Surface chemistry of alanine on Cu{111}: Adsorption geometry and temperature dependence

Adsorption of l-alanine on the Cu{111} single crystal surface was investigated as a model system for interactions between small chiral modifier molecules and close-packed metal surfaces. Synchrotron-based X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy are used to determine the chemical state, bond coordination and out-of-plane orientation of the molecule on the surface. Alanine adsorbs in its anionic form at room temperature, whilst at low temperature the overlayer consists of anionic and zwitterionic molecules. NEXAFS spectra exhibit a strong angular dependence of the π ⁎ resonance associated with the carboxylate group, which allows determining the tilt angle of this group with respect to the surface plane (48° ± 2°) at room temperature. Low-energy electron diffraction (LEED) shows a p(2√13x2√13)R13° superstructure with only one domain, which breaks the mirror symmetry of the substrate and, thus, induces global chirality to the surface. Temperature-programmed XPS (TP-XPS) and temperature-programmed desorption (TPD) experiments indicate that the zwitterionic form converts into the anionic species (alaninate) at 293 K. The latter desorbs/decomposes between 435 K and 445 K.

What limits insect fecundity? Body size- and temperature-dependent egg maturation and oviposition in a butterfly

1. Large female insects usually have high potential fecundity. Therefore selection should favour an increase in body size given that these females get opportunities to realize their potential advantage by maturing and laying more eggs. However, ectotherm physiology is strongly temperature-dependent, and activities are carried out sufficiently only within certain temperature ranges. Thus it remains unclear if the fecundity advantage of a large size is fully realized in natural environments, where thermal conditions are limiting. 2. Insect fecundity might be limited by temperature at two levels; first eggs need to mature, and then the female needs time for strategic ovipositing of the egg. Since a female cannot foresee the number of oviposition opportunities that she will encounter on a given day, the optimal rate of egg maturation will be governed by trade-offs associated with egg- and time-limited oviposition. As females of different sizes will have different amounts of body reserves, size-dependent allocation trade-offs between the mother’s condition and her egg production might be expected. 3. In the temperate butterfly Pararge aegeria , the time and temperature dependence of oviposition and egg maturation, and the interrelatedness of these two processes were investigated in a series of laboratory experiments, allowing a decoupling of the time budgets for the respective processes. 4. The results show that realized fecundity of this species can be limited by both the temperature dependence of egg maturation and oviposition under certain thermal regimes. Furthermore, rates of oviposition and egg maturation seemed to have regulatory effects upon each other. Early reproductive output was correlated with short life span, indicating a cost of reproduction. Finally, large females matured more eggs than small females when deprived of oviposition opportunities. Thus, the optimal allocation of resources to egg production seems dependent on female size. 5. This study highlights the complexity of processes underlying rates of egg maturation and oviposition in ectotherms under natural conditions. We further discuss the importance of temperature variation for egg- vs. time-limited fecundity and the consequences for the evolution of female body size in insects.

Atmospheric chemistry of C4F9OC2H5 (HFE-7200), C4F9OCH3 (HFE-7100), C3F7OCH3 (HFE-7000) and C3F7CH2OH: temperature dependence of the kinetics of their reactions with OH radicals, atmospheric lifetimes and global warming potentials

The atmospheric chemistry of several gases used in industrial applications, C4F9OC2H5 (HFE-7200), C4F9OCH3 (HFE-7100), C3F7OCH3 (HFE-7000) and C3F7CH2OH, has been studied. The discharge flow technique coupled with mass-spectrometric detection has been used to study the kinetics of their reactions with OH radicals as a function of temperature. The infrared spectra of the compounds have also been measured. The following Arrhenius expressions for the reactions were determined (in units of cm3 molecule-1 s-1): k(OH + HFE-7200) = (6.9+2.3-1.7) × 10-11 exp(-(2030 ± 190)/T); k(OH + HFE-7100) = (2.8+3.2-1.5) × 10-11 exp(-(2200 ± 490)/T); k(OH + HFE-7000) = (2.0+1.2-0.7) × 10-11 exp(-(2130 ± 290)/T); and k(OH + C3F7CH2OH) = (1.4+0.3-0.2) × 10-11 exp(-(1460 ± 120)/T). From the infrared spectra, radiative forcing efficiencies were determined and compared with earlier estimates in the literature. These were combined with the kinetic data to estimate 100-year time horizon global warming potentials relative to CO2 of 69, 337, 499 and 36 for HFE-7200, HFE-7100, HFE-7000 and CF3CF2CF2CH2OH, respectively.

Evaluating the potential of high pressure high temperature and thermal processing on volatile compounds, nutritional and structural properties of orange and yellow carrots

The present study compares the impact of thermal and high pressure high temperature(HPHT) processing on volatile profile (via a non-targeted headspace fingerprinting) and structural and nutritional quality parameter (via targeted approaches) of orange and yellow carrot purees. The effect of oil enrichment was also considered. Since oil enrichment affects compounds volatility, the effect of oil was not studied when comparing the volatile fraction. For the targeted part, as yellow carrot purees were shown to contain a very low amount of carotenoids, focus was given to orange carrot purees. The results of the non-targeted approach demonstrated HPHT processing exerts a distinct effect on the volatile fractions compared to thermal processing. In addition, different colored carrot varieties are characterized by distinct headspace fingerprints. From a structural point of view, limited or no difference could be observed between orange carrot purees treated with HPHT or HT processes, both for samples without and with oil. From nutritional point of view, only in samples with oil, significant isomerisation of all-trans-β-carotene occurred due to both processing. Overall, for this type of product and for the selected conditions, HPHT processing seems to have a different impact on the volatile profile but rather similar impact on the structural and nutritional attributes compared to thermal processing.

The retrieval of ice water content from radar reflectivity factor and temperature and its use in evaluating a mesoscale model

Ice clouds are an important yet largely unvalidated component of weather forecasting and climate models, but radar offers the potential to provide the necessary data to evaluate them. First in this paper, coordinated aircraft in situ measurements and scans by a 3-GHz radar are presented, demonstrating that, for stratiform midlatitude ice clouds, radar reflectivity in the Rayleigh-scattering regime may be reliably calculated from aircraft size spectra if the "Brown and Francis" mass-size relationship is used. The comparisons spanned radar reflectivity values from -15 to +20 dBZ, ice water contents (IWCs) from 0.01 to 0.4 g m(-3), and median volumetric diameters between 0.2 and 3 mm. In mixed-phase conditions the agreement is much poorer because of the higher-density ice particles present. A large midlatitude aircraft dataset is then used to derive expressions that relate radar reflectivity and temperature to ice water content and visible extinction coefficient. The analysis is an advance over previous work in several ways: the retrievals vary smoothly with both input parameters, different relationships are derived for the common radar frequencies of 3, 35, and 94 GHz, and the problem of retrieving the long-term mean and the horizontal variance of ice cloud parameters is considered separately. It is shown that the dependence on temperature arises because of the temperature dependence of the number concentration "intercept parameter" rather than mean particle size. A comparison is presented of ice water content derived from scanning 3-GHz radar with the values held in the Met Office mesoscale forecast model, for eight precipitating cases spanning 39 h over Southern England. It is found that the model predicted mean I WC to within 10% of the observations at temperatures between -30 degrees and - 10 degrees C but tended to underestimate it by around a factor of 2 at colder temperatures.

Time-resolved gas-phase kinetic and quantum chemical studies of the reaction of silylene with oxygen

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with O-2. The reaction was studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at five temperatures in the range 297-600 K. The second order rate constants at 10 Torr were fitted to the Arrhenius equation: log(k/cm(3) molecule(-1) s(-1)) = (-11.08 +/- 0.04) + (1.57 +/- 0.32 kJ mol(-1))/RT ln10 The decrease in rate constant values with increasing temperature, although systematic is very small. The rate constants showed slight increases in value with pressure at each temperature, but this was scarcely beyond experimental uncertainty. From estimates of Lennard-Jones collision rates, this reaction is occurring at ca. 1 in 20 collisions, almost independent of pressure and temperature. Ab initio calculations at the G3 level backed further by multi-configurational (MC) SCF calculations, augmented by second order perturbation theory (MRMP2), support a mechanism in which the initial adduct, H2SiOO, formed in the triplet state (T), undergoes intersystem crossing to the more stable singlet state (S) prior to further low energy isomerisation processes leading, via a sequence of steps, ultimately to dissociation products of which the lowest energy pair are H2O + SiO. The decomposition of the intermediate cyclo-siladioxirane, via O-O bond fission, plays an important role in the overall process. The bottleneck for the overall process appears to be the T -> S process in H2SiOO. This process has a small spin orbit coupling matrix element, consistent with an estimate of its rate constant of 1 x 10(9) s(-1) obtained with the aid of RRKM theory. This interpretation preserves the idea that, as in its reactions in general, SiH2 initially reacts at the encounter rate with O-2. The low values for the secondary reaction barriers on the potential energy surface account for the lack of an observed pressure dependence. Some comparisons are drawn with the reactions of CH2 + O-2 and SiCl2 + O-2.

Viscoelastic properties of high pressure and heat induced tofu gels

Tofu gels were rheologically examined to determine their storage or elastic (G′) and loss or viscous (G″) moduli as a function of frequency within their linear viscoelastic limits. The tofu gels were made using either glucono-δ-lactone (GDL) or calcium sulphate (CaSO4·2H2O), followed by either heat treatment (heated soymilk at 97 °C prior to coagulation and subsequently held at 70 °C for 60 min, HT) or high pressure treatment (400 MPa at 20 °C for 10 min, HP). The overall moduli values of the GDL gels and CaSO4·2H2O gels of both physical treatments were similar, each gave frequency profiles expected for weak viscoelastic materials. However, although both temperature and high pressure treatments could be used to produce tofu gels, the final products were not the same. Pressure formed gels, despite having a higher overall “consistency” (increasing values of their moduli), had a proportionately higher contribution from the loss modulus (increased tan δ). Differences could also be observed using confocal scanning laser microscopy. While such treatment may give rise to differing systems/structures, with new or modified organoleptic properties, the more “open” structures obtained by pressure treatment may well cause processing difficulties if subsequent reworking or moulding is required.

Viscoelastic properties of high pressure and heat induced tofu gels

Tofu gels were rheologically examined to determine their storage or elastic (G') and loss or viscous (G '') moduli as a function of frequency within their linear viscoelastic limits. The tofu gels were made using either glucono-delta-lactone (GDL) or calcium sulphate (CaSO4 center dot 2H(2)O), followed by either heat treatment (heated soymilk at >= 97 degrees C prior to coagulation and subsequently held at 70 degrees C for 60 min, HT) or high pressure treatment (400 MPa at 20 degrees C for 10 min, HP). The overall moduli values of the GDL gels and CaSO4 center dot 2H(2)O gels of both physical treatments were similar, each gave frequency profiles expected for weak viscoelastic materials. However, although both temperature and high pressure treatments could be used to produce tofu gels, the final products were not the same. Pressure formed gels, despite having a higher overall "consistency" (increasing values of their moduli), had a proportionately higher contribution from the loss modulus (increased tan delta). Differences could also be observed using confocal scanning laser microscopy. While such treatment may give rise to differing systems/structures, with new or modified organoleptic properties, the more "open" structures obtained by pressure treatment may well cause processing difficulties if subsequent reworking or moulding is required. (c) 2007 Elsevier Ltd. All rights reserved.

Effects of combined high-pressure and heat treatment on the textural properties of soya gels

sSPI, 7S, and 11S globulin at 12% (w/v) protein concentration, at neutral pH, did not form gels when heat-treated (90 degreesC, 15 min) or when high pressure-treated (300-700 MPa), except for the I IS, which formed a gel when heat-treated. The combination of heat and pressure (that is heating the solutions in a water bath and then pressure-treating at room temperature or the reverse sequence), led to differences: when heat-treatment was before high-pressure treatment, only the I IS fraction formed a self-standing gel; however, when the solutions were pressurised before heat treatment, all the proteins formed self-standing gels. The textural and water-holding properties were measured on the gels formed with the three different soy proteins. (C) 2002 Elsevier Science Ltd. All rights reserved.

Effect of small, acid-soluble proteins on spore resistance and germination under a combination of pressure and heat treatment

To find the range of pressure required for effective high-pressure inactivation of bacterial spores and to investigate the role of alpha/beta-type small, acid-soluble proteins (SASP) in spores under pressure treatment, mild heat was combined with pressure (room temperature to 65 degrees C and 100 to 500 MPa) and applied to wild-type and SASP-alpha(-/)beta(-) Bacillus subtilis spores. On the one hand, more than 4 log units of wild-type spores were reduced after pressurization at 100 to 500 MPa and 65 degrees C, On the other hand, the number of surviving mutant spores decreased by 2 log units at 100 MPa and by more than 5 log units at 500 MPa. At 500 MPa and 65 degrees C, both wild-type and mutant spore survivor counts were reduced by 5 log units. Interestingly, pressures of 100, 200, and 300 MPa at 65 degrees C inactivated wild-type SASP-alpha(+)/beta(+) spores more than mutant SASP-alpha(-)/beta(-) spores, and this was attributed to less pressure-induced germination in SASP-alpha(-)/beta(-) spores than in wild-type SASP-alpha(+)/beta(+) spores. However, there was no difference in the pressure resistance between SASP-alpha(+)/beta(+) and SASP-alpha(-)/beta(-) spores at 100 MPa and ambient temperature (approximately 22 degrees C) for 30 min. A combination of high pressure and high temperature is very effective for inducing spore germination, and then inactivation of the germinated spore occurs because of the heat treatment. This study showed that alpha/beta-type SASP play a role in spore inactivation by increasing spore germination under 100 to 300 MPa at high temperature.

Temperature dependence of protein dynamics simulated with three different water models

The effect of variation of the water model on the temperature dependence of protein and hydration water dynamics is examined by performing molecular dynamics simulations of myoglobin with the TIP3P, TIP4P, and TIP5P water models and the CHARMM protein force field at temperatures between 20 and 300 K. The atomic mean-square displacements, solvent reorientational relaxation times, pair angular correlations between surface water molecules, and time-averaged structures of the protein are all found to be similar, and the protein dynamical transition is described almost indistinguishably for the three water potentials. The results provide evidence that for some purposes changing the water model in protein simulations without a loss of accuracy may be possible.

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.

The annual-cycle modulation of meridional asymmetry in ENSO’s atmospheric response and its dependence on ENSO zonal structure

Previous studies documented that a distinct southward shift of central-Pacific low-level wind anomalies occurring during the ENSO decaying phase, is caused by an interaction between the Western Pacific annual cycle and El Niño-Southern Oscillation (ENSO) variability. The present study finds that the meridional movement of the central-Pacific wind anomalies appears only during traditional Eastern-Pacific (or EP) El Niño events rather than in Central-Pacific (CP) El Niño events in which sea surface temperature (SST) anomalies are confined to the central Pacific. The zonal structure of ENSO-related SST anomalies therefore has an important effect on meridional asymmetry in the associated atmospheric response and its modulation by the annual cycle. In contrast to EP El Niño events, the SST anomalies of CP El Niño events extend further west towards to the warm pool region with its climatological warm SSTs. In the warm pool region, relatively small SST anomalies thus are able to excite convection anomalies on both sides of the equator, even with a meridionally asymmetric SST background state. Therefore, almost meridionally symmetric precipitation and wind anomalies are observed over the central Pacific during the decaying phase of CP El Niño events. The SST anomaly pattern of La Niña events is similar to CP El Niño events with a reversed sign. Accordingly, no distinct southward displacement of the atmospheric response occurs over the central Pacific during the La Niña decaying phase. These results have important implications for ENSO climate impacts over East Asia, since the anomalous low-level anticyclone over the western North Pacific is an integral part of the annual cycle-modulated ENSO response.

Extended cusp-like regions and their dependence on the Polar orbit, seasonal variations, and interplanetary conditions

Extended cusp-like regions (ECRs) are surveyed, as observed by the Magnetospheric Ion Composition Sensor (MICS) of the Charge and Mass Magnetospheric Ion Composition Experiment (CAMMICE) instrument aboard Polar between 1996 and 1999. The first of these ECR events was observed on 29 May 1996, an event widely discussed in the literature and initially thought to be caused by tail lobe reconnection due to the coinciding prolonged interval of strong northward IMF. ECRs are characterized here by intense fluxes of magnetosheath-like ions in the energy-per-charge range of _1 to 10 keV e_1. We investigate the concurrence of ECRs with intervals of prolonged (lasting longer than 1 and 3 hours) orientations of the IMF vector and high solar wind dynamic pressure (PSW). Also investigated is the opposite concurrence, i.e., of the IMF and high PSW with ECRs. (Note that these surveys are asking distinctly different questions.) The former survey indicates that ECRs have no overall preference for any orientation of the IMF. However, the latter survey reveals that during northward IMF, particularly when accompanied by high PSW, ECRs are more likely. We also test for orbital and seasonal effects revealing that Polar has to be in a particular region to observe ECRs and that they occur more frequently around late spring. These results indicate that ECRs have three distinct causes and so can relate to extended intervals in (1) the cusp on open field lines, (2) the magnetosheath, and (3) the magnetopause indentation at the cusp, with the latter allowing magnetosheath plasma to approach close to the Earth without entering the magnetosphere.