The gas-phase reaction between silylene and 2-butyne: kinetics, isotope studies, pressure dependence studies and quantum chemical calculations

Time-resolved kinetic studies of the reactions of silylene, SiH2, and dideutero-silylene, SiD2, generated by laser. ash photolysis of phenylsilane and phenylsilane-d(3), respectively, have been carried out to obtain rate coefficients for their bimolecular reactions with 2-butyne, CH3C CCH3. The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas at five temperatures in the range 294-612 K. The second-order rate coefficients, obtained by extrapolation to the high pressure limits at each temperature, fitted the Arrhenius equations where the error limits are single standard deviations: log(k(H)(infinity)/cm(3) molecule(-1) s(-1)) = (-9.67 +/- 0.04) + (1.71 +/- 0.33) kJ mol(-1)/RTln10 log(k(D)(infinity)/cm(3) molecule(-1) s(-1)) = (-9.65 +/- 0.01) + (1.92 +/- 0.13) kJ mol(-1)/RTln10 Additionally, pressure-dependent rate coefficients for the reaction of SiH2 with 2-butyne in the presence of He (1-100 Torr) were obtained at 301, 429 and 613 K. Quantum chemical (ab initio) calculations of the SiC4H8 reaction system at the G3 level support the formation of 2,3-dimethylsilirene [cyclo-SiH2C(CH3)=C(CH3)-] as the sole end product. However, reversible formation of 2,3-dimethylvinylsilylene [CH3CH=C(CH3)SiH] is also an important process. The calculations also indicate the probable involvement of several other intermediates, and possible products. RRKM calculations are in reasonable agreement with the pressure dependences at an enthalpy value for 2,3-dimethylsilirene fairly close to that suggested by the ab initio calculations. The experimental isotope effects deviate significantly from those predicted by RRKM theory. The differences can be explained by an isotopic scrambling mechanism, involving H - D exchange between the hydrogens of the methyl groups and the D-atoms in the ring in 2,3-dimethylsilirene-1,1-d(2). A detailed mechanism involving several intermediate species, which is consistent with the G3 energy surface, is proposed to account for this.

The effects of the RAW filter on the climatology and forecast skill of the SPEEDY model

In a recent study, Williams introduced a simple modification to the widely used Robert–Asselin (RA) filter for numerical integration. The main purpose of the Robert–Asselin–Williams (RAW) filter is to avoid the undesired numerical damping of the RA filter and to increase the accuracy. In the present paper, the effects of the modification are comprehensively evaluated in the Simplified Parameterizations, Primitive Equation Dynamics (SPEEDY) atmospheric general circulation model. First, the authors search for significant changes in the monthly climatology due to the introduction of the new filter. After testing both at the local level and at the field level, no significant changes are found, which is advantageous in the sense that the new scheme does not require a retuning of the parameterized model physics. Second, the authors examine whether the new filter improves the skill of short- and medium-term forecasts. January 1982 data from the NCEP–NCAR reanalysis are used to evaluate the forecast skill. Improvements are found in all the model variables (except the relative humidity, which is hardly changed). The improvements increase with lead time and are especially evident in medium-range forecasts (96–144 h). For example, in tropical surface pressure predictions, 5-day forecasts made using the RAW filter have approximately the same skill as 4-day forecasts made using the RA filter. The results of this work are encouraging for the implementation of the RAW filter in other models currently using the RA filter.

Manipulation of Dhaka cheese curd and effects on cheese quality

Dhaka cheese is a semihard artisanal variety originating from Bangladesh where manual curd kneading is a normal stage in its manufacture. Dhaka cheeses were produced with different degrees of curd kneading to quantify the curd manipulation process in terms of pressure and to standardise the length of operation. The effect of manipulation on the composition, rheology, texture and microstructure of fresh cheese was also studied. Manipulation had significant effects (P < 0.05–0.001) on most of the parameters studied. One minute of curd manipulation was found to be sufficient for Dhaka cheesemaking

Thermal and high hydrostatic pressure inactivation of myrosinase from green cabbage: a kinetic study

Myrosinase, a family of enzymes which coexist with glucosinolates in all Brassica vegetables, catalyses the hydrolysis of glucosinolates to yield compounds that can have beneficial effects on human health. In this study, the thermal and pressure inactivation of myrosinase from green cabbage was kinetically investigated. Thermal inactivation started at 35 C and inactivation kinetics was studied in the temperature range 35–55 C. Thermal inactivation of green cabbage myrosinase followed the well known consecutive step model. Pressure inactivation started at 300 MPa, even at 10 C, and the consecutive step model effectively described pressure inactivation in the range 300–450 MPa at 10 C. The combined effects of applying various pressures and temperatures on myrosinase inactivation kinetics were studied in the ranges 35–50 C and, 100–400 MPa. The inactivation followed first-order kinetics at all of the applied combinations. This study demonstrates that myrosinase from green cabbage is highly susceptible to both thermal and high pressure processing. Furthermore, it is also noted that myrosinase stability during processing appears to vary widely between different Brassica species.

Wind-direction effects on urban-type flows

Practically all extant work on flows over obstacle arrays, whether laboratory experiments or numerical modelling, is for cases where the oncoming wind is normal to salient faces of the obstacles. In the field, however, this is rarely the case. Here, simulations of flows at various directions over arrays of cubes representing typical urban canopy regions are presented and discussed. The computations are of both direct numerical simulation and large-eddy simulation type. Attention is concentrated on the differences in the mean flow within the canopy region arising from the different wind directions and the consequent effects on global properties such as the total surface drag, which can change very significantly—by up to a factor of three in some circumstances. It is shown that for a given Reynolds number the typical viscous forces are generally a rather larger fraction of the pressure forces (principally the drag) for non-normal than for normal wind directions and that, dependent on the surface morphology, the average flow direction deep within the canopy can be largely independent of the oncoming wind direction. Even for regular arrays of regular obstacles, a wind direction not normal to the obstacle faces can in general generate a lateral lift force (in the direction normal to the oncoming flow). The results demonstrate this and it is shown how computations in a finite domain with the oncoming flow generated by an appropriate forcing term (e.g. a pressure gradient) then lead inevitably to an oncoming wind direction aloft that is not aligned with the forcing term vector.

The state estimation of flow demands in gas networks from sparse pressure telemetry

This paper presents novel observer-based techniques for the estimation of flow demands in gas networks, from sparse pressure telemetry. A completely observable model is explored, constructed by incorporating difference equations that assume the flow demands are steady. Since the flow demands usually vary slowly with time, this is a reasonable approximation. Two techniques for constructing robust observers are employed: robust eigenstructure assignment and singular value assignment. These techniques help to reduce the effects of the system approximation. Modelling error may be further reduced by making use of known profiles for the flow demands. The theory is extended to deal successfully with the problem of measurement bias. The pressure measurements available are subject to constant biases which degrade the flow demand estimates, and such biases need to be estimated. This is achieved by constructing a further model variation that incorporates the biases into an augmented state vector, but now includes information about the flow demand profiles in a new form.

Effect of high-hydrostatic pressure and pH on the rheological properties of gum arabic

The effect on the viscoelastic behaviour, of pressure-treating hydrated gumarabic samples (800 MPa) at different pH values (2.8, 4.2 and 8.0) was investigated, using controlled stress rheometry. The treated samples were analysed for their complex (G∗), storage (G′) and loss (G″) moduli as a function of frequency, using dynamic oscillatory testing. Significant changes in the rheologicalproperties were observed in both the pressurised gum solutions and in those previously buffered at pH 2.8. The gum, at its natural pH (4.25) and at alkaline pH (8.0), was enhanced by pressure treatment, but only for the already “good” quality gum samples. High-pressure treatment had substantial effects on the frequency-dependence of the moduli of both the pressurised and the pressurised/pH-treated solutions, with the latter being more pronounced, suggesting differing structures or changes in the overall degree of interaction of the gum systems after pressure treatment.

Separating the dynamical effects of climate change and ozone depletion. Part II: Southern Hemisphere troposphere

The separate effects of ozone depleting substances (ODSs) and greenhouse gases (GHGs) on forcing circulation changes in the Southern Hemisphere extratropical troposphere are investigated using a version of the Canadian Middle Atmosphere Model (CMAM) that is coupled to an ocean. Circulation-related diagnostics include zonal wind, tropopause pressure, Hadley cell width, jet location, annular mode index, precipitation, wave drag, and eddy fluxes of momentum and heat. As expected, the tropospheric response to the ODS forcing occurs primarily in austral summer, with past (1960-99) and future (2000-99) trends of opposite sign, while the GHG forcing produces more seasonally uniform trends with the same sign in the past and future. In summer the ODS forcing dominates past trends in all diagnostics, while the two forcings contribute nearly equally but oppositely to future trends. The ODS forcing produces a past surface temperature response consisting of cooling over eastern Antarctica, and is the dominant driver of past summertime surface temperature changes when the model is constrained by observed sea surface temperatures. For all diagnostics, the response to the ODS and GHG forcings is additive: that is, the linear trend computed from the simulations using the combined forcings equals (within statistical uncertainty) the sum of the linear trends from the simulations using the two separate forcings. Space time spectra of eddy fluxes and the spatial distribution of transient wave drag are examined to assess the viability of several recently proposed mechanisms for the observed poleward shift in the tropospheric jet.

The combined action of carvacrol and high hydrostatic pressure on Listeria monocytogenes Scott A

Aims: The aim of the study was to investigate the combined antimicrobial action of the plantderived volatile carvacrol and high hydrostatic pressure (HHP). Methods and Results: Combined treatments of carvacrol and HHP have been studied at different temperatures, using exponentially growing cells of Listeria monocytogenes, and showed a synergistic action. The antimicrobial effects were higher at 1°C than at 8 or 20°C. Furthermore, addition of carvacrol to cells exposed to sublethal HHP treatment caused similar reductions in viable numbers as simultaneous treatment with carvacrol and HHP. Synergism was also observed between carvacrol and HHP in semi-skimmed milk that was artifcially contaminated with L. monocytogenes. Conclusions: Carvacrol and HHP act synergistically and the antimicrobial effects of the combined treatment are greater at lower temperatures. Significance and Impact of the Study: The study demonstrates the synergistic antimicrobial effect of essential oils in combination with HHP and indicates the potential of these combined treatments in food processing.

Olive leaf phenolics and cardiovascular risk reduction: Physiological effects and mechanisms of action

Olive oil, an important component of the Mediterranean diet, is rich in polyphenols and is known to possess positive health effects relative to other dietary fats. In addition, the leaves of the olive plant (Olea europaea) contain similar phenolics (oleuropein, luteolin-7-glucoside, apigenin-7-glucoside, verbascoside and hydroxytyrosol) to those of olives and olive oil, although at higher concentrations. For example, the most abundant is the secoiridoid, oleuropein, representing 1–14% of olive leaf weight vs. 0.005–0.12% in olive oil. Although currently considered a waste product of the olive oil industry, recent research has suggested beneficial effects of phenolic-rich olive leaf extracts (OLE) in modifying cardiovascular risk biomarkers such as blood pressure, hyperglycaemia, oxidative stress and inflammation, as well as improving vascular function and lipid profiles. Despite this, data regarding the biological actions of OLE has mostly derived from animal, in vitro and ex vivo studies, with limited evidence deriving from human trials. Although the absorption and metabolism of olive oil phenolics has been investigated, less is known about the bioavailability of phenolics from OLE, limiting the interpretation of existing in vitro and ex vivo data. The current review will begin by describing the phenolic composition of olive leaves in comparison with that of the better studied olive oil. It will then review the effects of OLE on cardiovascular risk factors, covering both animal and human studies and will end by considering potential mechanisms of action

Correction of atmospheric delay effects in radar interferometry using a nested mesoscale atmospheric model

The temporal variability of the atmosphere through which radio waves pass in the technique of differential radar interferometry can seriously limit the accuracy with which the method can measure surface motion. A forward, nested mesoscale model of the atmosphere can be used to simulate the variable water content along the radar path and the resultant phase delays. Using this approach we demonstrate how to correct an interferogram of Mount Etna in Sicily associated with an eruption in 2004-5. The regional mesoscale model (Unified Model) used to simulate the atmosphere at higher resolutions consists of four nested domains increasing in resolution (12, 4, 1, 0.3 km), sitting within the analysis version of a global numerical model that is used to initiate the simulation. Using the high resolution 3D model output we compute the surface pressure, temperature and the water vapour, liquid and solid water contents, enabling the dominant hydrostatic and wet delays to be calculated at specific times corresponding to the acquisition of the radar data. We can also simulate the second-order delay effects due to liquid water and ice.

Does dairy food intake predict arterial stiffness and blood pressure in men? Evidence from the Caerphilly prospective study

Arterial stiffness is an independent predictor of cardiovascular disease events and mortality, and like blood pressure, may be influenced by dairy food intake. Few studies have investigated the effects of consumption of these foods on prospective measures of arterial stiffness. The present analysis aimed to investigate the prospective relationship between milk, cheese, cream, and butter consumption and aortic pulse wave velocity, augmentation index, systolic and diastolic blood pressure, as well as cross-sectional relationships between these foods and systolic and diastolic blood pressure and metabolic markers using data from the Caerphilly Prospective Study. Included in this cohort were 2512 men, aged 45 to 59 years, who were followed up at 5-year intervals for a mean of 22.8 years (number follow-up 787). Augmentation index was 1.8% lower in subjects in the highest quartiles of dairy product intake compared with the lowest (P trend=0.021), whereas in the highest group of milk consumption systolic blood pressure was 10.4 mm Hg lower (P trend=0.033) than in nonmilk consumers after a 22.8-year follow-up. Cross-sectional analyses indicated that across increasing quartiles of butter intake, insulin (P trend=0.011), triacylglycerol (P trend=0.023), total cholesterol (P trend=0.002), and diastolic blood pressure (P trend=0.027) were higher. Across increasing groups of milk intake and quartiles of dairy product intake, glucose (P trend=0.032) and triglyceride concentrations (P trend=0.031) were lower, respectively. The present results confirm that consumption of milk predicts prospective blood pressure, whereas dairy product consumption, excluding butter, is not detrimental to arterial stiffness and metabolic markers. Further research is needed to better understand the mechanisms that underpin these relationships.

Is fatty acid intake a predictor of arterial stiffness and blood pressure in men? Evidence from the Caerphilly Prospective Study

Background and aims: Arterial stiffness is an independent predictor of cardiovascular disease (CVD) events and all-cause mortality and may be differentially affected by dietary fatty acid (FA) intake. The aim of this study was to investigate the relationship between FA consumption and arterial stiffness and blood pressure in a community-based population. Methods and results: The Caerphilly Prospective Study recruited 2398 men, aged 45-59 years, who were followed up at 5-year intervals for a mean of 17.8-years (n 787). A semi-quantitative food frequency questionnaire estimated intakes of total, saturated, mono- and poly-unsaturated fatty acids (SFA, MUFA, PUFA). Multiple regression models investigated associations between intakes of FA at baseline with aortic pulse wave velocity (aPWV), augmentation index (AIx), systolic and diastolic blood pressure (SBP, DBP) and pulse pressure after a 17.8-year follow-up - as well as cross-sectional relationships with metabolic markers. After adjustment, higher SFA consumption at baseline was associated with higher SBP (P = 0.043) and DBP (P = 0.002) and after a 17.8-year follow-up was associated with a 0.51 m/s higher aPWV (P = 0.006). After adjustment, higher PUFA consumption at baseline was associated with lower SBP (P = 0.022) and DBP (P = 0.036) and after a 17.8-year follow-up was associated with a 0.63 m/s lower aPWV (P = 0.007). Conclusion: This study suggests that consumption of SFA and PUFA have opposing effects on arterial stiffness and blood pressure. Importantly, this study suggests that consumption of FA is an important risk factor for arterial stiffness and CVD.

Combined effects of global change pressures on animal-mediated pollination

Pollination is an essential process in the sexual reproduction of seed plants and a key ecosystem service to human welfare. Animal pollinators decline as a consequence of five major global change pressures: climate change, landscape alteration, agricultural intensification, non-native species, and spread of pathogens. These pressures, which differ in their biotic or abiotic nature and their spatiotemporal scales, can interact in nonadditive ways (synergistically or antagonistically), but are rarely considered together in studies of pollinator and/or pollination decline. Management actions aimed at buffering the impacts of a particular pressure could thereby prove ineffective if another pressure is present. Here, we focus on empirical evidence of the combined effects of global change pressures on pollination, highlighting gaps in current knowledge and future research needs.

Acute ingestion of beetroot bread increases endothelium-independent vasodilation and lowers diastolic blood pressure in healthy men: a randomized controlled trial

Dietary nitrate, from beetroot, has been reported to lower blood pressure (BP) by the sequential reduction of nitrate to nitrite and further to NO in the circulation. However, the impact of beetroot on microvascular vasodilation and arterial stiffness is unknown. In addition, beetroot is consumed by only 4.5% of the UK population, whereas bread is a staple component of the diet. Thus, we investigated the acute effects of beetroot bread (BB) on microvascular vasodilation, arterial stiffness, and BP in healthy participants. Twenty-three healthy men received 200 g bread containing 100 g beetroot (1.1 mmol nitrate) or 200 g control white bread (CB; 0 g beetroot, 0.01 mmol nitrate) in an acute, randomized, open-label, controlled crossover trial. The primary outcome was postprandial microvascular vasodilation measured by laser Doppler iontophoresis and the secondary outcomes were arterial stiffness measured by Pulse Wave Analysis and Velocity and ambulatory BP measured at regular intervals for a total period of 6 h. Plasma nitrate and nitrite were measured at regular intervals for a total period of 7 h. The incremental area under the curve (0-6 h after ingestion of bread) for endothelium-independent vasodilation was greater (P = 0.017) and lower for diastolic BP (DBP; P = 0.032) but not systolic (P = 0.99) BP after BB compared with CB. These effects occurred in conjunction with increases in plasma and urinary nitrate (P < 0.0001) and nitrite (P < 0.001). BB acutely increased endothelium-independent vasodilation and decreased DBP. Therefore, enriching bread with beetroot may be a suitable vehicle to increase intakes of cardioprotective beetroot in the diet and may provide new therapeutic perspectives in the management of hypertension.