX 15 or J0843.3-7905. None of them shows far-IR line emission at any other wavelength. The [OI] emission toward RECX 15 points to the presence of an outflow; however, the emission is not extended. We study Hα emission among η Cha members and conclude that RECX 4, 5, 9, 11, and 15 are actively accreting in at least one epoch. Conclusions: The SEDs of the discs in η Cha show a variety of shapes, from those in Taurus and in Upper Scorpius to sources showing excess over the Taurus median SED. Furthermore, the SEDs of RECX 3 and RECX 4 are typical of debris discs. The detection fraction for [OI] in η Cha is lower than younger regions like Taurus and Cha II, indicative of an evolutionary trend. The lack of [OI] emission, together with the intermediate values of the IR excess, can be explained by long-lived discs with a flattened geometry or by flared discs with a low UV flux, or by a combination of the two scenarios. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

Complete kinetic mechanism for recycling of the bacterial ribosome.

How EF-G and RRF act together to split a post-termination ribosomal complex into its subunits has remained obscure. Here, using stopped-flow experiments with Rayleigh light scattering detection and quench-flow experiments with radio-detection of GTP hydrolysis, we have clarified the kinetic mechanism of ribosome recycling and obtained precise estimates of its kinetic parameters. Ribosome splitting requires that EF-G binds to an already RRF-containing ribosome. EF-G binding to RRF-free ribosomes induces futile rounds of GTP hydrolysis and inhibits ribosome splitting, implying that while RRF is purely an activator of recycling, EF-G acts as both activator and competitive inhibitor of RRF in recycling of the post-termination ribosome. The ribosome splitting rate and the number of GTPs consumed per splitting event depend strongly on the free concentrations of EF-G and RRF. The maximal recycling rate, here estimated as 25 sec−1, is approached at very high concentrations of EF-G and RRF with RRF in high excess over EF-G. The present in vitro results, suggesting an in vivo ribosome recycling rate of ∼5 sec−1, are discussed in the perspective of rapidly growing bacterial cells.

What causes large submarine landslides on low gradient (<2°) continental slopes with slow (∼0.15 m/kyr) sediment accumulation?

AbstractSubmarine landslides can cause damaging tsunamis, the height of which scales up with the volume of the displaced mass. The largest underwater landslides are far bigger than any landslides on land, and these submarine megaslides tend to occur on open continental slopes with remarkably low gradients of less than 2°. For geohazard assessments it is essential to understand what preconditions and triggers slope failure on such low gradients. Previous work has suggested that generation of high excess pore pressure due to rapid sediment deposition plays a key role in such failures. However, submarine slope failure also occurs where sedimentation rates are low (<0.15 m/kyr), such as off northwest Africa. We use a fully coupled stress and fluid flow finite element model to test whether such low sedimentation rates can generate sufficient excess pore pressures to cause failure of a 2° slope. The sensitivity of overpressure generation and slope stability is assessed with respect to different sedimentation rates and patterns, sediment consolidation properties, and stratigraphic layer configurations. The simulations show that, in general, it is difficult to generate significant excess pore pressure if sediment accumulation is slow and the only pressure source. However, we identify a sediment compression behavior that can lead to submarine landslides in locations worldwide. Our results imply that compressibility is an important factor for the stability of low gradient continental slopes.

Diversity in Reduction with Short‐Chain Dehydrogenases: Tetrahydroxynaphthalene Reductase, Trihydroxynaphthalene Reductase, and Glucose Dehydrogenase

AbstractNAD(P)H‐dependent oxidoreductases from the short‐chain dehydrogenases/reductases (SDRs) family possess high functional diversity. Three SDRs, namely, tetrahydroxy‐ and trihydroxynaphthalene reductases (T4HNR, T3HNR) involved in the dihydroxynaphthalene‐melanin biosynthesis of the phytopathogenic fungus Magnaporthe grisea, and glucose dehydrogenase (GDH) from Bacillus subtilis, were characterized regarding their substrate range and functional behavior. T4HNR and T3HNR share activities towards the stereoselective reduction of 2‐tetralone derivatives and 2,3‐dihydro‐1,4‐naphthoquinones and show distinct but different stereochemical outcome in the case of epoxy‐1,4‐napthoquinones as substrates. GDH shares the activity towards 2,3‐dihydro‐1,4‐naphthoquinones, however, with low stereocontrol. Moreover, GDH reduces 2‐hydroxy‐2,3‐dihydro‐1,4‐naphthoquinone into trans‐4‐hydroxyscytalone with a high diastereomeric excess (96 %), whereas T4HNR gave the cis diastereomer (diastereomeric excess>99 %). Thus, SDRs provide a much higher functional and stereochemical diversity than previously thought, already exemplified by many transformations of three members of this enzyme family.

Erythrocytes do not produce biologically active NO

The main function of red blood cells (RBC), which is mediated by Hb, is the transport of oxygen and carbon dioxide in the body. In addition, RBC are strongly involved in regulation of vascular tone especially under hypoxic conditions. Hypoxic vasodilation is a fundamental physiological process which directly correlates with the oxygen saturation of Hb in RBC. Since discovery in 1980s that NO is a biological signalling molecule, numerous studies linked NO/Hb to the mechanisms underlying hypoxic vasodilation. According to calculations, mathematical modelling, and experimental data most of NO in blood is scavenged by Hb by the reaction of deoxyHb with NO which results in formation of metHb and nitrate. It has been also proposed that NO can bind by nitrosylation reaction of conserved cysteine on Hb β-chain (β93Cystein) to form SNO-Hb. Although different reactions between NO and Hb are clear and well established, the mechanisms of NO release from Hb and how, in physiological conditions of high excess of free Hb, NO can escape from scavenging by Hb are not so well established. Importantly, till now, there was never shown directly that RBC released biologically active NO can activate soluble guanylyl cyclae (sGC) in neighboring cells (platelets or vascular smooth muscle cells). Most experiments that prove NO release from RBC are done in blood vessel relaxation or in isolated washed RBC. However, both these experimental approaches are not sufficient to clearly answer the question whether RBC can produce biologically active NO because vasorelaxation is a complex reaction which is not mediated only by NO and in isolated RBC experiments it was never shown that RBC produced NO or other NO related radicals could activate sGC. To answer this question we used two different approaches which allow to directly measure NO-mediated activation of sGC in intact cells (platelets) and in purified enzyme. Endogenous NO is a well-known and potent inhibitor of platelet activation and platelet inhibitory effects of NO are mediated solely by sGC activation. Intact platelet sGC is highly sensitive to endogenous NO and even nanomolar NO concentrations are sufficient for cGMP generation. In platelets, the main mediator of cGMP is PKG which phosphorylates multiple substrates responsible for platelet inhibition. For evaluation of platelet sGC activity we used our well-established model based on NO/sGC/cGMP/PKG dependent vasodilator-stimulated phosphoprotein (VASP) phosphorylation in human platelets and purified sGC which is also very sensitive to low NO concentrations. In our experiments RBC were mixed with platelet suspension or with purified enzyme and sGC activation was assessed by VASP phosphorylation and cGMP formation. All our experiments clearly show that RBC, in any conditions, cannot be sources of NO, they act only as a strong NO scavengers and all our data, albeit indirectly, indicate that hypoxia/RBC induced vasodilation is not mediated by NO derived from RBC.

Management Sales Forecasts and Firm Market Power

Managers deciding whether to issue sales forecasts face a different cost-benefit trade-off than when deciding to issue the more commonly studied earnings forecasts because sales forecasts provide investors and competitors with a more transparent signal of a firm’s short-term demand information and the actions it will take in the product market. We provide evidence demonstrating that sales forecasts contain information about future sales that is incremental to earnings forecasts. We then investigate whether a firm’s market power relative to competitors within its product market affects managers’ decisions to issue sales forecasts and what effect market power has on the accuracy of these forecasts. We proxy for market power using market share and excess price-cost margin, two measures that directly relate to the sales forecasts we study. Controlling for industry-level effects, we find evidence that higher firm market power, as measured by excess margin, is associated with a higher likelihood of issuing sales forecasts. Higher excess margin is also associated with better forecast accuracy on average. Overall, our findings are consistent with higher-market-power firms being more willing to provide sales forecast information to investors through public disclosures.

SPECTRUM OF RELATIVISTIC AND SUBRELATIVISTIC COSMIC RAYS IN THE 100 pc CENTRAL REGION

From the rate of hydrogen ionization and the gamma ray flux, we derived the spectrum of relativistic and subrelativistic cosmic rays (CRs) nearby and inside the molecular cloud Sgr B2 near the Galactic Center (GC). We studied two cases of CR propagation in molecular clouds: free propagation and scattering of particles by magnetic fluctuations excited by the neutral gas turbulence. We showed that in the latter case CR propagation inside the cloud can be described as diffusion with the coefficient $\sim 3\times 10^{27}$ cm$^2$ s$^{-1}$. For the case of hydrogen ionization by subrelativistic protons, we showed that their spectrum outside the cloud is quite hard with the spectral index $\delta>-1$. The energy density of subrelativistic protons ($>50$ eV cm$^{-3}$) is one order of magnitude higher than that of relativistic CRs. These protons generate the 6.4 keV emission from Sgr B2, which was about 30\% of the flux observed by Suzaku in 2013. Future observations for the period after 2013 may discover the background flux generated by subrelativistic CRs in Sgr B2. Alternatively hydrogen ionization of the molecular gas in Sgr B2 may be caused by high energy electrons. We showed that the spectrum of electron bremsstrahlung is harder than the observed continuum from Sgr B2, and in principle this X-ray component provided by electrons could be seen from the INTEGRAL data as a stationary high energy excess above the observed spectrum $E_x^{-2}$.

ChemInform Abstract: Asymmetric Synthesis of α‐Hydroxymethylphosphonates and Phosphonic Acids via Hydrophosphonylation of Aldehydes with Chiral H‐Phosphonate.

AbstractThe scalable reaction is performed using aryl, hetaryl, and alkyl aldehydes and provides the corresponding α‐hydroxymethylphosphonates with high yield and high diastereomeric excess.

Stalactite drip-water monitoring and tracer tests approach to assess hydrogeologic behavior of karst vadose zone: case study of Han-sur-Lesse (Belgium)

This paper focuses on the unsaturated zone and epikarst of karst aquifers in order to identify the hydrogeological behavior of these important but poorly understood parts of karst systems. A high-resolution monitoring of stalactite drips and artificial tracer test experiment in the vadose zone allows to draw a conceptual model for the local recharge processes through the unsaturated zone of karst aquifers. Those aquifers represent major groundwater resources in Belgium. Seven years of high-resolution stalactite dripping were recorded on 3 sites of the Han-sur-Lesse cave system (South of Belgium). The three sites show very different discharge variations but a similar behavior from one year to another. Analysis and comparison of the dripping cycles over 7 years highlight the vadose zone behavior and its relationship with surface infiltration (water excess). For each site, a water excess threshold at the beginning of the winter has been identified. This threshold is needed to refill the vadose zone/epikarst capacity before the dripping. The value of the threshold is relatively constant for each site during the 7 years, indicating the regularity of the capacitive system of the vadose zone. Unknown features have also been observed with discharge decrease during high water excess periods, linked to the drainage processes of epikarst. Finally, artificial tracer test reveals the duality of the unsaturated zone behavior, with fast transmissive pathways (velocity of >6 m/h) related to a highly capacitive system (>150 days of tracer restitution).

Moisture sources and synoptic to seasonal variability of North Atlantic water vapor isotopic composition

AbstractThe isotopic composition of near surface (or planetary boundary layer) water vapor on the south coast of Iceland (63.83°N, 21.47°W) has been monitored in situ between November 2011 and April 2013. The calibrated data set documents seasonal variations in the relationship between δ18O and local humidity (ppmv) and between deuterium excess and δ18O. These seasonal variations are attributed to seasonal changes in atmospheric transport. A strong linear relationship is observed between deuterium excess and atmospheric relative humidity calculated at regional sea surface temperature. Surprisingly, we find a similar relationship between deuterium excess and relative humidity as observed in the Bermuda Islands. During days with low amount of isotopic depletion (more enriched values), our data significantly deviate from the global meteoric water line. This feature can be explained by a supply of an evaporative flux into the planetary boundary layer above the ocean, which we show using a 1‐d box model. Based on the close relationship identified between moisture origin and deuterium excess, we combine deuterium excess measurements performed in Iceland and south Greenland with moisture source diagnostics based on back trajectory calculations to establish the distribution of d‐excess moisture uptake values across the North Atlantic. We map high deuterium excess in the Arctic and low deuterium excess for vapor in the subtropics and midlatitudes. This confirms the role of North Atlantic water vapor isotopes as moisture origin tracers.

Time trends for risk of severe age-related diseases in individuals with and without HIV infection in Denmark: a nationwide population-based cohort study

Whether the reported high risk of age-related diseases in HIV-infected people is caused by biological ageing or HIV-associated risk factors such as chronic immune activation and low-grade inflammation is unknown. We assessed time trends in age-standardised and relative risks of nine serious age-related diseases in a nationwide cohort study of HIV-infected individuals and population controls. We identified all HIV-infected individuals in the Danish HIV Cohort Study who had received HIV care in Denmark between Jan 1, 1995, and June 1, 2014. Population controls were identified from the Danish Civil Registration System and individually matched in a ratio of nine to one to the HIV-infected individuals for year of birth, sex, and date of study inclusion. Individuals were included in the study if they had a Danish personal identification number, were aged 16 years or older, and were living in Denmark at the time of study inclusion. Data for study outcomes were obtained from the Danish National Hospital Registry and the Danish National Registry of Causes of Death and were cardiovascular diseases (myocardial infarction and stroke), cancers (virus associated, smoking related, and other), severe neurocognitive disease, chronic kidney disease, chronic liver disease, and osteoporotic fractures. We calculated excess and age-standardised incidence rates and adjusted incidence rate ratios of outcomes for time after HIV diagnosis, highly active antiretroviral therapy (ART) initiation, and calendar time. The regression analyses were adjusted for age, sex, calendar time, and origin. We identified 5897 HIV-infected individuals and 53,073 population controls; median age was 36·8 years (IQR 30·6-44·4), and 76% were men in both cohorts. Dependent on disease, the HIV cohort had 55,050-57,631 person-years of follow-up and the population controls had 638,204-659,237 person-years of follow-up. Compared with the population controls, people with HIV had high excess and relative risk of all age-related diseases except other cancers. Overall, the age-standardised and relative risks of cardiovascular diseases, cancers, and severe neurocognitive disease did not increase substantially with time after HIV diagnosis or ART initiation. Except for chronic kidney diseases, the age-standardised and relative risks of age-related diseases did not increase with calendar time. Severe age-related diseases are highly prevalent in people with HIV, and continued attention and strategies for risk reduction are needed. The findings from our study do not suggest that accelerated ageing is a major problem in the HIV-infected population. Preben og Anna Simonsens Fond, Novo Nordisk Foundation, Danish AIDS Foundation, Augustinus Foundation, and Odense University Hospitals Frie Fonds Midler.

Variation in grain size distribution in debris flow

Grain composition of debris flow varies considerably from fluid to deposit, making it uncertain to estimate flow properties (e.g., density, velocity and discharge) using deposit as done in practice. Tracing the variation of grain composition is thus more important than estimating some certain properties of flow because every debris flow event consists of a series of surges that are distinct in properties and flow regimes. We find that the materials of debris flows, both the fluid and the source soils, satisfy a universal grain size distribution (GSD) in a form of P (D) = CD - mu exp( -D/D (c)), where the parameters C, mu and D (c) are determined by fitting the function to the grain size frequency. A small A mu implies a small porosity and possible high excess pore pressure in flow; and a large D (c) means a wide range of grain composition and hence a high sediment concentration. Flow density increases as A mu decreases or D (c) increases, in a power law form. A debris flow always achieves a state of certain mobility and density that can be well described by the coupling of A mu and D (c) , which imposes a constraint on the fluctuations of flow surges. The GSD also describes the changes in grain composition in that it is always satisfied during the course of debris flow developing. Numerical simulation using the GSD can well illustrate the variation of A mu and D (c) from source soils to deposits.

Is ‘excess’ mortality in Glasgow an artefact of measurement?

ObjectivesA previous investigation of Glasgow's excess mortality showed that the (income) deprivation profiles for Glasgow, Liverpool and Manchester were nearly identical. Despite this, premature deaths in Glasgow were found to be more than 30% higher, and all deaths 15% higher, than in the English cities.This study aimed to explore the extent to which Glasgow's higher mortality could be explained by the use of a potentially more sensitive measure of deprivation employed at a suitably small and consistent geographical spatial unit. Study DesignAnalyses of mortality based on the creation of a three-city index of deprivation using rates of ‘car/van ownership’ deprivation for small areas (average population size: 1600) in Glasgow, Liverpool and Manchester derived from the census. MethodsRates of ‘car/van ownership deprivation were calculated for small areas in Glasgow, Liverpool and Manchester. All-cause and cause-specific standardized mortality ratios were calculated for Glasgow relative to Liverpool and Manchester, standardizing for age, gender and deprivation decile. ResultsThe overall levels of car/van ownership based deprivation in Glasgow, Liverpool and Manchester, in 2001, differed. Glasgow had a higher percentage of its population who did not have access to a car compared with Liverpool and Manchester.All-cause mortality, after adjustment for age, sex and this measure of deprivation, for deaths <65 years were 15% higher and 8% higher for all deaths for males and females respectively. However, this was lower than the excess observed in the previous study. ‘Excess’ mortality was greatest in the working age groups of 15–44 years and 45–64 years, where it was 23% and 15% higher respectively.For deaths at all ages after adjustment, analysis by deprivation decile showed that excess mortality in Glasgow was seen in half the deciles, including four of the five most deprived deciles. However, the greatest excess was seen in comparison of the least deprived neighbourhoods. For premature mortality (deaths under 65 years), the excess was mainly driven by higher mortality in the five most deprived deciles (6–10); again, however, a high excess was seen in comparisons of the least deprived areas. ConclusionsThe higher mortality in Glasgow compared to equally income-deprived Liverpool and Manchester cannot be fully explained by a deprivation index based on lack of access to a car or van, but this index does explain more of the excess than income deprivation. Further work to establish better measures of deprivation and to explain this excess are required.

A route to produce renewable diesel from algae: Synthesis and characterization of biodiesel via in situ transesterification of Chlorella alga and its catalytic deoxygenation to renewable diesel

Abstract In situ transesterification of Chlorella alga was performed using 5–20 wt% sulfuric acid as a catalyst at either 60 or 100 °C. The maximum ester yield in the range of 96–98% is comparative to the specification of ester content in biodiesel, 96%. A high excess of methanol was used in transesterification ensured also a high ester yield. The FAME was purified via adsorption of chlorophyll and carotenoids onto a clay. Properties of the purified biodiesel were investigated with several methods. The results showed that the Chlorella based biodiesel exhibits slightly lower oxidative and thermal stability compared to soybean based biodiesel due to the presence of polyunsaturated FAMEs. In addition to biodiesel, also the residual biomass was characterized showing that it contained sugars and proteins. An additional hydrogenation would increase the oxidative stability. Hydrodeoxygenation of Chlorella based biodiesel was also demonstrated over 5 wt% Ni–HY-80 zeolite with SiO2/Al2O3 ratio of 80 and with 5 wt% Pd/C at 300 °C and 30 bar in dodecane as a solvent. Ni–HY-80 was superior to Pd/C catalyst giving more than 95% yield of hydrocarbons.