Self-assembled molecular complexes and coordination polymers of CdII, hexamine, and monocarboxylates: structural analysis and theoretical studies of supramolecular interactions

Four new cadmium(II) complexes [Cd-2(bz)(4)(H2O)(4)(mu 2-hmt)]center dot Hbz center dot H2O (1), [Cd-3(bz)(6)(H2O)(6)(mu 2-hmt)(2)]center dot 6H(2)O (2), [Cd(pa)(2)(H2O)(mu(2)-hmt)](n) (3), and {[Cd-3(ac)(6)(H2O)(3)(mu(3)-hmt)(2)]center dot 6H(2)O}(n) (4) with hexamine (hmt) and monocarboxylate ions, benzoate (bz), phenylacetate (pa), or acetate (ac) have been synthesized and characterized structurally. Structure determinations reveal that 1 is dinuclear, 2 is trinuclear, 3 is a one-dimensional (1D) infinite chain, and 4 is a two-dimensional (2D) polymer with fused hexagonal rings consisting of Cd-II and hmt. All the Cd-II atoms in the four complexes (except one CdII in 2) possess seven-coordinate pentagonal bipyramidal geometry with the various chelating bidentate carboxylate groups in equatorial sites. One of the CdII ions in 2, a complex that contains two monodentate carboxylates is in a distorted octahedral environment. The bridging mode of hmt is mu 2- in complexes 1-3 but is mu 3- in complex 4. In all complexes, there are significant numbers of H-bonds, C-H/pi, and pi-pi interactions which play crucial roles in forming the supramolecular networks. The importance of the noncovalent interactions in terms of energies and geometries has been analyzed using high level ab initio calculations. The effect of the cadmium coordinated to hmt on the energetic features of the C-H/pi interaction is analyzed. Finally, the interplay between C-H/pi and pi-pi interactions observed in the crystal structure of 3 is also studied.

A kinetics and mechanistic study of the atmospherically relevant reaction between molecular chlorine and dimethyl sulfide (DMS)

A gas-phase kinetics study of the atmospherically important reaction between Cl2 and dimethyl sulfide (DMS)Cl2 + CH3SCH3 → productshas been made using a flow-tube interfaced to a photoelectron spectrometer. The rate constant for this reaction has been measured at 1.6 and 3.0 torr at T = (294 ± 2) K as (3.4 ± 0.7) × 10−14 cm3 molecule−1 s−1. Reaction (1) has been found to proceed via an intermediate, (CH3)2SCl2, to give CH3SCH2Cl and HCl as the products. The mechanism of this reaction and the structure of the intermediate were investigated using electronic structure calculations. A comparison of the mechanisms of the reactions between Cl atoms and DMS, and Cl2 and DMS has been made and the relevance of the results to atmospheric chemistry is discussed.

A study of the atmospherically relevant reaction between molecular chlorine and dimethylsulfide (DMS): establishing the reaction intermediate and measurement of absolute photoionization cross-sections

In a study using UV photoelectron spectroscopy (PES) of the atmospherically relevant reaction CH3SCH3 + Cl2 → CH3SCH2Cl + HCl bands associated with a reaction intermediate have been observed. These have been assigned to ionization of the covalently bound molecule (CH3)2SCl2 on the basis of the intensity of the observed bands as a function of reaction time, molecular orbital calculations of vertical ionization energies and evidence from infrared spectroscopy. A method has also been developed, with the flow-tube/PE spectrometer combination used, to measure photoionization cross-sections of the reagents and products at the photon energy utilized and this has allowed the photoionization cross-section of the intermediate to be estimated. This work augments an earlier study in which the rate constant of the reaction between CH3SCH3 (DMS) and Cl2 has been measured at room temperature.

The molecular structure and one-pot synthesis of [Li(thf)3·Sn(SiMe3)3]

The molecular structure of [Li(thf)3 · Sn(SiMe3)3], prepared by a new, one-pot synthesis in 44% yield, has been determined by a single crystal X-ray diffraction study using synchrotron radiation and a CCD detector. The +Li(thf)3 and −Sn(SiMe3)3 moieties are joined by a Li–Sn bond, 2.865(5) Å in length. [Li(thf)3 · Sn(SiMe3)3] is isomorphous with its germanium analogue.

Urban microclimates and simulation

This chapter examines the workings of urban microclimates and looks at the associated causes and effects of the urban heat island (UHI). It also clarifies the relationship between urban form and the key climatic parameters (sun, daylight, wind, temperature). A particular section is devoted to the concepts of UHI intensity and sky view factor (SVF); these are useful indicators for researchers in this area. The challenge of how to model urban microclimates is covered, featuring the six archetypal urban forms familiar to analysts involved in using simulation software. The latter sections address the issue of urban thermal comfort, the importance of urban ventilation and finally what mitigating strategies can be implemented to curb negative UHI effects.

Evaluation of a photosynthesis-based biogenic isoprene emission scheme in JULES and simulation of isoprene emissions under present-day climate conditions

We have incorporated a semi-mechanistic isoprene emission module into the JULES land-surface scheme, as a first step towards a modelling tool that can be applied for studies of vegetation – atmospheric chemistry interactions, including chemistry-climate feedbacks. Here, we evaluate the coupled model against local above-canopy isoprene emission flux measurements from six flux tower sites as well as satellite-derived estimates of isoprene emission over tropical South America and east and south Asia. The model simulates diurnal variability well: correlation coefficients are significant (at the 95 % level) for all flux tower sites. The model reproduces day-to-day variability with significant correlations (at the 95 % confidence level) at four of the six flux tower sites. At the UMBS site, a complete set of seasonal observations is available for two years (2000 and 2002). The model reproduces the seasonal pattern of emission during 2002, but does less well in the year 2000. The model overestimates observed emissions at all sites, which is partially because it does not include isoprene loss through the canopy. Comparison with the satellite-derived isoprene-emission estimates suggests that the model simulates the main spatial patterns, seasonal and inter-annual variability over tropical regions. The model yields a global annual isoprene emission of 535 ± 9 TgC yr−1 during the 1990s, 78 % of which from forested areas.

A molecular, morphological and cytological investigation of the identity of non-native Ludwigia (Onagraceae) populations in Britain

A combined molecular, morphological and cytological analysis was used to study the identity and number of species of Ludwigia section Oligospermum occurring in British waterways. Only one taxon was identified for which the name L. grandiflora subsp. hexapetala (Hook. & Arn.) G.L. Nesom & Kartesz is preferred. A chromosome count of 2n = 80 was made for all plants tested and DNA evidence demonstrates that at least two clones are present in Britain. Morphological characters to differentiate L.grandiflora subsp. hexapetala and L. peploides subsp. montevidensis (Spreng.) P.H. Raven are provided. Though the production of fruit in Britain by apparently isolated populations is noted, repeated introduction into the wild from gardens is judged to be primarily responsible for the British distribution of the taxon. Legislative implications are considered and an amendment to Schedule 9 of the UK Wildlife and Countryside Act (1981) is strongly advocated.

Complex-valued B-spline neural networks for modeling and inverting Hammerstein systems

Many communication signal processing applications involve modelling and inverting complex-valued (CV) Hammerstein systems. We develops a new CV B-spline neural network approach for efficient identification of the CV Hammerstein system and effective inversion of the estimated CV Hammerstein model. Specifically, the CV nonlinear static function in the Hammerstein system is represented using the tensor product from two univariate B-spline neural networks. An efficient alternating least squares estimation method is adopted for identifying the CV linear dynamic model’s coefficients and the CV B-spline neural network’s weights, which yields the closed-form solutions for both the linear dynamic model’s coefficients and the B-spline neural network’s weights, and this estimation process is guaranteed to converge very fast to a unique minimum solution. Furthermore, an accurate inversion of the CV Hammerstein system can readily be obtained using the estimated model. In particular, the inversion of the CV nonlinear static function in the Hammerstein system can be calculated effectively using a Gaussian-Newton algorithm, which naturally incorporates the efficient De Boor algorithm with both the B-spline curve and first order derivative recursions. The effectiveness of our approach is demonstrated using the application to equalisation of Hammerstein channels.