Hyaluronic acid : evaluation as a potential delivery vehicle for vitronectin:growth factor complexes in wound healing applications

We have previously reported that novel vitronectin:growth factor (VN:GF) complexes significantly increase re-epithelialization in a porcine deep dermal partial-thickness burn model. However, the potential exists to further enhance the healing response through combination with an appropriate delivery vehicle which facilitates sustained local release and reduced doses of VN:GF complexes. Hyaluronic acid (HA), an abundant constituent of the interstitium, is known to function as a reservoir for growth factors and other bioactive species. The physicochemical properties of HA confer it with an ability to sustain elevated pericellular concentrations of these species. This has been proposed to arise via HA prolonging interactions of the bioactive species with cell surface receptors and/or protecting them from degradation. In view of this, the potential of HA to facilitate the topical delivery of VN:GF complexes was evaluated. Two-dimensional (2D) monolayer cell cultures and 3D de-epidermised dermis (DED) human skin equivalent (HSE) models were used to test skin cell responses to HA and VN:GF complexes. Our 2D studies revealed that VN:GF complexes and HA stimulate the proliferation of human fibroblasts but not keratinocytes. Experiments in our 3D DED-HSE models showed that VN:GF complexes, both alone and in conjunction with HA, led to enhanced development of both the proliferative and differentiating layers in the DED-HSE models. However, there was no significant difference between the thicknesses of the epidermis treated with VN:GF complexes alone and VN:GF complexes together with HA. While the addition of HA did not enhance all the cellular responses to VN:GF complexes examined, it was not inhibitory, and may confer other advantages related to enhanced absorption and transport that could be beneficial in delivery of the VN:GF complexes to wounds.

Structural Systematics of the Anhydrous 1:1 Proton-Transfer Compounds of 3,5-Dinitrosalicylic Acid with Aniline and Monosubstituted Anilines

The crystal structures of the proton-transfer compounds of 3,5-dinitrosalicylic acid (DNSA) with a series of aniline-type Lewis bases [aniline, 2-hydroxyaniline, 2-methoxyaniline, 3-methoxyaniline, 4-fluoroaniline, 4-chloroaniline and 2-aminoaniline] have been determined and their hydrogen-bonding systems analysed. All are anhydrous 1:1 salts: [(C6H8N)+(C7H3N2O7)-], (1), [(C6H8NO)+(C7H3N2O7)-], (2), [(C7H10NO)+(C7H3N2O7)-], (3), [(C7H10NO)+(C7H3N2O7)-], (4), [(C6H7FN)+(C7H3N2O7)-], (5), [(C6H7ClN)+(C7H3N2O7)-], (6), and [(C6H9N2)+(C7H3N2O7)-], (7) respectively. Crystals of 1 and 6 are triclinic, space group P-1 while the remainder are monoclinic with space group either P21/n (2, 4, 5 and 7) or P21 (3). Unit cell dimensions and contents are: for 1, a = 7.2027(17), b = 7.5699(17), c = 12.9615(16) Å, α = 84.464(14), β = 86.387(15), γ = 75.580(14)o, Z = 2; for 2, a = 7.407(3), b = 6.987(3), c = 27.653(11) Å, β = 94.906(7)o, Z = 4; for 3, a = 8.2816(18), b = 23.151(6), c = 3.9338(10), β = 95.255(19)o, Z = 2; for 4, a = 11.209(2), b = 8.7858(19), c = 15.171(3) Å, β = 93.717(4)o, Z = 4; for 5, a = 26.377(3), b = 10.1602(12), c = 5.1384(10) Å, β = 91.996(13)o, Z = 4; for 6, a = 11.217(3), b = 14.156(5), c = 4.860(3) Å, α = 99.10(4), β = 96.99(4), γ = 76.35(2)o, Z = 2; for 7, a = 12.830(4), b = 8.145(3), c = 14.302(4) Å, β = 102.631(6)o, Z = 4. In all compounds at least one primary linear intermolecular N+-H…O(carboxyl) hydrogen-bonding interaction is present which, together with secondary hydrogen bonding results in the formation of mostly two-dimensional network structures, exceptions being with compounds 4 and 5 (one-dimensional) and compound 6 (three-dimensional). In only two cases [compounds 1 and 4], are weak cation-anion or cation-cation π-π interactions found while weak aromatic C-H…O interactions are insignificant. The study shows that all compounds fit the previously formulated classification scheme for primary and secondary interactive modes for proton-transfer compounds of 3,5-dinitrosalicylic acid but there are some unusual variants.

Controls on iron in soils and soil waters of a forested, coastal catchment in subtropical Australia

Soluble organic matter derived from exotic Pinus vegetation forms stronger complexes with iron (Fe) than the soluble organic matter derived from most native Australian species. This has lead to concern about the environmental impacts related to the establishment of extensive exotic Pinus plantations in coastal southeast Queensland, Australia. It has been suggested that the Pinus plantations may enhance the solubility of Fe in soils by increasing the amount of organically complexed Fe. While this remains inconclusive, the environmental impacts of an increased flux of dissolved, organically complexed Fe from soils to the fluvial system and then to sensitive coastal ecosystems are potentially damaging. Previous work investigated a small number of samples, was largely laboratory based and had limited application to field conditions. These assessments lacked field-based studies, including the comparison of the soil water chemistry of sites associated with Pinus vegetation and undisturbed native vegetation. In addition, the main controls on the distribution and mobilisation of Fe in soils of this subtropical coastal region have not been determined. This information is required in order to better understand the relative significance of any Pinus enhanced solubility of Fe. The main aim of this thesis is to determine the controls on Fe distribution and mobilisation in soils and soil waters of a representative coastal catchment in southeast Queensland (Poona Creek catchment, Fraser Coast) and to test the effect of Pinus vegetation on the solubility and speciation of Fe. The thesis is structured around three individual papers. The first paper identifies the main processes responsible for the distribution and mobilisation of labile Fe in the study area and takes a catchment scale approach. Physicochemical attributes of 120 soil samples distributed throughout the catchment are analysed, and a new multivariate data analysis approach (Kohonen’s self organising maps) is used to identify the conditions associated with high labile Fe. The second paper establishes whether Fe nodules play a major role as an iron source in the catchment, by determining the genetic mechanism responsible for their formation. The nodules are a major pool of Fe in much of the region and previous studies have implied that they may be involved in redox-controlled mobilisation and redistribution of Fe. This is achieved by combining a detailed study of a ferric soil profile (morphology, mineralogy and micromorphology) with the distribution of Fe nodules on a catchment scale. The third component of the thesis tests whether the concentration and speciation of Fe in soil solutions from Pinus plantations differs significantly from native vegetation soil solutions. Microlysimeters are employed to collect unaltered, in situ soil water samples. The redox speciation of Fe is determined spectrophotometrically and the interaction between Fe and dissolved organic matter (DOM) is modelled with the Stockholm Humic Model. The thesis provides a better understanding of the controls on the distribution, concentration and speciation of Fe in the soils and soil waters of southeast Queensland. Reductive dissolution is the main mechanism by which mobilisation of Fe occurs in the study area. Labile Fe concentrations are low overall, particularly in the sandy soils of the coastal plain. However, high labile Fe is common in seasonally waterlogged and clay-rich soils which are exposed to fluctuating redox conditions and in organic-rich soils adjacent to streams. Clay-rich soils are most common in the upper parts of the catchment. Fe nodules were shown to have a negligible role in the redistribution of dissolved iron in the catchment. They are formed by the erosion, colluvial transport and chemical weathering of iron-rich sandstones. The ferric horizons, in which nodules are commonly concentrated, subsequently form through differential biological mixing of the soil. Whereas dissolution/ reprecipitation of the Fe cements is an important component of nodule formation, mobilised Fe reprecipitates locally. Dissolved Fe in the soil waters is almost entirely in the ferrous form. Vegetation type does not affect the concentration and speciation of Fe in soil waters, although Pinus DOM has greater acidic functional group site densities than DOM from native vegetation. Iron concentrations are highest in the high DOM soil waters collected from sandy podosols, where they are controlled by redox potential. Iron concentrations are low in soil solutions from clay and iron oxide rich soils, in spite of similar redox potentials. This is related to stronger sorption to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for microbial metabolisation and reductive dissolution of Fe. Modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxidising conditions. Thus, inputs of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides and increase the flux of dissolved iron out of the catchment. Such inputs are most likely from the lower catchment, where podosols planted with Pinus are most widely distributed. Significant outcomes other than the main aims were also achieved. It is shown that mobilisation of Fe in podosols can occur as dissolved Fe(II) rather than as Fe(III)-organic complexes. This has implications for the large body of work which assumes that Fe(II) plays a minor role. Also, the first paper demonstrates that a data analysis approach based on Kohonen’s self organising maps can facilitate the interpretation of complex datasets and can help identify geochemical processes operating on a catchment scale.

Iron biogeochemistry and associated greenhouse gas evolution in a forested subtropical Australian coastal catchment : Poona Creek, Southeast Queensland

Iron (Fe) is the fourth most abundant element in the Earth’s crust. Excess Fe mobilization from terrestrial into aquatic systems is of concern for deterioration of water quality via biofouling and nuisance algal blooms in coastal and marine systems. Substantial Fe dissolution and transport involve alternate Fe(II) oxidation followed by Fe(III) reduction, with a diversity of Bacteria and Archaea acting as the key catalyst. Microbially-mediated Fe cycling is of global significance with regard to cycles of carbon (C), sulfur (S) and manganese (Mn). However, knowledge regarding microbial Fe cycling in circumneutral-pH habitats that prevail on Earth has been lacking until recently. In particular, little is known regarding microbial function in Fe cycling and associated Fe mobilization and greenhouse (CO2 and CH4, GHG) evolution in subtropical Australian coastal systems where microbial response to ambient variations such as seasonal flooding and land use changes is of concern. Using the plantation-forested Poona Creek catchment on the Fraser Coast of Southeast Queensland (SEQ), this research aimed to 1) study Fe cycling-associated bacterial populations in diverse terrestrial and aquatic habitats of a representative subtropical coastal circumneutral-pH (4–7) ecosystem; and 2) assess potential impacts of Pinus plantation forestry practices on microbially-mediated Fe mobilization, organic C mineralization and associated GHG evolution in coastal SEQ. A combination of wet-chemical extraction, undisturbed core microcosm, laboratory bacterial cultivation, microscopy and 16S rRNA-based molecular phylogenetic techniques were employed. The study area consisted primarily of loamy sands, with low organic C and dissolved nutrients. Total reactive Fe was abundant and evenly distributed within soil 0–30 cm profiles. Organic complexation primarily controlled Fe bioavailability and forms in well-drained plantation soils and water-logged, native riparian soils, whereas tidal flushing exerted a strong “seawater effect” in estuarine locations and formed a large proportion of inorganic Fe(III) complexes. There was a lack of Fe(II) sources across the catchment terrestrial system. Mature, first-rotation plantation clear-felling and second-rotation replanting significantly decreased organic matter and poorly crystalline Fe in well-drained soils, although variations in labile soil organic C fractions (dissolved organic C, DOC; and microbial biomass C, MBC) were minor. Both well-drained plantation soils and water-logged, native-vegetation soils were inhabited by a variety of cultivable, chemotrophic bacterial populations capable of C, Fe, S and Mn metabolism via lithotrophic or heterotrophic, (micro)aerobic or anaerobic pathways. Neutrophilic Fe(III)-reducing bacteria (FeRB) were most abundant, followed by aerobic, heterotrophic bacteria (heterotrophic plate count, HPC). Despite an abundance of FeRB, cultivable Fe(II)-oxidizing bacteria (FeOB) were absent in associated soils. A lack of links between cultivable Fe, S or Mn bacterial densities and relevant chemical measurements (except for HPC correlated with DOC) was likely due to complex biogeochemical interactions. Neither did variations in cultivable bacterial densities correlate with plantation forestry practices, despite total cultivable bacterial densities being significantly lower in estuarine soils when compared with well-drained plantation soils and water-logged, riparian native-vegetation soils. Given that bacterial Fe(III) reduction is the primary mechanism of Fe oxide dissolution in soils upon saturation, associated Fe mobilization involved several abiotic and biological processes. Abiotic oxidation of dissolved Fe(II) by Mn appeared to control Fe transport and inhibit Fe dissolution from mature, first-rotation plantation soils post-saturation. Such an effect was not observed in clear-felled and replanted soils associated with low SOM and potentially low Mn reactivity. Associated GHG evolution post-saturation mainly involved variable CO2 emissions, with low, but consistently increasing CH4 effluxes in mature, first-rotation plantation soil only. In comparison, water-logged soils in the riparian native-vegetation buffer zone functioned as an important GHG source, with high potentials for Fe mobilization and GHG, particularly CH4 emissions in riparian loam soils associated with high clay and crystalline Fe fractions. Active Fe–C cycling was unlikely to occur in lower-catchment estuarine soils associated with low cultivable bacterial densities and GHG effluxes. As a key component of bacterial Fe cycling, neutrophilic FeOB widely occurred in diverse aquatic, but not terrestrial, habitats of the catchment study area. Stalked and sheathed FeOB resembling Gallionella and Leptothrix were limited to microbial mat material deposited in surface fresh waters associated with a circumneutral-pH seep, and clay-rich soil within riparian buffer zones. Unicellular, Sideroxydans-related FeOB (96% sequence identity) were ubiquitous in surface and subsurface freshwater environments, with highest abundance in estuary-adjacent shallow coastal groundwater water associated with redox transition. The abundance of dissolved C and Fe in the groundwater-dependent system was associated with high numbers of cultivable anaerobic, heterotrophic FeRB, microaerophilic, putatively lithotrophic FeOB and aerobic, heterotrophic bacteria. This research represents the first study of microbial Fe cycling in diverse circumneutral-pH environments (terrestrial–aquatic, freshwater–estuarine, surface–subsurface) of a subtropical coastal ecosystem. It also represents the first study of its kind in the southern hemisphere. This work highlights the significance of bacterial Fe(III) reduction in terrestrial, and bacterial Fe(II) oxidation in aquatic catchment Fe cycling. Results indicate the risk of promotion of Fe mobilization due to plantation clear-felling and replanting, and GHG emissions associated with seasonal water-logging. Additional significant outcomes were also achieved. The first direct evidence for multiple biomineralization patterns of neutrophilic, microaerophilic, unicellular FeOB was presented. A putatively pure culture, which represents the first cultivable neutrophilic FeOB from the southern hemisphere, was obtained as representative FeOB ubiquitous in diverse catchment aquatic habitats.

Effect of geometry on the melting rates of iron rods burning in high pressure oxygen

The effect of sample geometry on the melting rates of burning iron rods was assessed. Promoted-ignition tests were conducted with rods having cylindrical, rectangular, and triangular cross-sectional shapes over a range of cross-sectional areas. The regression rate of the melting interface (RRMI) was assessed using a statistical approach which enabled the quantification of confidence levels for the observed differences in RRMI. Statistically significant differences in RRMI were observed for rods with the same cross-sectional area but different cross-sectional shape. The magnitude of the proportional difference in RRMI increased with the cross-sectional area. Triangular rods had the highest RRMI, followed by rectangular rods, and then cylindrical rods. The dependence of RRMI on rod shape is shown to relate to the action of molten metal at corners. The corners of the rectangular and triangular rods melted faster than the faces due to their locally higher surface area to volume ratios. This phenomenon altered the attachment geometry between liquid and solid phases, increasing the surface area available for heat transfer, causing faster melting. Findings relating to the application of standard flammability test results in industrial situations are also presented.

Effective adsorption of sodium dodecylsulfate (SDS) by hydrocalumite (CaAl-LDH-Cl) induced by self-dissolution and re-precipitation mechanism

Hydrocalumite (CaAl-LDH-Cl) were synthesized through a rehydration method involving a freshly prepared tricalcium aluminate (C3A) with CaCl2 solution. To understand the intercalation behaviour of sodium dodecylsulfate (SDS) with CaAl-LDH-Cl, X-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-atomic emission spectrometer (ICP) and elemental analysis have been undertaken. The sorption isotherms with SDS reveal that the maximum sorption amount of SDS by CaAl-LDH-Cl could reach 3.67 mmol•g-1. The results revealed that CaAl-LDH-Cl holds a self-dissolution property, about 20-30% of which is dissolved. And the dissolved Ca2+, Al3+ ions are combined with SDS to form CaAl-SDS or Ca-SDS precipitation. It has been highlighted that the composition of resulting products is strongly dependent upon the SDS concentration. With increasing SDS concentrations, the main resulting product changes from CaAl-SDS to Ca-SDS, and the value of interlayer spacing increased to 3.27 nm.

Sensing properties of e-beam evaporated nanostructured pure and iron-doped tungsten oxide thin films

Gas sensing properties of nanostructured pure and iron-doped WO3 thin films are discussed. Electron beam evaporation technique has been used to obtain nanostructured thin films of WO3 and WO3:Fe with small grain size and porosity. Atomic force microscopy has been employed to study the microstructure. High sensitivity of both films towards NO2 is observed. Doping of the tungsten oxide film with Fe decreased the material resistance by a factor of about 30 when exposed to 5 ppm NO2. The high sensitivity is attributed to an improved microstructure of the films obtained through e-beam evaporation technique, and subsequent annealing at 300oC for 1 hour.

Sulfated fibrous ZrO2/Al2O3 core and shell nanocomposites : a novel strong acid catalyst with hierarchically macro-mesoporous nanostructure

A series of solid strong acid catalysts were synthesised from fibrous ZrO2/Al2O3 core and shell nanocomposites. In this series, the zirconium molar percentage was varied from 2 % to 50 %. The ZrO2/Al2O3 nanocomposites and their solid strong acid counterparts were characterised by a variety of techniques including 27Al magic angle spinning nuclear magnetic resonance (MAS-NMR), scanned electronic microscopy (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), Nitrogen adsorption and infrared emission spectroscopy (IES). NMR results show that the interaction between zirconia species and alumina strongly correlates with pentacoordinated aluminium sites. This can also be detected by the change in binding energy of the 3d electrons of the zirconium. The acidity of the obtained solid acids was tested by using them as catalysts for the benzolyation of toluene. It was found that a sample with a 50 % zirconium molar percentage possessed the highest surface acidity equalling that of pristine sulfated zirconia despite the reduced mass of zirconia.

The influence of architecture on degradation and tissue ingrowth into three-dimensional poly(lactic-co-glycolic acid) scaffolds in vitro and in vivo

The in vitro and in vivo degradation properties of poly(lactic-co-glycolic acid) (PLGA) scaffolds produced by two different technologies - thermally induced phase separation (TIPS), and solvent casting and particulate leaching (SCPL) were compared. Over 6 weeks, in vitro degradation produced changes in SCPL scaffold dimension, mass, internal architecture and mechanical properties. TIPS scaffolds produced far less changes in these parameters providing significant advantages over SCPL. In vivo results were based on a microsurgically created arteriovenous (AV) loop sandwiched between two TIPS scaffolds placed in a polycarbonate chamber under rat groin skin. Histologically, a predominant foreign body giant cell response and reduced vascularity was evident in tissue ingrowth between 2 and 8 weeks in TIPS scaffolds. Tissue death occurred at 8 weeks in the smallest pores. Morphometric comparison of TIPS and SCPL scaffolds indicated slightly better tissue ingrowth but greater loss of scaffold structure in SCPL scaffolds. Although advantageous in vitro, large surface area:volume ratios and varying pore sizes in PLGA TIPS scaffolds mean that effective in vivo (AV loop) utilization will only be achieved if the foreign body response can be significantly reduced so as to allow successful vascularisation, and hence sustained tissue growth, in pores less than 300 μm. © 2005 Elsevier Ltd. All rights reserved.

Optimum utilisation of rolling stocks for iron ore mining industries

In this paper, a generic and flexible optimisation methodology is developed to represent, model, solve and analyse the iron ore supply chain system by integrating of iron ore shipment, stockpiles and railing within a whole system. As a result, an integrated train-stockpile-ship timetable is created and optimised for improving efficiency of overall supply chain system. The proposed methodology provides better decision making on how to significantly improve rolling stock utilisation with the best cost-effectiveness ratio. Based on extensive computational experiments and analysis, insightful and quantitative advices are suggested for iron ore mine industry practitioners. The proposed methodology contributes to the sustainability of the environment by reducing pollution due to better utilisation of transportation resources and fuel.

4-(4-Aminophenylsulfonyl)aniline-3,5-dinitrobenzoic acid (1/1)

In the title co-crystalline adduct of the drug Dapsone with 3,5-dinitrobenzoic acid, C~12~H~12~N~2~O~2~S . C~7~H~4~N~4~O~6~, the dihedral angle between the two aromatic rings of the Dapsone molecule is 75.4(2)deg. and those between these rings and that of the 3,5-dinitrobenzoic acid are 64.5(2) and 68.4(2)deg. A strong inter-species carboxylic acid O-H---N(amine) hydrogen-bond is found, which together with intermolecular amine N-H...O hydrogen-bonding associations with carboxyl, nitro and sulfone O-atom acceptors as well as weak pi-pi interactions between one of the Dapsone phenyl rings and the 3,5-dinitrobenzoic acid ring [minimum ring centroid separation 3.774(2)Ang.], give a two-dimensional network structure.

Mapping of shallow coastal groundwaters, their hydrology and environmental geochemistry : Pumicestone catchment, Southeast Queensland

Blooms of the toxic cyanobacterium majuscula Lyngbya in the coastal waters of southeast Queensland have caused adverse impacts on both environmental health and human health, and on local economies such as fishing and tourism. A number of studies have confirmed that the main limiting nutrients (“nutrients of concern”) that contribute to these blooms area Fe, DOC, N, P and also pH. This study is conducted to establish the distribution of these parameters in a typical southeast Queensland coastal setting. The study maps the geochemistry of shallow groundwater in the mainland Pumicestone catchment with an emphasis on the nutrients of concern to understand how these nutrients relate to aquifer materials, landuse and anthropogenic activities. The results of the study form a GIS information layer which will be incorporated into a larger GIS model being produced by Queensland Department of Environment and Resource Management (DERM) to support landuse management to avoid/minimize blooms of Lyngbya in Moreton Bay, southeast Queensland, and other similar settings. A total of 38 boreholes were established in the mainland Pumicestone region and four sampling rounds of groundwater carried out in both dry and wet conditions. These groundwater samples were measured in the field for physico-chemical parameters, and in the laboratory analyses for the nutrients of concern, and other major and minor ions. Aquifer materials were confirmed using the Geological Survey of Queensland digital geology map, and geomaterials were assigned to seven categories which are A (sands), B (silts, sandy silts), C (estuarine mud, silts), D (humid soils), E (alluvium), F (sandstone) and G (other bedrock). The results of the water chemistry were examined by use of the software package AquaChem/AqQA, and divided into six groundwater groups, based on groundwater chemical types and location of boreholes. The type of aquifer material and location, and proximity to waterways was found to be important because they affected physico-chemical properties and concentrations of nutrients of concern and dissolved ions. The analytical results showed that iron concentrations of shallow groundwaters were high due to acid sulfate soils, and also mud and silt, but were lower in sand materials. DOC concentrations of these shallow groundwaters in the sand material were high probably due to rapid infiltration. In addition, DOC concentrations in some boreholes were high because they were installed in organic rich wetlands. The pH values of boreholes were from acidic to near neutral; some boreholes with pH values were low (< 4), showing acid sulfate soils in these boreholes. Concentrations of total nitrogen and total phosphorus of groundwaters were generally low, and the main causes of elevated concentrations of total nitrogen and total phosphorus are largely due to animal and human wastes and tend to be found in localized source areas. Comparison of the relative percentage of nitrogen species (NH3/NH4< Org-N, NO3-N and NO2-N) demonstrated that they could be related to sources such as animal waste, residential and agricultural fertilizers, forest and vegetation, mixed residents and farms, and variable setting and vegetation covers. Total concentrations of dissolved ions in sampling round 3 (dry period) were higher than those in sampling round 2 (wet period) due to both evaporation of groundwater in the dry period and the dilution of rainfall in the wet period. This showed that the highest concentrations of nutrients of concern were due to acid sulfate soils, aquifer materials, landuse and anthropogenic activities and were typically in aquifer materials of E (alluvium) and C (estuarine muds) and locations of Burpengary, Caboolture, and Glass Mountain catchments.

4-Amino-N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide-4-nitrobenzoic acid

In the asymmetric unit of the title co-crystal, C12H14N4O2S . C7H5NO4 there are two independent but conformationally similar heterodimers, which are formed through intermolecular N-H...O(carboxy) and carboxyl O-H...N hydrogen-bond pairs, giving a cyclic motif [graph set R2/2(8)]. The dihedral angles between the rings in the sulfonamide molecules are 78.77(8) and 82.33(9)deg. while the dihedral angles between the ring and the CO2H group in the acids are 2.19(9) and 7.02(10)deg. A two-dimensional structure parallel to the ab plane is generated from the heterodimer units through hydrogen-bonding associations between NH2 and sulfone groups. Between neighbouring two-dimensional arrays there are two types of aromatic pi-pi stacking interactions involving either one of the pyrimidine rings and a 4-nitrobenzoic acid molecule [minimum ring centroid separation = 3.5886(9)A] or two acid molecules [minimum ring centroid separation = 3.7236(10)A].

Phenolics in sugar cane juice : potential degradation by hydrogen peroxide and Fenton's reagent

The presence of colour in raw sugar plays a key role in the marketing strategy of the Australian raw sugar industry. Some sugars are relatively difficult to decolourise during refining and develop colour during storage. A new approach that might result in efficient and cost-effective colour removal during the sugar manufacturing process is the use of an advanced oxidation process (AOP), known as Fenton oxidation, that is, catalytic production of hydroxyl radicals from the decomposition of hydrogen peroxide using ferrous iron. As a first step towards developing this technology, this study determined the composition of colour precursors present in the juice of cane harvested by three different methods. The methods were harvesting cane after burning, harvesting the whole crop with half of the trash extracted and harvesting the whole crop with no trash extracted. The study also investigated the degradation at pH 3, 4 and 5 of a phenolic compound, caffeic acid (3,4–dihydroxycinnamic acid), which is present in sugar cane juice, using both hydrogen peroxide and Fenton’s reagent. The results show that juice expressed from whole crop cane has significantly higher colour than juices expressed from burnt cane. However, the concentrations of phenolic acids were lower in the juices expressed from whole crop cane. The main phenolic acids present in these juices were p-coumaric, vanillic, 2,3–dihydroxybenzoic, gallic and 3,4–dihydroxybenzoic acids. The degradation of caffeic acid significantly improved using Fenton’s reagent in comparison to hydrogen peroxide alone. The Fenton oxidation was optimum at pH 5 when up to ~86 % of caffeic acid degraded within 5 min.