Night-time tropospheric chemistry of the unsaturated alcohols (Z)-pent-2-en-1-ol and pent-1-en-3-ol: Kinetic studies of reactions of NO3 and N2O5 with stress-induced plant emissions

The night-time tropospheric chemistry of two stress-induced volatile organic compounds (VOCs), (Z)-pent-2-en-1-ol and pent-1-en-3-ol, has been studied at room temperature. Rate coefficients for reactions of the nitrate radical (NO3) with these pentenols were measured using the discharge-flow technique. Because of the relatively low volatility of these compounds, we employed off-axis continuous-wave cavity-enhanced absorption spectroscopy for detection of NO3 in order to be able to work in pseudo first-order conditions with the pentenols in large excess over NO3. The rate coefficients were determined to be (1.53 +/- 0.23) x 10(-13) and (1.39 +/- 0.19) x 10(-14) cm(3) molecule(-1) s(-1) for reactions of NO3 with (Z)-pent-2-en-1-ol and pent-1-en-3-ol. An attempt to study the kinetics of these reactions with a relative-rate technique, using N2O5 as source of NO3 resulted in significantly higher apparent rate coefficients. Performing relative-rate experiments in known excesses of NO2 allowed us to determine the rate coefficients for the N2O5 reactions to be (5.0 +/- 2.8) x 10(-19) cm(3) molecule(-1) s(-1) for (Z)-pent-2-en-1-ol, and (9.1 +/- 5.8) x 10(-19) cm(3) molecule(-1) s(-1) for pent-1-en-3-ol. We show that these relatively slow reactions can indeed interfere with rate determinations in conventional relative-rate experiments.

Unusual isotope effect in the reaction of chlorosilylene with trimethylsilane-1-d: Absolute rate studies and quantum chemical and Rice–Ramsperger–Kassel–Marcus calculations provide strong evidence for the involvement of an intermediate complex

Time-resolved studies of chlorosilylene, ClSiH, generated by the 193 nm laser flash photolysis of 1-chloro-1- silacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reaction with trimethylsilane-1-d, Me3SiD, in the gas phase. The reaction was studied at total pressures up to 100 Torr (with and without added SF6) over the temperature range of 295−407 K. The rate constants were found to be pressure independent and gave the following Arrhenius equation: log[(k/(cm3 molecule−1 s−1)] = (−13.22 ± 0.15) + [(13.20 ± 1.00) kJ mol−1]/(RT ln 10). When compared with previously published kinetic data for the reaction of ClSiH with Me3SiH, kinetic isotope effects, kD/kH, in the range from 7.4 (297 K) to 6.4 (407 K) were obtained. These far exceed values of 0.4−0.5 estimated for a single-step insertion process. Quantum chemical calculations (G3MP2B3 level) confirm not only the involvement of an intermediate complex, but also the existence of a low-energy internal isomerization pathway which can scramble the D and H atom labels. By means of Rice−Ramsperger−Kassel−Marcus modeling and a necessary (but small) refinement of the energy surface, we have shown that this mechanism can reproduce closely the experimental isotope effects. These findings provide the first experimental evidence for the isomerization pathway and thereby offer the most concrete evidence to date for the existence of intermediate complexes in the insertion reactions of silylenes.

Latitude and longitude vertical disparities

The literature on vertical disparity is complicated by the fact that several different definitions of the term “vertical disparity” are in common use, often without a clear statement about which is intended or a widespread appreciation of the properties of the different definitions. Here, we examine two definitions of retinal vertical disparity: elevation-latitude and elevation-longitude disparities. Near the fixation point, these definitions become equivalent, but in general, they have quite different dependences on object distance and binocular eye posture, which have not previously been spelt out. We present analytical approximations for each type of vertical disparity, valid for more general conditions than previous derivations in the literature: we do not restrict ourselves to objects near the fixation point or near the plane of regard, and we allow for non-zero torsion, cyclovergence, and vertical misalignments of the eyes. We use these expressions to derive estimates of the latitude and longitude vertical disparities expected at each point in the visual field, averaged over all natural viewing. Finally, we present analytical expressions showing how binocular eye position—gaze direction, convergence, torsion, cyclovergence, and vertical misalignment—can be derived from the vertical disparity field and its derivatives at the fovea.

Tannin-containing plants for animal nutrition and health

Abstract 13.12.1

Influence of counter anions on the structures and magnetic properties of trinuclear Cu(II) complexes containing a mu(3)-OH core and Schiff base ligands

Four trinuclear Cu(II) complexes, [(CuL1)(3)(mu(3)-OH)](NO3)(2) (1), [(CuL2)(3)(mu(3)-OH)](I)(2)center dot H2O (2), [(CuL3)(3)(mu(3)-OH)](I)(2) (3) and [(CuL1)(3)(mu(3)-OH)][(CuI3)-I-1] (4), where HL1 (8-amino-4-methyl-5-azaoct-3-en-2-one), HL2 [7-amino-4-methyl-5-azaoct-3-en-2-one] and HL3 [7-amino-4-methyl-5-azahept-3-en-2- one] are the three tridentate Schiff bases, have been synthesized and structurally characterized by X-ray crystallography. All four complexes contain a partial cubane core, [(CuL)(3)(mu(3)-OH)](2+) in which the three [CuL] subunits are interconnected through two types of oxygen bridges afforded by the oxygen atoms of the ligands and the central OH- group. The copper(II) ions are in a distorted square-pyramidal environment. The equatorial plane consists of the bridging oxygen of the central OH- group together with three atoms (N, N, O) from the Schiff base. The oxygen atom of the Schiff base also coordinates to the axial position of Cu(II) of another subunit to form the cyclic trimer. Magnetic susceptibilities have been determined for these complexes over the temperature range of 2-300 K. The isotropic Hamiltonian, H = -J(12)S(1)S(2) - J(13)S(1)S(3) - J(23)S(2)S(3) has been used to interpret the magnetic data. The best fit parameters obtained are: J = - 54.98 cm(-1) g = 2.24 for 1; J = - 56.66 cm(-1), g = 2.19 for 2; J = -44.39 cm(-1), g = 2.16 for 3; J = - 89.92 cm(-1), g = 2.25 for 4. The EPR data at low temperature indicate that the phenomenon of spin frustration occurs for complexes 1-3. (c) 2007 Elsevier B.V. All rights reserved.

Interceptive timing: prior knowledge matters

Fast interceptive actions, such as catching a ball, rely upon accurate and precise information from vision. Recent models rely on flexible combinations of visual angle and its rate of expansion of which the tau parameter is a specific case. When an object approaches an observer, however, its trajectory may introduce bias into tau-like parameters that render these computations unacceptable as the sole source of information for actions. Here we show that observer knowledge of object size influences their action timing, and known size combined with image expansion simplifies the computations required to make interceptive actions and provides a route for experience to influence interceptive action.

Synthesis and evaluation of lipophilic BTBP ligands for An/Ln separation in nuclear waste treatment: the effect of alkyl substitution on extraction properties and implications for ligand design

Four new 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) ligands, which contain either additional alkyl groups on the pyridine rings or seven-membered aliphatic rings attached to the triazine rings, have been synthesized, and the effects of the additional alkyl substitution in the 4- and 4′-positions of the pyridine rings on their extraction properties with LnIII and AnIII cations in simulated nuclear waste solutions have been studied. The speciation of ligand 13 with some trivalent lanthanide nitrates was elucidated by 1H NMR spectroscopic titrations and ESI-MS. Although 13 formed both 1:1 and 1:2 complexes with LaIII and YIII, only 1:2 complexes were observed with EuIII and CeIII. Quite unexpectedly, both alkyl-substituted ligands 12 and 13 showed lower solubilities in certain diluents than the unsubstituted ligand CyMe4-BTBP. Compared to CyMe4-BTBP, alkyl-substitution was found to decrease the rates of metal-ion extraction of the ligands in both 1-octanol and cyclohexanone. A highly efficient (DAm > 10) and selective (SFAm/Eu > 90) extraction was observed for 12 and 13 in cyclohexanone and for 13 in 1-octanol in the presence of a phase-transfer agent. The implications of these results for the design of improved extractants for radioactive waste treatment are discussed.

Two macrocyclic pentaaza compounds containing pyridine evaluated as novel chelating agents in copper(II) and nickel(II) overload

Two pentaaza macrocycles containing pyridine in the backbone, namely 3,6,9,12,18-pentaazabicyclo[12.3.1] octadeca-1(18),14,16-triene ([15]pyN(5)), and 3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca-1(19),15,17-triene ([16]pyN(5)), were synthesized in good yields. The acid-base behaviour of these compounds was studied by potentiometry at 298.2 K in aqueous solution and ionic strength 0.10 M in KNO3. The protonation sequence of [15]pyN(5) was investigated by H-1 NMR titration that also allowed the determination of protonation constants in D2O. Binding studies of the two ligands with Ca2+, Ni2+, Cu2+, Zn2+, Cd2+, and Pb2+ metal ions were performed under the same experimental conditions. The results showed that all the complexes formed with the 15-membered ligand, particularly those of Cu2+ and especially Ni2+, are thermodynamically more stable than with the larger macrocycle. Cyclic voltammetric data showed that the copper(II) complexes of the two macrocycles exhibited analogous behaviour, with a single quasi-reversible one-electron transfer reduction process assigned to the Cu(II)/Cu(I) couple. The UV-visible-near IR spectroscopic and magnetic moment data of the nickel(II) complexes in solution indicated a tetragonal distorted coordination geometry for the metal centre. X-band EPR spectra of the copper(II) complexes are consistent with distorted square pyramidal geometries. The crystal structure of [Cu([15]pyN(5))](2+) determined by X-ray diffraction showed the copper(II) centre coordinated to all five macrocyclic nitrogen donors in a distorted square pyramidal environment.

Are the winters 2010 and 2012 archetypes exhibiting extreme opposite behavior of the North Atlantic jet stream?

The atmospheric circulation over the North Atlantic-European sector experienced exceptional but highly contrasting conditions in the recent 2010 and 2012 winters (November-March; with the year dated by the relevant January). Evidence is given for the remarkably different locations of the eddy-driven westerly jet over the North Atlantic. In the 2010 winter the maximum of the jet stream was systematically between 30ºN and 40ºN (in the ‘south jet regime’), while in the 2012 winter it was predominantly located around 55ºN (north jet regime). These jet features underline the occurrence of either weak flow (2010) or strong and persistent ridges throughout the troposphere (2012). This is confirmed by the very different occurrence of blocking systems over the North Atlantic, associated with episodes of strong cyclonic (anticyclonic) Rossby wave breaking in 2010 (2012) winters. These dynamical features underlie strong precipitation and temperature anomalies over parts of Europe, with detrimental impacts on many socioeconomic sectors. Despite the highly contrasting atmospheric states, mid and high-latitude boundary conditions do not reveal strong differences in these two winters. The two winters were associated with opposite ENSO phases, but there is no causal evidence of a remote forcing from the Pacific sea surface temperatures. Finally, the exceptionality of the two winters is demonstrated in relation to the last 140 years. It is suggested that these winters may be seen as archetypes of North Atlantic jet variability under current climate conditions.

Synoptic preconditions for extreme flooding during the summer Asian Monsoon in the Mumbai area

The summer monsoon season is an important hydrometeorological feature of the Indian subcontinent and it has significant socioeconomic impacts. This study is aimed at understanding the processes associated with the occurrence of catastrophic flood events. The study has two novel features that add to the existing body of knowledge about the South Asian Monsoon: 1) combine traditional hydrometeorological observations (rain gauge measurements) with unconventional data (media and state historical records of reported flooding) to produce value-added century-long time-series of potential flood events, and 2) identify the larger regional synoptic conditions leading to days with flood potential in the time-series. The promise of mining unconventional data to extend hydrometeorological records is demonstrated in this study. The synoptic evolution of flooding events in the western-central coast of India and the densely populated Mumbai area are shown to correspond to active monsoon periods with embedded low-pressure centers and have far upstream influence from the western edge of the Indian Ocean basin. The coastal processes along the Arabian Peninsula where the currents interact with the continental shelf are found to be key features of extremes during the South Asian Monsoon

The extreme European summer 2012

The European summer of 2012 was marked by strongly contrasting rainfall anomalies, which led to flooding in northern Europe and droughts and wildfires in southern Europe. This season was not an isolated event, rather the latest in a string of summers characterized by a southward shifted Atlantic storm track as described by the negative phase of the SNAO. The degree of decadal variability in these features suggests a role for forcing from outside the dynamical atmosphere, and preliminary numerical experiments suggest that the global SST and low Arctic sea ice extent anomalies are likely to have played a role and that warm North Atlantic SSTs were a particular contributing factor. The direct effects of changes in radiative forcing from greenhouse gas and aerosol forcing are not included in these experiments, but both anthropogenic forcing and natural variability may have influenced the SST and sea ice changes.

ENSO impact on Kelvin waves and associated tropical convection

The impact of El Nino–Southern Oscillation (ENSO) on atmospheric Kelvin waves and associated tropical convection is investigated using the ECMWF Re-Analysis, NOAA outgoing longwave radiation (OLR), and the analysis technique introduced in a previous study. It is found that the phase of ENSO has a substantial impact on Kelvin waves and associated convection over the equatorial central-eastern Pacific. El Nino (La Nina) events enhance (suppress) variability of the upper-tropospheric Kelvin wave and the associated convection there, both in extended boreal winter and summer. The mechanism of the impact is through changes in the ENSO-related thermal conditions and the ambient flow. In El Nino years, because of SST increase in the equatorial central-eastern Pacific, variability of eastward-moving convection, which is mainly associated with Kelvin waves, intensifies in the region. In addition, owing to the weakening of the equatorial eastern Pacific westerly duct in the upper troposphere in El Nino years, Kelvin waves amplify there. In La Nina years, the opposite occurs. However, the stronger westerly duct in La Nina winters allows more NH extratropical Rossby wave activity to propagate equatorward and force Kelvin waves around 200 hPa, partially offsetting the in situ weakening effect of the stronger westerlies on the waves. In general, in El Nino years Kelvin waves are more convectively and vertically coupled and propagate more upward into the lower stratosphere over the central-eastern Pacific. The ENSO impact in other regions is not clear, although in winter over the eastern Indian and western Pacific Oceans Kelvin waves and their associated convection are slightly weaker in El Nino than in La Nina years.

Eddy-driven exchange between the open ocean and a sub-ice shelf cavity

The exchange between the open ocean and sub-ice shelf cavities is important to both water mass transformations and ice shelf melting. Here we use a high-resolution (500 m) numerical model to investigate to which degree eddies produced by frontal instability at the edge of a polynya are capable of transporting dense High Salinity Shelf Water (HSSW) underneath an ice shelf. The applied surface buoyancy flux and ice shelf geometry is based on Ronne Ice Shelf in the southern Weddell Sea, an area of intense wintertime sea ice production where a flow of HSSW into the cavity has been observed. Results show that eddies are able to enter the cavity at the southwestern corner of the polynya where an anticyclonic rim current intersects the ice shelf front. The size and time scale of simulated eddies are in agreement with observations close to the Ronne Ice Front. The properties and strength of the inflow are sensitive to the prescribed total ice production, flushing the ice shelf cavity at a rate of 0.2–0.4 × 106 m3 s−1 depending on polynya size and magnitude of surface buoyancy flux. Eddy-driven HSSW transport into the cavity is reduced by about 50% if the model grid resolution is decreased to 2-5 km and eddies are not properly resolved.