Solvothermal syntheses, crystal structures and properties of five new thloantimonates(III) containing the [Sb4S7](2-) anion

Five new thioantimonates have been synthesized in the presence of organic amines under solvothermal conditions and their structures determined by single-crystal X-ray diffraction. All of the compounds are layered and contain antimony-sulphide anions of stoichiometry [Sb4S7](2-), but the structure of the anion formed is dependent on the amine used in synthesis. (H3N(CH2)(4)NH3)[Sb4S7] (1) contains [Sb4S7](2-) double chains directed along [010]. Weak interchain Sb-S interactions between neighbouring chains cause the double chains to pack into layers in the ab plane. In the [001] direction, the layers of double chains alternate with doubly protonated diaminobutane molecules to which the chains are hydrogen bonded. Compounds of general formula (TH)(2)[Sb4S7] (T= CH3(CH2)(2)NH2 (2), (CH3)(2)CHNH2 (3), CH3(CH2)(3)NH2 (4) and CH3(CH2)(4)NH2 (5)) adopt a more complex structure in which [Sb3S8](7-) units are linked by Sb-3(3-) pyramids to form chains, which in turn are bridged by sulphur atoms to create sheets containing large heterorings. Pairs of such sheets form double layers of four atoms thickness that are stacked along [001]. Protonated amine molecules are located between anionic antimony-sulphide layers to which they are hydrogen bonded. Thermal analysis reveals that the decomposition temperature of materials containing [Sb4S7](2-) anions is dependent both on the structure of the anion, the lowest decomposition temperature being that of the low-dimensional phase (1) and on the identity of the amine, the decomposition temperature decreasing with an increasing number of carbon atoms and decreasing density. (c) 2005 Elsevier Inc. All rights reserved.

Chiral poly(aromatic amide ester) dendrimers bearing an amino acid derived C-3-symmetric core: synthesis and properties

The effect of hyperbranched macromolecular architectures (dendrimers) upon chirality has received significant attention in recent years in the light of the proposal of amplification of chirality. In particular, several studies have been carried out on the chiroptical properties of dendrimers that contain a chiral core and achiral branches in order to determine if the chirality of the central core can be transmitted to the distal. region of the macromolecule. In addition to interest of a pure academic nature, the presence of such chiral conformational order would be extremely useful in the development of asymmetric catalysts. In this paper, a novel class of chiral dendrimers is described - these perfect hyperbranched macromolecules have been prepared by a convergent route by the coupling of a chiral central core based upon tris(2-aminoethyl)amine and poly(aromatic amide ester) dendritic branches. The chiral properties of these dendrimers have been investigated by detailed optical rotation studies and circular dichroism analysis; the results of these studies are described herein. (C) Wiley-VCH Verlag GmbH Co.

Urea organogelators: synthesis and properties

A series of aromatic ureas have been synthesised and found to exhibit strong gelation or even supergelation characteristics in organic solvents to afford colourless or translucent gel materials. The synthesis of these materials, assessment of their gelation characteristics and rheological properties are reported in this paper.

Estimates of global multicomponent aerosol optical depth and direct radiative perturbation in the Laboratoire de Météorologie Dynamique general circulation model

The global cycle of multicomponent aerosols including sulfate, black carbon (BC),organic matter (OM), mineral dust, and sea salt is simulated in the Laboratoire de Me´te´orologie Dynamique general circulation model (LMDZT GCM). The seasonal open biomass burning emissions for simulation years 2000–2001 are scaled from climatological emissions in proportion to satellite detected fire counts. The emissions of dust and sea salt are parameterized online in the model. The comparison of model-predicted monthly mean aerosol optical depth (AOD) at 500 nm with Aerosol Robotic Network (AERONET) shows good agreement with a correlation coefficient of 0.57(N = 1324) and 76% of data points falling within a factor of 2 deviation. The correlation coefficient for daily mean values drops to 0.49 (N = 23,680). The absorption AOD (ta at 670 nm) estimated in the model is poorly correlated with measurements (r = 0.27, N = 349). It is biased low by 24% as compared to AERONET. The model reproduces the prominent features in the monthly mean AOD retrievals from Moderate Resolution Imaging Spectroradiometer (MODIS). The agreement between the model and MODIS is better over source and outflow regions (i.e., within a factor of 2).There is an underestimation of the model by up to a factor of 3 to 5 over some remote oceans. The largest contribution to global annual average AOD (0.12 at 550 nm) is from sulfate (0.043 or 35%), followed by sea salt (0.027 or 23%), dust (0.026 or 22%),OM (0.021 or 17%), and BC (0.004 or 3%). The atmospheric aerosol absorption is predominantly contributed by BC and is about 3% of the total AOD. The globally and annually averaged shortwave (SW) direct aerosol radiative perturbation (DARP) in clear-sky conditions is �2.17 Wm�2 and is about a factor of 2 larger than in all-sky conditions (�1.04 Wm�2). The net DARP (SW + LW) by all aerosols is �1.46 and �0.59 Wm�2 in clear- and all-sky conditions, respectively. Use of realistic, less absorbing in SW, optical properties for dust results in negative forcing over the dust-dominated regions.

Relationships between lightning and properties of convective cloud clusters

Satellite observations of convective system properties and lightning flash rate are used to investigate the ability of potential lightning parameterizations to capture both the dominant land-ocean contrast in lightning occurrence and regional differences between Africa, the Amazon and the islands of the maritime continent. As found in previous studies, the radar storm height is tightly correlated with the lightning flash rate. A roughly second order power-law fit to the mean radar echo top height above the 0C isotherm is shown to capture both regional and land-ocean contrasts in lightning occurrence and flash rate using a single set of parameters. Recent developments should soon make it possible to implement a parameterization of this kind in global models. Parameterizations based on cloud top height, convective rain rate and convective rain fraction all require the use of separate fits over land and ocean and fail to capture observed differences between continental regions.

Preparation and properties of gallaborane, GaBH6: structure of the gaseous molecule H2Ga(μ-H)2BH2 as determined by vibrational, electron diffraction, and ab initio studies, and structure of the crystalline solid at 110 K as determined by x-ray diffraction``

Gallaborane (GaBH6, 1), synthesized by the metathesis of LiBH4 with [H2GaCl]n at ca. 250 K, has been characterized by chemical analysis and by its IR and 1H and 11B NMR spectra. The IR spectrum of the vapor at low pressure implies the presence of only one species, viz. H2Ga(μ-H)2BH2, with a diborane-like structure conforming to C2v symmetry. The structure of this molecule has been determined by gas-phase electron diffraction (GED) measurements afforced by the results of ab initio molecular orbital calculations. Hence the principal distances (rα in Å) and angles ( α in deg) are as follows: r(Ga•••B), 2.197(3); r(Ga−Ht), 1.555(6); r(Ga−Hb), 1.800(6); r(B−Ht), 1.189(7); r(B−Hb), 1.286(7); Hb−Ga−Hb, 71.6(4); and Hb−B−Hb, 110.0(5) (t = terminal, b = bridging). Aggregation of the molecules occurs in the condensed phases. X-ray crystallographic studies of a single crystal at 110 K reveal a polymeric network with helical chains made up of alternating pseudotetrahedral GaH4 and BH4 units linked through single hydrogen bridges; the average Ga•••B distance is now 2.473(7) Å. The compound decomposes in the condensed phases at temperatures exceeding ca. 240 K with the formation of elemental Ga and H2 and B2H6. The reactions with NH3, Me3N, and Me3P are also described.

In vitro microbial inoculum: A review of its function and properties

This review considers microbial inocula used in in vitro systems from the perspective of their ability to degrade or ferment a particular substrate, rather than the microbial species that it contains. By necessity, this required an examination of bacterial, protozoal and fungal populations of the rumen and hindgut with respect to factors influencing their activity. The potential to manipulate these populations through diet or sampling time are examined, as is inoculum preparation and level. The main alternatives to fresh rumen fluid (i.e., caecal digesta or faeces) are discussed with respect to end-point degradabilities and fermentation dynamics. Although the potential to use rumen contents obtained from donor animals at slaughter offers possibilities, the requirement to store it and its subsequent loss of activity are limitations. Statistical modelling of data, although still requiring a deal of developmental work, may offer an alternative approach. Finally, with respect to the range of in vitro methodologies and equipment employed, it is suggested that a degree of uniformity could be obtained through generation of a set of guidelines relating to the host animal, sampling technique and inoculum preparation. It was considered unlikely that any particular system would be accepted as the 'standard' procedure. However, before any protocol can be adopted, additional data are required (e.g., a method to assess inoculum 'quality' with respect to its fermentative and/or degradative activity), preparation/inoculation techniques need to be refined and a methodology to store inocula without loss of efficacy developed. (c) 2005 Elsevier B.V. All rights reserved.

Synthesis, structure and properties of cobalt(II/III) seleno-bisphenolate complexes containing NN bidentate co-ligands: kinetic studies on the reduction of a cobalt(III) complex by ascorbic acid in 80% MeCN-20% water

Two cobalt complexes, [Co(L-Se)(phen)]center dot CH2Cl2 (1) and [Co(L-Se)(N,N-Me(2)en)(CH3COO-)] (2) have been synthesized and characterized by elemental analyses, magnetic measurements, i.r. studies etc. Single crystal X- ray studies reveal that in complex (1) cobalt atom is in +2 oxidation state with trigonal bipyramidal geometry, while in complex (2) it is in +3 oxidation state and surrounded octahedrally. The asymmetric unit of complex (2) contains two crystallographically independent discrete molecules. Complex (1) was found to be paramagnetic with mu(eff) = 2.19 BM indicating a low spin cobalt(II) d(7) system, whereas complex (2) is found to be diamagnetic with cobalt(III) in low spin d(6) state. The kinetic studies on the reduction of (2) by ascorbic acid in 80% MeCN-20% H2O (v/v) at 25 degrees C reveal that the reaction proceeds through the rapid formation of inner-sphere adduct, probably by replacing the loosely coordinated AcO- group, followed by electron transfer in a slow step and is supported by a large Q (formation constant) value.