Gallium-sulphide supertetrahedral clusters as building blocks of covalent organic-inorganic networks

The synthesis and characterisation of novel covalent organic-inorganic architectures containing organically-functionalised supertetrahedra is described. The structures of these unique materials consist of one-dimensional zigzag chains or of honeycomb-type layers, in which gallium-sulfide supertetrahedral clusters and dipyridyl ligands alternate.

Global and local expression of chirality in serine on the Cu{110} surface

Establishing a molecular-level understanding of enantioselectivity and chiral resolution at the organic−inorganic interfaces is a key challenge in the field of heterogeneous catalysis. As a model system, we investigate the adsorption geometry of serine on Cu{110} using a combination of low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The chirality of enantiopure chemisorbed layers, where serine is in its deprotonated (anionic) state, is expressed at three levels: (i) the molecules form dimers whose orientation with respect to the substrate depends on the molecular chirality, (ii) dimers of l- and d-enantiomers aggregate into superstructures with chiral (−1 2; 4 0) lattices, respectively, which are mirror images of each other, and (iii) small islands have elongated shapes with the dominant direction depending on the chirality of the molecules. Dimer and superlattice formation can be explained in terms of intra- and interdimer bonds involving carboxylate, amino, and β−OH groups. The stability of the layers increases with the size of ordered islands. In racemic mixtures, we observe chiral resolution into small ordered enantiopure islands, which appears to be driven by the formation of homochiral dimer subunits and the directionality of interdimer hydrogen bonds. These islands show the same enantiospecific elongated shapes those as in low-coverage enantiopure layers.

Poly[(2,2 '-bipyridine-kappa N-2,N ')-(mu(2)-dihydrogen phosphato-kappa O-2 : O ')-(mu(2)-hydrogen phosphato-kappa O-2 : O ')-aluminium(III)], Al(2,2 '/bipy)-(HPO4)(H2PO4), a layered inorganic - organic hybrid material

The title compound, [Al(HPO4)(H2PO4)(C10H8N2)]n, consists of AlO4N2 octahedra vertex-linked to H2PO4 and HPO4 tetrahedra to form layers based on a (4,12)- net. The layers stack in an AAA fashion, held in place by pi-pi interactions between 2,2 '-bipyridine molecules coordinated to Al atoms in adjacent layers.

Synthesis and characterization of inorganic-organic hybrid gallium selenides

Two semiconducting hybrid gallium selenides, [Ga6Se9(C6H14N2)4][H2O] (1) and [C6H14N2][Ga4Se6(C6H14N2)2] (2), were prepared using a solvothermal method in the pres-ence of 1,2-diaminocyclohexane (1,2-DACH). Both materials consist of neutral inorganic layers, in which 1,2-DACH is co-valently bonded to gallium. In (1), the organic amine acts as a monodentate and a bidentate ligand, while in (2) bidentate and uncoordinated 1,2-DACH molecules coexist.

Contributions of labile and resistant organic materials to the immobilization of inorganic soil N when used in the restoration of abandoned agricultural fields

We have examined the contributions sucrose and sawdust make to the net immobilization of inorganic soil N and assimilation of both C and N into microbial biomass when they are used as part of a restoration plan to promote the establishment of indigenous vegetation on abandoned agricultural fields on the Central Hungarian Plain. Both amendments led to net N immobilization. Sucrose addition also led to mobilization of N from the soil organic N pool and its immobilization into microbial biomass, whereas sawdust addition apparently immobilized soil N into a non-biomass compartment or a biomass component that was not detected by the conventional biomass N assay (CHCl3 fumigation and extraction). This suggests that the N was either cycled through the biomass, but not immobilized within it, or that it was immobilized in a protected biomass fraction different to the fraction into which N was immobilized in response to sucrose addition.

Decomposition and phosphorus release from organic residues as affected by residue quality and added inorganic phosphorus

The combined use of organic residue and inorganic fertiliser-phosphorus (P) is appropriate in meeting both the short and long-term P requirement of crops. To assess the influence of added inorganic fertiliser-P on the processes of decomposition and P release from the residue and the relationships with quality, prunings of Gliricidia sepium, Leucaena leucocephela, Senna siamea, Acacia mangium and Paraserienthus falcataria were incubated without and with added inorganic fertiliser-P for 56 days. Soil was added only as inoculum. Decomposition rate and amounts of acid extractable-P (P release) were in the same order: G. sepium > S. siamea > L. leucocepheta > P falcataria > A. mangium. Unlike the other residues, A. mangium released no P despite the loss of half its mass during the 8 weeks of incubation. The residue P content correlated with P release. However, decomposition rate did not correlate with residue P content but with the lignin, polyphenol and cellulose content, and ratios to P. These ratios were negatively correlated with P release suggesting that lignin and polyphenol contents influence P release more when the residue-P content is low. Results suggest that rate of decomposition influences the release of P. The critical residue P content for P release was estimated to be 0.12% < P < 0.19%. Added P had no effect on decomposition and P release from the residues.

Contributions of labile and resistant organic materials to the immobilization of inorganic soil N when used in the restoration of abandoned agricultural fields

We have examined the contributions sucrose and sawdust make to the net immobilization of inorganic soil N and assimilation of both C and N into microbial biomass when they are used as part of a restoration plan to promote the establishment of indigenous vegetation on abandoned agricultural fields on the Central Hungarian Plain. Both amendments led to net N immobilization. Sucrose addition also led to mobilization of N from the soil organic N pool and its immobilization into microbial biomass, whereas sawdust addition apparently immobilized soil N into a non-biomass compartment or a biomass component that was not detected by the conventional biomass N assay (CHCl3 fumigation and extraction). This suggests that the N was either cycled through the biomass, but not immobilized within it, or that it was immobilized in a protected biomass fraction different to the fraction into which N was immobilized in response to sucrose addition.

Syntheses and crystal structures of two new coordination polymers of Cd(II) using organic spacer and inorganic-bridging ligands

Two new cadmium (II) complexes [Cd(hmt)(dca)(2)] (n) (1) and [Cd-3(hmt)(2)(SeCN)(6)(H2O)(2)] (n) (2) (hmt=hexamethylenetetramine, dca=dicyanamide) have been synthesized and characterized by X-ray single-crystal analysis. The complex 1 is a 2D rectangular grid of octahedral cadmium (II) with CdN6 chromophore where cadmium centers are doubly bridged by dicyanamide and hmt along a-axis, which are interlinked by dicyanamide running along c-axis. Whereas, complex 2 is a 1D chain of octahedral cadmium (II) with a three-leg ladder topology running along a-axis. The Cd(II) centers are doubly bridged through SeCN (infinite rail) along a-axis and singly bridged by hmt (two-step rung) along c-axis, having cadmium centers with CdSe2N3O and CdSe2N4 chromophores. The adjacent chains through H-bonding between coordinated water and hmt, and (SeSe)-Se-... interaction are extended to 2D supramolecular architecture.

Hybrid materials through linkage of chalcogenide tetrahedral clusters

Tetrahedral chalcogenide clusters, with their well-defined molecular structures and interesting properties, are attractive building blocks for hybrid materials, in which porosity may be integrated with electronic or optical properties. Linkage of tetrahedral clusters often occurs through bridging chalcogenolate ligands, and results in extended structures of inorganic connectivity. However, linkage of tetrahedral clusters via organic ligands is also possible and a number of coordination polymers have already been reported. Recent advances on the synthesis and crystal structures of extended hybrid structures based on tetrahedral clusters are described here.

Comparative growth of ectomycorrhizal fungi (Hebeloma spp.) on organic and inorganic nitrogen

In the largely organic soils in which ectomycorrhizas are commonly found, a preference for absorbing organic nitrogen over mineral forms is likely to be an advantage, especially where mineralisation rates are low. To determine rates of both independent and preferential growth of ectomycorrhizal basidiomycetes on organic and inorganic nitrogen, strains of Hebeloma were grown on nutrient agar media containing either NH4+ or glutamic acid as the sole source of nitrogen, on both single medium and split plate Petri dishes. Growth rates on the split plate Petri dishes, where the fungi had access to both nitrogen sources, were generally greater than on the single medium dishes. Growth on glutamic acid was at least equal to, and usually greater than, that on NH4+. In some cases growth on NH4+ alone appeared severely inhibited, a condition that was partially alleviated by access to glutamic acid on the split plates Petri dishes. This highlights a potential pitfall of single nitrogen source growth studies. The greater growth of most strains on glutamic acid suggests an adaptation to organic nitrogen utilisation in these strains. If this is so in soils with low mineralisation rates, direct uptake of amino acids by ectomycorrhizal plants could by-pass the bottle neck that requires mineral nitrogen to be made available for plant uptake.

Soil mobility of sewage sludge-derived dissolved organic matter, copper, nickel and zinc

A soil (sandy loam) column leaching study aimed to determine the extent of mobility and co-mobility of Cu, Ni, Zn and dissolved organic matter (DOM) released from a surface-application (equivalent to 50 t ds ha(-1)) of anaerobically-digested sewage sludge. Leaching of DOM through It the soil column was found to be almost un-retarded. Decidedly similar behaviour was exhibited by Ni suggesting that it migrated as organic complexes. Whilst Cu was also found to be leached, significant retardation was evident. However, the importance of DOM in promoting the mobility of both Cu and Ni was evidenced by their lack of mobility when added to the soil column as inorganic forms. The presence of DOM did not prevent Zn from becoming completely adsorbed by the soil solid phase. In relation to WHO drinking water guidelines, only Ni concentrations showed potential environmental significance. due to the relatively poor retention of Ni by the sludge solid phase. (C) 2003 Elsevier Ltd. All rights reserved.

The use of FT-IR as a screening technique for organic residue analysis of archaeological samples

A range of archaeological samples have been examined using FT-IR spectroscopy. These include suspected coprolite samples from the Neolithic site of Catalhoyuk in Turkey, pottery samples from the Roman site of Silchester, UK and the Bronze Age site of Gatas, Spain and unidentified black residues on pottery sherds from the Roman sites of Springhead and Cambourne, UK. For coprolite samples the aim of FT-IR analysis is identification. Identification of coprolites in the field is based on their distinct orange colour; however, such visual identifications can often be misleading due to their similarity with deposits such as ochre and clay. For pottery the aim is to screen those samples that might contain high levels of organic residues which would be suitable for GC-MS analysis. The experiments have shown coprolites to have distinctive spectra, containing strong peaks from calcite, phosphate and quartz; the presence of phosphorus may be confirmed by SEM-EDX analysis. Pottery containing organic residues of plant and animal origin has also been shown to generally display strong phosphate peaks. FT-IR has distinguished between organic resin and non-organic compositions for the black residues, with differences also being seen between organic samples that have the same physical appearance. Further analysis by CC-MS has confirmed the identification of the coprolites through the presence of coprostanol and bile acids, and shows that the majority of organic pottery residues are either fatty acids or mono- or di-acylglycerols from foodstuffs, or triterpenoid resin compounds exposed to high temperatures. One suspected resin sample was shown to contain no organic residues. and it is seen that resin samples with similar physical appearances have different chemical compositions. FT-IR is proposed as a quick and cheap method of screening archaeological samples before subjecting them to the more expensive and time-consuming method of GC-MS. This will eliminate inorganic samples such as clays and ochre from CC-MS analysis, and will screen those samples which are most likely to have a high concentration of preserved organic residues. (C) 2008 Elsevier B.V. All rights reserved.

Promoting microbial immobilization of soil nitrogen during restoration of abandoned agricultural fields by organic additions

Application of organic materials to soils to enhance N immobilization into microbial biomass, thereby reducing inorganic N concentrations, was studied as a management option to accelerate the reestablishment of the native vegetation on abandoned arable fields on sandy soils the Kiskunsag National Park, Hungary. Sucrose and sawdust were used at three different topographic sites over 4 years. N availability and extractable inorganic N concentrations were significantly reduced in all sites. Soil microbial biomass C and microbial biomass N increased significantly following C additions, but the microbial C to microbial N ratio remained unaffected. It is concluded that the combined application of the rapidly utilized C source (sucrose) promoted N immobilization, whereas the addition of the slowly utilized C source (sawdust) maintained the elevated microbial biomass C and microbial biomass N in the field.

Effects of cultural system (organic and conventional) on growth, photosynthesis and yield components of sweet corn (zea mays L.) under semi-arid environment

Organic sweet maize consists of a new industrial crop product. Field experiment was conducted to determine the effects of cultural systems on growth, photosynthesis and yield components of sweet maize crop (Zea mays L. F-1 hybrid 'Midas'). A randomized complete block design was employed with four replicates per treatment (organic fertilization: cow manure (5, 10 and 20 t ha(-1)), poultry manure (5, 10 and 20 t ha(-1)) and barley mulch (5, 10 and 20 t ha(-1)), synthetic fertilizer (240 kg N ha(-1)): 21-0-0 and control). The lowest dry weight, height and leaf area index and sod organic matter were measured in the control treatment. Organic matter content was proportionate to the amount of manure applied. The control plots had the lowest yield (1593 kg ha(-1)) and the double rate cow manure plots the had,greatest one. (6104 kg ha(-1)). High correlation between sweet corn yield and organic matter was registered. Moreover, the lowest values of 1000-grain weight were obtained with control plot. The fertilizer plot gave values which were similar to the full rate cow manure treatment. The photosynthetic race of the untreated control was significantly lower than that of the other treatments. The phorosynthetic rate increased as poultry manure and barley mulch ram decreased and as cow manure increased. Furthermore the untreated control had the lowest stomatal conductance and chlorophyll content. Our results indicated that sweet corn growth and yield in the organic plots was significantly higher than those in the conventional plots.