Estimation of electronic coupling in π -stacked donor-bridge-acceptor systems: correction of the two-state model

Comparison of donor-acceptor electronic couplings calculated within two-state and three-state models suggests that the two-state treatment can provide unreliable estimates of Vda because of neglecting the multistate effects. We show that in most cases accurate values of the electronic coupling in a π stack, where donor and acceptor are separated by a bridging unit, can be obtained as Ṽ da = (E2 - E1) μ12 Rda + (2 E3 - E1 - E2) 2 μ13 μ23 Rda2, where E1, E2, and E3 are adiabatic energies of the ground, charge-transfer, and bridge states, respectively, μij is the transition dipole moments between the states i and j, and Rda is the distance between the planes of donor and acceptor. In this expression based on the generalized Mulliken-Hush approach, the first term corresponds to the coupling derived within a two-state model, whereas the second term is the superexchange correction accounting for the bridge effect. The formula is extended to bridges consisting of several subunits. The influence of the donor-acceptor energy mismatch on the excess charge distribution, adiabatic dipole and transition moments, and electronic couplings is examined. A diagnostic is developed to determine whether the two-state approach can be applied. Based on numerical results, we showed that the superexchange correction considerably improves estimates of the donor-acceptor coupling derived within a two-state approach. In most cases when the two-state scheme fails, the formula gives reliable results which are in good agreement (within 5%) with the data of the three-state generalized Mulliken-Hush model

Improvement of strategies for the management of fire blight (Erwinia amylovora). Evaluation and optimization of physical and chemical control methods, and use of decision support systems

El foc bacterià és una malaltia que afecta a plantes de la família de la rosàcies, causada pel bacteri Erwinia amylovora. El seu rang d'hostes inclou arbres fruiters, com la perera, la pomera o el codonyer, i plantes ornamentals de gran interès comercial i econòmic. Actualment, la malaltia s'ha dispersat i es troba àmpliament distribuïda en totes les zones de clima temperat del món. A Espanya, on la malaltia no és endèmica, el foc bacterià es va detectar per primer cop al 1995 al nord del país (Euskadi) i posteriorment, han aparegut varis focus en altres localitzacions, que han estat convenientment eradicats. El control del foc bacterià, és molt poc efectiu en plantes afectades per la malaltia, de manera que es basa en mesures encaminades a evitar la dispersió del patogen, i la introducció de la malaltia en regions no endèmiques. En aquest treball, la termoteràpia ha estat avaluada com a mètode d'eradicació d'E. amylovora de material vegetal de propagació asimptomàtic. S'ha demostrat que la termoteràpia és un mètode viable d'eradicar E. amylovora de material de propagació. Gairebé totes les espècies i varietats de rosàcies mantingudes en condicions d'humitat sobrevivien 7 hores a 45 ºC i més de 3 hores a 50 ºC, mentre que més d'1 hora d'exposició a 50 ºC amb calor seca produïa danys en el material vegetal i reduïa la brotació. Tractaments de 60 min a 45 ºC o 30 min a 50 ºC van ser suficients per reduir la població epífita d'E. amylovora a nivells no detectables (5 x 102 ufc g-1 p.f.) en branques de perera. Els derivats dels fosfonats i el benzotiadiazol són efectius en el control del foc bacterià en perera i pomera, tant en condicions de laboratori, com d'hivernacle i camp. Els inductors de defensa de les plantes redueixen els nivells de malaltia fins al 40-60%. Els intervals de temps mínims per aconseguir el millor control de la malaltia van ser 5 dies pel fosetil-Al, i 7 dies per l'etefon i el benzotiadiazol, i les dosis òptimes pel fosetil-Al i el benzotiadiazol van ser 3.72 g HPO32- L-1 i 150 mg i.a. L-1, respectivament. Es millora l'eficàcia del fosetil-Al i del benzotiadiazol en el control del foc bacterià, quan es combinen amb els antibiòtics a la meitat de la dosi d'aquests últims. Tot i que l'estratègia de barrejar productes és més pràctica i fàcil de dur a terme a camp, que l'estratègia de combinar productes, el millor nivell de control de la malaltia s'aconsegueix amb l'estratègia de combinar productes. Es va analitzar a nivell histològic i ultrastructural l'efecte del benzotiadiazol i dels fosfonats en la interacció Erwinia amylovora-perera. Ni el benzotiadiazol, ni el fosetil-Al, ni l'etefon van induir canvis estructurals en els teixits de perera 7 dies després de la seva aplicació. No obstant, després de la inoculació d'E. amylovora es va observar en plantes tractades amb fosetil-Al i etefon una desorganització estructural cel·lular, mentre que en les plantes tractades amb benzotiadiazol aquestes alteracions tissulars van ser retardades. S'han avaluat dos models (Maryblyt, Cougarblight) en un camp a Espanya afectat per la malaltia, per determinar la precisió de les prediccions. Es van utilitzar dos models per elaborar el mapa de risc, el BRS-Powell combinat i el BIS95 modificat. Els resultats van mostrar dos zones amb elevat i baix risc de la malaltia. Maryblyt i Cougarblight són dos models de fàcil ús, tot i que la seva implementació en programes de maneig de la malaltia requereix que siguin avaluats i validats per un període de temps més llarg i en àrees on la malaltia hi estigui present.

Simulating metals and mine discharges in river basins using a new integrated catchment model for metals: pollution impacts and restoration strategies in the Aries-Mures river system in Transylvania, Romania

The INtegrated CAtchment (INCA) model has been developed to simulate the impact of mine discharges on river systems. The model accounts for the key kinetic chemical processes operating as well as the dilution, mixing and redistribution of pollutants in rivers downstream of mine discharges or acid rock drainage sites. The model is dynamic and simulates the day-to-day behaviour of hydrology and eight metals (cadmium, mercury, copper, zinc, lead, arsenic, manganese and chromium) as well as cyanide and ammonia. The model is semi-distributed and can simulate catchments, sub-catchment and in-stream river behaviour. The model has been applied to the Roia Montan Mine in Transylvania, Romania, and used to assess the impacts of old mine adits on the local catchments as well as on the downstream Aries and Mures river system. The question of mine restoration is investigated and a set of clean-up scenarios investigated. It is shown that the planned restoration will generate a much improved water quality from the mine and also alleviate the metal pollution of the river system.

Evaluating the century C model using long-term fertilizer trials in the Indo-Gangetic Plains, India

The GEFSOC Project developed a system for estimating soil carbon (C) stocks and changes at the national and sub-national scale. As part of the development of the system, the Century ecosystem model was evaluated for its ability to simulate soil organic C (SOC) changes in environmental conditions in the Indo-Gangetic Plains, India (IGP). Two long-term fertilizer trials (LTFT), with all necessary parameters needed to run Century, were used for this purpose: a jute (Corchorus capsularis L.), rice (Oryza sativa L.) and wheat (Triticum aestivum L.) trial at Barrackpore, West Bengal, and a rice-wheat trial at Ludhiana, Punjab. The trials represent two contrasting climates of the IGP, viz. semi-arid, dry with mean annual rainfall (MAR) of < 800 mm and humid with > 1600 turn. Both trials involved several different treatments with different organic and inorganic fertilizer inputs. In general, the model tended to overestimate treatment effects by approximately 15%. At the semi-arid site, modelled data simulated actual data reasonably well for all treatments, with the control and chemical N + farm yard manure showing the best agreement (RMSE = 7). At the humid site, Century performed less well. This could have been due to a range of factors including site history. During the study, Century was calibrated to simulate crop yields for the two sites considered using data from across the Indian IGP. However, further adjustments may improve model performance at these sites and others in the IGP. The availability of more longterm experimental data sets (especially those involving flooded lowland rice and triple cropping systems from the IGP) for testing and validation is critical to the application of the model's predictive capabilities for this area of the Indian sub-continent. (C) 2007 Elsevier B.V. All rights reserved.

Human exposure modelling for chemical risk assessment: a review of current approaches and research and policy implications

A wide variety of exposure models are currently employed for health risk assessments. Individual models have been developed to meet the chemical exposure assessment needs of Government, industry and academia. These existing exposure models can be broadly categorised according to the following types of exposure source: environmental, dietary, consumer product, occupational, and aggregate and cumulative. Aggregate exposure models consider multiple exposure pathways, while cumulative models consider multiple chemicals. In this paper each of these basic types of exposure model are briefly described, along with any inherent strengths or weaknesses, with the UK as a case study. Examples are given of specific exposure models that are currently used, or that have the potential for future use, and key differences in modelling approaches adopted are discussed. The use of exposure models is currently fragmentary in nature. Specific organisations with exposure assessment responsibilities tend to use a limited range of models. The modelling techniques adopted in current exposure models have evolved along distinct lines for the various types of source. In fact different organisations may be using different models for very similar exposure assessment situations. This lack of consistency between exposure modelling practices can make understanding the exposure assessment process more complex, can lead to inconsistency between organisations in how critical modelling issues are addressed (e.g. variability and uncertainty), and has the potential to communicate mixed messages to the general public. Further work should be conducted to integrate the various approaches and models, where possible and regulatory remits allow, to get a coherent and consistent exposure modelling process. We recommend the development of an overall framework for exposure and risk assessment with common approaches and methodology, a screening tool for exposure assessment, collection of better input data, probabilistic modelling, validation of model input and output and a closer working relationship between scientists and policy makers and staff from different Government departments. A much increased effort is required is required in the UK to address these issues. The result will be a more robust, transparent, valid and more comparable exposure and risk assessment process. (C) 2006 Elsevier Ltd. All rights reserved.

Effect of manure application on crop yield and soil chemical properties in a long-term field trial of semi-arid Kenya

The sustainability of cereal/legume intercropping was assessed by monitoring trends in grain yield, soil organic C (SOC) and soil extractable P (Olsen method) measured over 13 years at a long-term field trial on a P-deficient soil in semi-arid Kenya. Goat manure was applied annually for 13 years at 0, 5 and 10 t ha(-1) and trends in grain yield were not identifiable because of season-to-season variations. SOC and Olsen P increased for the first seven years of manure application and then remained constant. The residual effect of manure applied for four years only lasted another seven to eight years when assessed by yield, SOC and Olsen P. Mineral fertilizers provided the same annual rates of N and P as in 5 t ha(-1) manure and initially ,gave the same yield as manure, declining after nine years to about 80%. Therefore, manure applications could be made intermittently and nutrient requirements topped-up with fertilizers. Grain yields for sorghum with continuous manure were described well by correlations with rainfall and manure input only, if data were excluded for seasons with over 500 mm rainfall. A comprehensive simulation model should correctly describe crop losses caused by excess water.

Quasi-biennial oscillation and tracer distributions in a coupled chemistry-climate model

[ 1] We have used a fully coupled chemistry-climate model (CCM), which generates its own wind and temperature quasi-biennial oscillation (QBO), to study the effect of coupling on the QBO and to examine the QBO signals in stratospheric trace gases, particularly ozone. Radiative coupling of the interactive chemistry to the underlying general circulation model tends to prolong the QBO period and to increase the QBO amplitude in the equatorial zonal wind in the lower and middle stratosphere. The model ozone QBO agrees well with Stratospheric Aerosol and Gas Experiment II and Total Ozone Mapping Spectrometer satellite observations in terms of vertical and latitudinal structure. The model captures the ozone QBO phase change near 28 km over the equator and the column phase change near +/- 15 degrees latitude. Diagnosis of the model chemical terms shows that variations in NOx are the main chemical driver of the O-3 QBO around 35 km, i.e., above the O-3 phase change.

Forest fire plumes over the North Atlantic: p-TOMCAT model simulations with aircraft and satellite measurements from the ITOP/ICARTT campaign

Intercontinental Transport of Ozone and Precursors (ITOP) (part of International Consortium for Atmospheric Research on Transport and Transformation (ICARTT)) was an intense research effort to measure long-range transport of pollution across the North Atlantic and its impact on O3 production. During the aircraft campaign plumes were encountered containing large concentrations of CO plus other tracers and aerosols from forest fires in Alaska and Canada. A chemical transport model, p-TOMCAT, and new biomass burning emissions inventories are used to study the emissions long-range transport and their impact on the troposphere O3 budget. The fire plume structure is modeled well over long distances until it encounters convection over Europe. The CO values within the simulated plumes closely match aircraft measurements near North America and over the Atlantic and have good agreement with MOPITT CO data. O3 and NOx values were initially too great in the model plumes. However, by including additional vertical mixing of O3 above the fires, and using a lower NO2/CO emission ratio (0.008) for boreal fires, O3 concentrations are reduced closer to aircraft measurements, with NO2 closer to SCIAMACHY data. Too little PAN is produced within the simulated plumes, and our VOC scheme's simplicity may be another reason for O3 and NOx model-data discrepancies. In the p-TOMCAT simulations the fire emissions lead to increased tropospheric O3 over North America, the north Atlantic and western Europe from photochemical production and transport. The increased O3 over the Northern Hemisphere in the simulations reaches a peak in July 2004 in the range 2.0 to 6.2 Tg over a baseline of about 150 Tg.

Chemical composition and fermentation characteristics of grain and different parts of the stover from maize land races harvested at different growing periods in two zones of central Mexico

The objective of this work was to determine the rumen fermentation characteristics of maize land races used as forage in central Mexico. In vitro gas production (ml per 200 mg dry matter (DM)) incubations were carried out, and cumulative gas volumes were fitted to the Krishnamoorthy et al. (1991) model. The trial used a split-plot design with cultivation practices associated with maize colour (COL) as the main plot with three levels: white, yellow and black maize; growing periods (PER) were the split plots where PER1, PER2 and PER3 represented the first, second and third periods, respectively and two contrasting zones (Z1 = valley and Z2 = mountain) were used as blocking factors. The principal effects observed were associated with the maturity of the plants and potential gas production increased (P < 0.05) in stems (PER 1 = 51.8, PER2 = 56.3, PER3 = 58.4 ml per 200 mg DM) and in whole plant (PER 1 = 60.9, PER2 = 60.8, PER3= 70.9 ml per 200 mg DM). An inverse effect was observed with fermentation rates in leaves (P < 0.01) with 0.061, 0.053 and 0.0509 (per h) and in whole plant (P < 0.05) with 0.068, 0.057, 0.050 (per h) in PER1, PER2 and PER3 respectively. The digestibility of the neutral-detergent fibre (NDF) decreased with maturity especially in leaves (P < 0.05) with values of 0.71, 0.67 and 0.66 g/kg; in rachis (P < 0.01) 0.75, 0.72, and 0.65 in PER1, PER2 and PER3 respectively. The NDF content in leaves in leaves (668, 705 and 713 g/kg DM for PER1, PER2 and PER3, respectively), stems (580, 594 and 644 g/kg DM) and, husk (663, 774 and, 808 g/kg DM) increased (P < 0.05) with increasing plant maturity, rachis were significantly different between periods (P < 0.01). The structure with-the best nutritive characteristics was the husk, because it had the lowest fibre contents, especially in acid-detergent lignin, with values of 22.6, 28.6 and 37.6 g/kg DM in PER1, PER2 and PER3, respectively.

Results of a mechanistic model estimating methane in relation to methane emissions measured in dairy cows

This investigation determines the accuracy of estimation of methanogenesis by a dynamic mechanistic model with real data determined in a respiration trial, where cows were fed a wide range of different carbohydrates included in the concentrates. The model was able to predict ECM (Energy corrected milk) very well, while the NDF digestibility of fibrous feed was less well predicted. Methane emissions were predicted quite well, with the exception of one diet containing wheat. The mechanistic model is therefore a helpful tool to estimate methanogenesis based on chemical analysis and dry matter intake, but the prediction can still be improved.

Surprisingly slow reaction of dimethylsilylene with dimethylgermane: time-resolved kinetic studies and related quantum chemical calculations

Time-resolved studies of silylene, SiH2, and dimethylsilylene, SiMe2, generated by the 193 nm laser flash photolysis of appropriate precursor molecules have been carried out to obtain rate constants for their bimolecular reactions with dimethylgermane, Me2GeH2, in the gas phase. SiMe2 + Me2GeH2 was studied at five temperatures in the range 299-555 K. Problems of substrate UV absorption at 193 nm at temperatures above 400 K meant that only three temperatures could be used reliably for rate constant measurement. These rate constants gave the Arrhenius parameters log(A/cm(3) molecule(-1) s(-1)) = -13.25 +/- 0.16 and E-a = -(5.01 +/- 1.01) kJ mol(-1). Only room temperature studies of SiH2 were carried out. These gave values of (4.05 +/- 0.06) x 10(-10) cm(3) molecule(-1) s(-1) (SiH2 + Me2GeH2 at 295 K) and also (4.41 +/- 0.07) x 10(-10) cm(3) molecule(-1) s(-1) (SiH2 + MeGeH3 at 296 K). Rate constant comparisons show the surprising result that SiMe2 reacts 12.5 times slower with Me2GeH2 than with Me2SiH2. Quantum chemical calculations (G2(MP2,SVP)//B3LYP level) of the model Si-H and Ge-H insertion processes of SiMe2 with SiH4/MeSiH3 and GeH4/MeGeH3 support these findings and show that the lower reactivity of SiMe2 with Ge-H bonds is caused by a higher secondary barrier for rearrangement of the initially formed complexes. Full details of the structures of intermediate complexes and the discussion of their stabilities are given in the paper. Other, related, comparisons of silylene reactivity are also presented.

An investigation of the germylene addition reaction, GeH2+C2H2: Time-resolved gas-phase kinetic studies and quantum chemical calculations of the reaction energy surface

Time resolved studies of germylene, GeH2, generated by laser flash photolysis of 3,4-dimethylgermacyclopentene-3, have been carried out to obtain rate constants for its bimolecular reaction with acetylene, C2H2. The reaction was studied in the gas-phase over the pressure range 1-100 Tort, with SF6 as bath gas, at 5 temperatures in the range 297-553 K. The reaction showed a very slight pressure dependence at higher temperatures. The high pressure rate constants (obtained by extrapolation at the three higher temperatures) gave the Arrhenius equation: log(k(infinity)/cm(3) molecule(-1) s(-1)) (-10.94 +/- 0.05) + (6.10 +/- 0.36 kJ mol(-1))/RTln10. These Arrhenius parameters are consistent with a fast reaction occurring at approximately 30% of the collision rate at 298 K. Quantum chemical calculations (both DFT and ab initio G2//B3LYP and G2//QCISD) of the GeC2H4 potential energy surface (PES), show that GeH2 + C2H2 react initially to form germirene which can isomerise to vinylgermylene with a relatively low barrier. RRKM modelling, based on a loose association transition state, but assuming vinylgermylene is the end product (used in combination with a weak collisional deactivation model) predicts a strong pressure dependence using the calculated energies, in conflict with the experimental evidence. The detailed GeC2H4 PES shows considerable complexity with ten other accessible stable minima (B3LYP level), the three most stable of which are all germylenes. Routes through this complex surface were examined in detail. The only product combination which appears capable of satisfying the (P-3) + C2H4.C2H4 was confirmed as a product by GC observed lack of a strong pressure dependence is Ge(P-3) + C2H4. C2H4 was confirmed as a product by GC analysis. Although the formation of these products are shown to be possible by singlet-triplet curve crossing during dissociation of 1-germiranylidene (1-germacyclopropylidene), it seems more likely (on thermochernical grounds) that the triplet biradical, (GeCH2CH2.)-Ge-., is the immediate product precursor. Comparisons are made with the reaction of SiH2 with C2H2.

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

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 NO. 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 299-592 K. The second-order rate constants at 10 Torr fitted the Arrhenius equation log(k/cm(3) molecule(-1) s(-1)) = (- 11.66 +/- 0.01) + (6.20 +/- 0.10 kJ mol(-1))IRT In 10 The rate constants showed a variation with pressure of a factor of ca. 2 over the available range, almost independent of temperature. The data could not be fitted by RRKM calculations to a simple third body assisted association reaction alone. However, a mechanistic model with an additional (pressure independent) side channel gave a reasonable fit to the data. Ab initio calculations at the G3 level supported a mechanism in which the initial adduct, bent H2SiNO, can ring close to form cyclo-H2SiNO, which is partially collisionally stabilized. In addition, bent H2SiNO can undergo a low barrier isomerization reaction leading, via a sequence of steps, ultimately to dissociation products of which the lowest energy pair are NH2 + SiO. The rate controlling barrier for this latter pathway is only 16 kJ mol(-1) below the energy of SiH2 + NO. This is consistent with the kinetic findings. A particular outcome of this work is that, despite the pressure dependence and the effects of the secondary barrier (in the side reaction), the initial encounter of SiH2 with NO occurs at the collision rate. Thus, silylene can be as reactive with odd electron molecules as with many even electron species. Some comparisons are drawn with the reactions of CH2 + NO and SiCl2 + NO.

Low-molecular-weight gelators: Elucidating the principles of gelation based on gelator solubility and a cooperative self-assembly model

This paper highlights the key role played by solubility in influencing gelation and demonstrates that many facets of the gelation process depend on this vital parameter. In particular, we relate thermal stability (T-gel) and minimum gelation concentration (MGC) values of small-molecule gelation in terms of the solubility and cooperative self-assembly of gelator building blocks. By employing a van't Hoff analysis of solubility data, determined from simple NMR measurements, we are able to generate T-calc values that reflect the calculated temperature for complete solubilization of the networked gelator. The concentration dependence of T-calc allows the previously difficult to rationalize "plateau-region" thermal stability values to be elucidated in terms of gelator molecular design. This is demonstrated for a family of four gelators with lysine units attached to each end of an aliphatic diamine, with different peripheral groups (Z or Bee) in different locations on the periphery of the molecule. By tuning the peripheral protecting groups of the gelators, the solubility of the system is modified, which in turn controls the saturation point of the system and hence controls the concentration at which network formation takes place. We report that the critical concentration (C-crit) of gelator incorporated into the solid-phase sample-spanning network within the gel is invariant of gelator structural design. However, because some systems have higher solubilities, they are less effective gelators and require the application of higher total concentrations to achieve gelation, hence shedding light on the role of the MGC parameter in gelation. Furthermore, gelator structural design also modulates the level of cooperative self-assembly through solubility effects, as determined by applying a cooperative binding model to NMR data. Finally, the effect of gelator chemical design on the spatial organization of the networked gelator was probed by small-angle neutron and X-ray scattering (SANS/SAXS) on the native gel, and a tentative self-assembly model was proposed.

Simulating the detailed chemical composition of secondary organic aerosol formed on a regional scale during the TORCH 2003 campaign in the southern UK

Following on from the companion study (Johnson et al., 2006), a photochemical trajectory model (PTM) has been used to simulate the chemical composition of organic aerosol for selected events during the 2003 TORCH (Tropospheric Organic Chemistry Experiment) field campaign. The PTM incorporates the speciated emissions of 124 nonmethane anthropogenic volatile organic compounds (VOC) and three representative biogenic VOC, a highly-detailed representation of the atmospheric degradation of these VOC, the emission of primary organic aerosol (POA) material and the formation of secondary organic aerosol (SOA) material. SOA formation was represented by the transfer of semi and non-volatile oxidation products from the gas-phase to a condensed organic aerosol-phase, according to estimated thermodynamic equilibrium phase-partitioning characteristics for around 2000 reaction products. After significantly scaling all phase-partitioning coefficients, and assuming a persistent background organic aerosol (both required in order to match the observed organic aerosol loadings), the detailed chemical composition of the simulated SOA has been investigated in terms of intermediate oxygenated species in the Master Chemical Mechanism, version 3.1 ( MCM v3.1). For the various case studies considered, 90% of the simulated SOA mass comprises between ca. 70 and 100 multifunctional oxygenated species derived, in varying amounts, from the photooxidation of VOC of anthropogenic and biogenic origin. The anthropogenic contribution is dominated by aromatic hydrocarbons and the biogenic contribution by alpha-and beta-pinene (which also constitute surrogates for other emitted monoterpene species). Sensitivity in the simulated mass of SOA to changes in the emission rates of anthropogenic and biogenic VOC has also been investigated for 11 case study events, and the results have been compared to the detailed chemical composition data. The role of accretion chemistry in SOA formation, and its implications for the results of the present investigation, is discussed.