Rational modification of the hierarchy of intermolecular interactions in molecular crystal structures by using tunable halogen bonds

A family of 16 isomolecular salts (3-XpyH)(2)[MX'(4)] (3-XpyH=3-halopyridinium; M=Co, Zn; X=(F), Cl, Br, (I); X'=Cl, Br, I) each containing rigid organic cations and tetrahedral halometallate anions has been prepared and characterized by X-ray single crystal and/or powder diffraction. Their crystal structures reflect the competition and cooperation between non-covalent interactions: N-H center dot center dot center dot X'-M hydrogen bonds, C-X center dot center dot center dot X'-M halogen bonds and pi-pi stacking. The latter are essentially unchanged in strength across the series, but both halogen bonds and hydrogen bonds are modified in strength upon changing the halogens involved. Changing the organic halogen (X) from F to I strengthens the C-X center dot center dot center dot X'-M halogen bonds, whereas an analogous change of the inorganic halogen (X') weakens both halogen bonds and N-H center dot center dot center dot X'-M hydrogen bonds. By so tuning the strength of the putative halogen bonds from repulsive to weak to moderately strong attractive interactions, the hierarchy of the interactions has been modified rationally leading to systematic changes in crystal packing. Three classes of crystal structure are obtained. In type A (C-F center dot center dot center dot X'-M) halogen bonds are absent. The structure is directed by N-H center dot center dot center dot X'-M hydrogen bonds and pi-stacking interactions. In type B structures, involving small organic halogens (X) and large inorganic halogens (X'), long (weak) C-X center dot center dot center dot X'-M interactions are observed with type I halogen-halogen interaction geometries (C-X center dot center dot center dot X' approximate to X center dot center dot center dot X'-M approximate to 155 degrees), but hydrogen bonds still dominate. Thus, minor but quite significant perturbations from the type A structure arise. In type C, involving larger organic halogens (X) and smaller inorganic halogens (X'), stronger halogen bonds are formed with a type II halogen-halogen interaction geometry (C-X center dot center dot center dot X' approximate to 180 degrees; X center dot center dot center dot X'-M approximate to 110 degrees) that is electrostatically attractive. The halogen bonds play a major role alongside hydrogen bonds in directing the type C structures, which as a result are quite different from type A and B.

Reconciliation of halogen-induced ozone loss with the total-column ozone record

The observed depletion of the ozone layer from the 1980s onwards is attributed to halogen source gases emitted by human activities. However, the precision of this attribution is complicated by year-to-year variations in meteorology, that is, dynamical variability, and by changes in tropospheric ozone concentrations. As such, key aspects of the total-column ozone record, which combines changes in both tropospheric and stratospheric ozone, remain unexplained, such as the apparent absence of a decline in total-column ozone levels before 1980, and of any long-term decline in total-column ozone levels in the tropics. Here we use a chemistry–climate model to estimate changes in halogen-induced ozone loss between 1960 and 2010; the model is constrained by observed meteorology to remove the effects of dynamical variability, and driven by emissions of tropospheric ozone precursors to separate out changes in tropospheric ozone. We show that halogen-induced ozone loss closely followed stratospheric halogen loading over the studied period. Pronounced enhancements in ozone loss were apparent in both hemispheres following the volcanic eruptions of El Chichon and, in particular, Mount Pinatubo, which significantly enhanced stratospheric aerosol loads. We further show that approximately 40% of the long-term non-volcanic ozone loss occurred before 1980, and that long-term ozone loss also occurred in the tropical stratosphere. Finally, we show that halogen-induced ozone loss has declined by over 10% since stratospheric halogen loading peaked in the late 1990s, indicating that the recovery of the ozone layer is well underway.

Reactive Halogens in the Marine Boundary Layer (RHaMBLe): the tropical North Atlantic experiments

The NERC UK SOLAS-funded Reactive Halogens in the Marine Boundary Layer (RHaMBLe) programme comprised three field experiments. This manuscript presents an overview of the measurements made within the two simultaneous remote experiments conducted in the tropical North Atlantic in May and June 2007. Measurements were made from two mobile and one ground-based platforms. The heavily instrumented cruise D319 on the RRS Discovery from Lisbon, Portugal to São Vicente, Cape Verde and back to Falmouth, UK was used to characterise the spatial distribution of boundary layer components likely to play a role in reactive halogen chemistry. Measurements onboard the ARSF Dornier aircraft were used to allow the observations to be interpreted in the context of their vertical distribution and to confirm the interpretation of atmospheric structure in the vicinity of the Cape Verde islands. Long-term ground-based measurements at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente were supplemented by long-term measurements of reactive halogen species and characterisation of additional trace gas and aerosol species during the intensive experimental period. This paper presents a summary of the measurements made within the RHaMBLe remote experiments and discusses them in their meteorological and chemical context as determined from these three platforms and from additional meteorological analyses. Air always arrived at the CVAO from the North East with a range of air mass origins (European, Atlantic and North American continental). Trace gases were present at stable and fairly low concentrations with the exception of a slight increase in some anthropogenic components in air of North American origin, though NOx mixing ratios during this period remained below 20 pptv. Consistency with these air mass classifications is observed in the time series of soluble gas and aerosol composition measurements, with additional identification of periods of slightly elevated dust concentrations consistent with the trajectories passing over the African continent. The CVAO is shown to be broadly representative of the wider North Atlantic marine boundary layer; measurements of NO, O3 and black carbon from the ship are consistent with a clean Northern Hemisphere marine background. Aerosol composition measurements do not indicate elevated organic material associated with clean marine air. Closer to the African coast, black carbon and NO levels start to increase, indicating greater anthropogenic influence. Lower ozone in this region is possibly associated with the increased levels of measured halocarbons, associated with the nutrient rich waters of the Mauritanian upwelling. Bromide and chloride deficits in coarse mode aerosol at both the CVAO and on D319 and the continuous abundance of inorganic gaseous halogen species at CVAO indicate significant reactive cycling of halogens. Aircraft measurements of O3 and CO show that surface measurements are representative of the entire boundary layer in the vicinity both in diurnal variability and absolute levels. Above the inversion layer similar diurnal behaviour in O3 and CO is observed at lower mixing ratios in the air that had originated from south of Cape Verde, possibly from within the ITCZ. ECMWF calculations on two days indicate very different boundary layer depths and aircraft flights over the ship replicate this, giving confidence in the calculated boundary layer depth.

The ASSET intercomparison of ozone analyses: method and first results

This paper aims to summarise the current performance of ozone data assimilation (DA) systems, to show where they can be improved, and to quantify their errors. It examines 11 sets of ozone analyses from 7 different DA systems. Two are numerical weather prediction (NWP) systems based on general circulation models (GCMs); the other five use chemistry transport models (CTMs). The systems examined contain either linearised or detailed ozone chemistry, or no chemistry at all. In most analyses, MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) ozone data are assimilated; two assimilate SCIAMACHY (Scanning Imaging Absorption Spectrometer for Atmospheric Chartography) observations instead. Analyses are compared to independent ozone observations covering the troposphere, stratosphere and lower mesosphere during the period July to November 2003. Biases and standard deviations are largest, and show the largest divergence between systems, in the troposphere, in the upper-troposphere/lower-stratosphere, in the upper-stratosphere and mesosphere, and the Antarctic ozone hole region. However, in any particular area, apart from the troposphere, at least one system can be found that agrees well with independent data. In general, none of the differences can be linked to the assimilation technique (Kalman filter, three or four dimensional variational methods, direct inversion) or the system (CTM or NWP system). Where results diverge, a main explanation is the way ozone is modelled. It is important to correctly model transport at the tropical tropopause, to avoid positive biases and excessive structure in the ozone field. In the southern hemisphere ozone hole, only the analyses which correctly model heterogeneous ozone depletion are able to reproduce the near-complete ozone destruction over the pole. In the upper-stratosphere and mesosphere (above 5 hPa), some ozone photochemistry schemes caused large but easily remedied biases. The diurnal cycle of ozone in the mesosphere is not captured, except by the one system that includes a detailed treatment of mesospheric chemistry. These results indicate that when good observations are available for assimilation, the first priority for improving ozone DA systems is to improve the models. The analyses benefit strongly from the good quality of the MIPAS ozone observations. Using the analyses as a transfer standard, it is seen that MIPAS is similar to 5% higher than HALOE (Halogen Occultation Experiment) in the mid and upper stratosphere and mesosphere (above 30 hPa), and of order 10% higher than ozonesonde and HALOE in the lower stratosphere (100 hPa to 30 hPa). Analyses based on SCIAMACHY total column are almost as good as the MIPAS analyses; analyses based on SCIAMACHY limb profiles are worse in some areas, due to problems in the SCIAMACHY retrievals.

Evaluation of ozone and water vapor fields from the ECMWF reanalysis ERA-40 during 1991-1999 in comparison with UARS satellite and MOZAIC aircraft observations

[ 1] The European Centre for Medium-Range Weather Forecasts (ECMWF) 40-year Reanalysis (ERA-40) ozone and water vapor reanalysis fields during the 1990s have been compared with independent satellite data from the Halogen Occultation Experiment (HALOE) and Microwave Limb Sounder (MLS) instruments on board the Upper Atmosphere Research Satellite (UARS). In addition, ERA-40 has been compared with aircraft data from the Measurements of Ozone and Water Vapour by Airbus In-Service Aircraft (MOZAIC) program. Overall, in comparison with the values derived from the independent observations, the upper stratosphere in ERA-40 has about 5 - 10% more ozone and 15 - 20% less water vapor. This dry bias in the reanalysis appears to be global and extends into the middle stratosphere down to 40 hPa. Most of the discrepancies and seasonal variations between ERA-40 and the independent observations occur within the upper troposphere over the tropics and the lower stratosphere over the high latitudes. ERA-40 reproduces a weaker Antarctic ozone hole, and of less vertical extent, than the independent observations; values in the ozone maximum in the tropical stratosphere are lower for the reanalysis. ERA-40 mixing ratios of water vapor are considerably larger than those for MOZAIC, typically by 20% in the tropical upper troposphere, and they may exceed 60% in the lower stratosphere over high latitudes. The results imply that the Brewer-Dobson circulation in the ECMWF reanalysis system is too fast, as is also evidenced by deficiencies in the way ERA-40 reproduces the water vapor "tape recorder'' signal in the tropical stratosphere. Finally, the paper examines the biases and their temporal variation during the 1990s in the way ERA-40 compares to the independent observations. We also discuss how the evaluation results depend on the instrument used, as well as on the version of the data.

In-street wind direction variability in the vicinity of a busy intersection in central London

We present results from fast-response wind measurements within and above a busy intersection between two street canyons (Marylebone Road and Gloucester Place) in Westminster, London taken as part of the DAPPLE (Dispersion of Air Pollution and Penetration into the Local Environment; www.dapple.org.uk) 2007 field campaign. The data reported here were collected using ultrasonic anemometers on the roof-top of a building adjacent to the intersection and at two heights on a pair of lamp-posts on opposite sides of the intersection. Site characteristics, data analysis and the variation of intersection flow with the above-roof wind direction (θref) are discussed. Evidence of both flow channelling and recirculation was identified within the canyon, only a few metres from the intersection for along-street and across-street roof-top winds respectively. Results also indicate that for oblique rooftop flows, the intersection flow is a complex combination of bifurcated channelled flows, recirculation and corner vortices. Asymmetries in local building geometry around the intersection and small changes in the background wind direction (changes in 15-min mean θref of 5–10 degrees) were also observed to have profound influences on the behaviour of intersection flow patterns. Consequently, short time-scale variability in the background flow direction can lead to highly scattered in-street mean flow angles masking the true multi-modal features of the flow and thus further complicating modelling challenges.

Multi-model assessment of stratospheric ozone return dates and ozone recovery in CCMVal-2 models

Projections of stratospheric ozone from a suite of chemistry-climate models (CCMs) have been analyzed. In addition to a reference simulation where anthropogenic halogenated ozone depleting substances (ODSs) and greenhouse gases (GHGs) vary with time, sensitivity simulations with either ODS or GHG concentrations fixed at 1960 levels were performed to disaggregate the drivers of projected ozone changes. These simulations were also used to assess the two distinct milestones of ozone returning to historical values (ozone return dates) and ozone no longer being influenced by ODSs (full ozone recovery). The date of ozone returning to historical values does not indicate complete recovery from ODSs in most cases, because GHG-induced changes accelerate or decelerate ozone changes in many regions. In the upper stratosphere where CO2-induced stratospheric cooling increases ozone, full ozone recovery is projected to not likely have occurred by 2100 even though ozone returns to its 1980 or even 1960 levels well before (~2025 and 2040, respectively). In contrast, in the tropical lower stratosphere ozone decreases continuously from 1960 to 2100 due to projected increases in tropical upwelling, while by around 2040 it is already very likely that full recovery from the effects of ODSs has occurred, although ODS concentrations are still elevated by this date. In the midlatitude lower stratosphere the evolution differs from that in the tropics, and rather than a steady decrease in ozone, first a decrease in ozone is simulated from 1960 to 2000, which is then followed by a steady increase through the 21st century. Ozone in the midlatitude lower stratosphere returns to 1980 levels by ~2045 in the Northern Hemisphere (NH) and by ~2055 in the Southern Hemisphere (SH), and full ozone recovery is likely reached by 2100 in both hemispheres. Overall, in all regions except the tropical lower stratosphere, full ozone recovery from ODSs occurs significantly later than the return of total column ozone to its 1980 level. The latest return of total column ozone is projected to occur over Antarctica (~2045–2060) whereas it is not likely that full ozone recovery is reached by the end of the 21st century in this region. Arctic total column ozone is projected to return to 1980 levels well before polar stratospheric halogen loading does so (~2025–2030 for total column ozone, cf. 2050–2070 for Cly+60×Bry) and it is likely that full recovery of total column ozone from the effects of ODSs has occurred by ~2035. In contrast to the Antarctic, by 2100 Arctic total column ozone is projected to be above 1960 levels, but not in the fixed GHG simulation, indicating that climate change plays a significant role.

Developing protocols for nursery based scheduling trials

Most existing crop scheduling models are cultivar specific and are developed using academic resources. As such they rarely meet the particular needs of a grower. A series of protocols have been created to generate effective schedules for a changing product range using data generated on site at a commercial nursery. A screening programme has been developed to help determine a cultivar's photoperiod sensitivity and vernalisation requirement. Experimental conditions were obtained using a cold store facility set to 5degreesC and photoperiod cloches. Eight and 16 hour photoperiod treatments were achieved at low cost by growing plants in cloches of opaque plastic with a motorised rolling screen. Natural light conditions were extended where necessary using a high pressure sodium lamp. Batches of plants were grown according to different schedules based on these treatments. The screening programme found Coreopsis grandiflora 'Flying Saucers' to be a long day plant. Data to form the basis of graphical tracks was taken using variations on commercial schedules. The work provides a nursery based approach to the continuous improvement of crop scheduling practises.

Photocatalytic degradation of humic acid in saline waters part 2. Effects of various photocatalytic materials

The present study explores for the first time, the effectiveness of photocatalytic oxidation of. humic acid (HA) in the increasingly important highly saline water. TiO2 (Degussa P25), TiO2 (Anatase), TiO2 (Rutile), TiO2 (Mesoporous) and ZnO dispersions were used as catalysts employing a medium pressure mercury lamp. The effect of platinum loading on P25 and zinc oxide was also investigated. The zinc oxide with 0.3% platinum loading was the most efficient catalyst. The preferred medium for the degradation of HA using ZnO is alkaline, whereas for TiO2 it is acidic. In addition, a comparative study of HA decomposition in artificial seawater (ASW) and natural seawater (NSW) is reported, and the surface areas and band gaps of the catalysts employed were also determined. A spectrophotometric method was used to estimate the extent of degradation of HA. (C) 2003 Elsevier Science B.V. All rights reserved.

Photocatalytic degradation of humic acid in saline waters. Part 1. Artificial seawater: influence of TiO2, temperature, pH, and air-flow

We report the first systematic study on the photocatalytic oxidation of humic acid (HA) in artificial seawater (ASW). TiO2 (Degussa P25) dispersions were used as the catalyst with irradiation from a medium-pressure mercury lamp. The optimum quantity of catalyst was found to be between 2 and 2.5 g l(-1); whiled the decomposition was fastest at low pH values (pH 4.5 in the range examined), and the optimum air-flow, using an immersion well reactor with a capacity of 400 ml, was 850 ml min(-1). Reactivity increased with air-flow up to this figure, above which foaming prevented operation of the reactor. Using pure. oxygen, an optimal flow rate was observed at 300 nil min(-1), above which reactivity remains essentially constant. Following treatment for 1 h, low-salinity water (2700 mg l(-1)) was completely mineralised, whereas ASW (46000 mg l(-1)) had traces of HA remaining. These effects are interpreted and kinetic data presented. To avoid problems of precipitation due to change of ionic strength humic substances were prepared directly in ASW, and the effects of ASW on catalyst suspension and precipitation have been taken into account. The Langmuir-Hinshelwood kinetic model has been shown to be followed only approximately for the catalytic oxidation of HA in ASW. The activation energy for the reaction derived from an Arrhenius treatment was 17 ( +/-0.6) kJ mol(-1). (C) 2003 Elsevier Science Ltd. All rights reserved.

Evaluation of the binding ability of a novel dioxatetraazamacrocyclic receptor that contains two phenanthroline units: selective uptake of carboxylate anions

The novel dioxatetraaza macrocycle [26]phen(2)N(4)O(2), which incorporates two phenanthroline units, has been synthesized, and its acid-base behavior has been evaluated by potentiometric and H-1 NMR methods. Six protonation constants were determined, and the protonation sequence was established by NMR. The location of the fifth proton on the phen nitrogen was confirmed by X-ray determinations of the crystal structures of the receptor as bromide and chloride salts. The two compounds have the general molecular formula {(H-5[26]phen(2)N(4)O(2))X-n(H2O)(5-n)}X(n-1)(.)mH(2)O, where X = Cl, n = 3, and m = 6 or X = Br, n = 4, and m = 5.5. In the solid state, the (H-5[26]phen(2)N(4)O(2))(5+) cation adopts a "horseshoe" topology with sufficient room to encapsulate three or four halogen anions through the several N-(HX)-X-... hydrogen-bonding interactions. Two supermolecules {(H-5[26]phen(2)N(4)O(2))X-n(H2O)(5-n)}((5-n)+) form an interpenetrating dimeric species, which was also found by ESI mass spectrum. Binding studies of the protonated macrocycle with aliphatic (ox(2-), mal(2-), suc(2-), cit(3-), cta(3-)) and aromatic (bzc(-), naphc(-), anthc(-), pyrc(-), ph(2-), iph(2-), tph(2-), btc(3-)) anions were determined in water by potentiometric methods. These studies were complemented by H-1 NMR titrations in D2O of the receptor with selected anions. The H-i[26]phen(2)N(4)O(2)(i+) receptor can selectively uptake highly charged or extended aromatic carboxylate anions, such as btc(3-) and pyrc(-), in the pH ranges of 4.0-8.5 and < 4.0, respectively, from aqueous solution that contain the remaining anions as pollutants or contaminants. To obtain further insight into these structural and experimental findings, molecular dynamics (MD) simulations were carried out in water solution.

The kinetics of the 2π+2π photodimerisation reactions of single-crystalline derivatives of trans-cinnamic acid: a study by infrared microspectroscopy

The kinetics of the photodimerisation reactions of the 2- and 4-β-halogeno-derivatives of trans-cinnamic acid (where the halogen is fluorine, chlorine or bromine) have been investigated by infrared microspectroscopy. It is found that none of the reactions proceed to 100% yield. This is in line with a reaction mechanism developed by Wernick and his co-workers that postulates the formation of isolated monomers within the solid, which cannot react. β-4-Bromo and β-4-chloro-trans-cinnamic acids show approximately first order kinetics, although in both cases the reaction accelerates somewhat as it proceeds. First order kinetics is explained in terms of a reaction between one excited- and one ground-state monomer molecule, while the acceleration of the reaction implies that it is promoted as defects are formed within the crystal. By contrast β-2-chloro-trans-cinnamic acid shows a strongly accelerating reaction which models closely to the contracting cube equation. β-2-Fluoro- and β-4-fluoro-trans-cinnamic acids show a close match to first order kinetics. The 4-fluoro-derivative, however, shows a reaction that proceeds via a structural intermediate. The difference in behaviour between the 2-fluoro- and 4-fluoro-derivative may be due to different C–HF hydrogen bonds observed within these single-crystalline starting materials.

Gas-solid reactions of single crystals: a study of the reaction of bromine with single crystals of trans-cinnamic acid and a range of its derivatives by infrared and Raman microspectroscopy

Single crystals of trans-cinnamic acid and of a range of derivatives of this compound containing halogen substituents on the aromatic ring have been reacted with 165 Torr pressure of bromine vapour in a sealed desiccator at 20 degrees C for 1 week. Infrared and Raman microspectroscopic examination of the crystals shows that bromination of the aliphatic double bond, but not of the aromatic ring, has occurred. It is demonstrated also that the reaction is truly gas-solid in nature. A time-dependent study of these reactions shows that they do not follow a smooth diffusion-controlled pathway. Rather the reactions appear to be inhomogeneous and to occur at defects within the crystal. The reaction products are seen to flake from the surface of the crystal. It is shown, therefore, that these are not single crystal to single crystal transitions, as have been observed previously for the photodimerisation of trans-cinnamic acid and several of its derivatives. It is shown that there are no by-products of the reaction and that finely ground samples react to form the same products as single crystals.

Reactions of hydroxyl radicals with trichloroethene and tetrachloroethene in argon matrices at 12 K

Irradiation of argon matrices at 12 K containing hydrogen peroxide and tetrachloroethene using the output from a medium-pressure mercury lamp gives rise to the carbonyl compound trichloroacetyl chloride (CCl3CClO). Similarly trichloroethene gives dichloroacetyl chloride ( CCl2HCClO) - predominantly in the gauche form - under the same conditions. It appears that the reaction is initiated by homolysis of the O-O bond of H2O2 to give OH radicals, one of which adds to the double bond of an alkene molecule. The reaction then proceeds by abstraction of the H atom of the hydroxyl group and Cl-atom migration. This mechanism has been explored by the use of DFT calculations to back up the experimental findings. The mechanism is analogous to that shown by the simple hydrocarbon alkenes.

Correlations for gas-phase reactions of NO3, OH and O3 with alkenes: an update

Methods are developed for predicting rate coefficients for reactions of initiators of tropospheric oxidation with unsaturated compounds that are abundant in the atmosphere; prognostic tools of this kind are essential for atmospheric chemists and modellers. To pursue the aim of exploring such tools, the kinetics of reactions of NO3, OH and O-3 with a series of alkenes are examined for correlations relating the logarithms of the rate coefficients to the energies of the highest occupied molecular orbitals (HOMOs) of the alkenes. A comparison of the values predicted by the correlations with experimental data (where the latter exist) allowed us to assess the reliability of our method. We used a series of theoretical methods to calculate the HOMO energies, and found that higher computational effort improves the agreement of the predicted rate coefficients with experimental values, especially for reactions of NO3 with alkenes that possess vinyllic halogen substituents. As a consequence, it is expedient to suggest new correlations to replace those presented by us and others that were based on the lower level of theory. We propose the following correlations for the reactions of NO3, OH and O-3 with alkenes: ln(k(NO3)/cm(3) molecule(-1) s(-1)) = 6.40(E-HOMO/eV) + 31.69, ln(k(OH)/cm(3) molecule(-1) s(-1)) = 1.21 (E-HOMO/eV)-12.34 and ln(k(O3)/cm(3) molecule(-1) s(-1)) = 3.28(E-HOMO/eV)-6.78. These new correlations have been developed using the larger experimental data sets now available, and the impact of the extended data on the quality of the correlations is examined in the paper. Atmospheric lifetimes have been calculated from both experimental and estimated rate coefficients to provide an overview of removal efficiencies for different classes of alkenes with respect to oxidative processes initiated by NO3, OH and O-3. A figure is presented to show the spatial scales over which alkenes may survive transport in competition with attack by NO3, OH and O-3. Removal by NO3 or OH is always more important than removal by O-3, and reactions with NO3 dominate for scales up to a few hundred metres.