Fluorescent probe:complexation of Fe3+ with the myo-inositol 1,2,3-trisphosphate motif

Natural myo-inositol phosphate antioxidants containing the 1,2,3-trisphosphate motif bind Fe3+ in the unstable penta-axial conformation.

Utiliza����o de quitosana obtida de res��duos de camar��o para avaliar a capacidade de adsor����o de ��ons Fe3+

A quitosana �� produzida atrav��s de uma desacetila����o alcalina da quitina, a qual �� encontrada em exoesqueleto de crust��ceos, parede celular de fungos e materiais biol��gicos. Calcula-se que os res��duos de camar��o apresentam de 5 a 7% do seu peso total na forma de quitina, sugerindo que estes sejam utilizados para obten����o do biopol��mero. Os processos para obten����o destes biopol��meros consiste nas seguintes etapas: desmineraliza����o, desproteiniza����o e desodoriza����o, obtendo-se assim, a quitina ��mida. Ap��s seca, passa por uma desacetila����o qu��mica para a convers��o em quitosana ��mida, sendo purificada e posteriormente seca. A quitosana, por apresentar grupamentos amino livres em sua estrutura, �� uma mol��cula capaz de formar complexos est��veis com c��tions met��licos. O objetivo geral deste trabalho foi obter quitina a partir de res��duos de camar��o (Penaeus brasiliensis) com posterior produ����o de quitosana, e avaliar sua capacidade de complexa����o com ��ons Fe3+, em solu����o. A quitosana produzida foi caracterizada atrav��s do grau de desacetilia����o e da massa molecular viscosim��trica, Para caracteriza����o estrutural das amostras de quitosana, utilizaram-se espectrometria de infravermelho e espectrofotometria UV-Vis��vel, bem como para o complexo formado de quitosana e ferro. Para analisar a efici��ncia da remo����o deste ��on, foram feitas an��lises em espectrometria de absor����o at��mica em chama e em espectrofotometria UV-Vis��vel. Uma an��lise estat��stica foi realizada para avaliar a percentagem de remo����o do ��on ferro das solu����es, sendo utilizado um planejamento fatorial em dois n��veis, tendo como vari��veis independentes o pH do meio, a quantidade de quitosana adicionada, a granulometria da mesma e o tempo de rea����o. A quitosana apresentou grau de desacetila����o de 87��2% e massa molecular viscosim��trica de 196��4kDa, sendo esses valores, compar��veis �� quitosana dispon��vel comercialmente. Na melhor regi��o de trabalho definida pela an��lise estat��stica, obteve-se uma remo����o m��xima de 85 % do ��on ferro das solu����es.

Hydrothermal synthesis of dioctahedral smectites: The Al-Fe3+chemical series. Part II: crystal-chemistry

The crystal-chemistry of a series of synthetic Al-Fe3+ smectites was studied in detail using near and mid infrared spectroscopy. Chemical and NIR data indicated a quite complete range of octahedral Al for Fe3+ substitution, and therefore, the solid-solution between beidellite and nontronite end-members was continuous and complete. The wavenumbers of several infrared absorption bands were correlated with the chemistry of the synthetic smectites, providing a useful tool to constrain their structural formulae and also for assisting in assignments of similar bands in natural smectites. The Al and Fe3+ cations were shown to be randomly distributed in the octahedral sheet of synthesized smectites. Despite the high availability of iron during synthesis, generally only a small amount of tetrahedral Fe3+ was observed.

Raman spectroscopic study of vivianites of different origins

Raman spectroscopy has been used to study a selection of vivianites from different origins. A band is identified at around 3480 cm-1 whose intensity is sample dependent. The band is attributed to the stretching vibration of Fe3+ OH units which are formed through the autooxidation of the vivianite minerals either by self-oxidation or by photocatalytic oxidation according to the reaction: (Fe2+)3(PO4)2��8H2O + 1/2O2 (Fe2+)3��� x(Fe3+)x(PO4)2(OH)x��(8���x)H2O in which some of the water of crystallization is converted to hydroxyl anions. Complexity of the OH stretching region through the overlap of broad bands is reflected in the water HOH deformation modes at 1660 cm���1. Using the infrared bands at 3281, 3105 and 3025 cm���1, hydrogen bond distances of 2.734(5), 2.675(2) and 2.655(2) �� are calculated. Vivianites are characterised by an intense band at 950 cm���1 assigned to the PO4 symmetric stretching vibration. Low Raman intensity bands are observed at ~1077, ~1050, 1015 and ~ 985 cm���1 assigned to the phosphate PO4 antisymmetric stretching vibrations. Multiple antisymmetric stretching vibrations are due to the reduced tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Two bands are observed at ~ 423 and ~ 456 cm���1 assigned to the2bending modes. For the vivianites four bands are observed at ~ 584, ~ 571, ~ 545 and ~ 525 cm���1 assigned to the 4modes of vivianite.

Characterisation of Ni carbonate-bearing minerals by UV-Vis-NIR spectroscopy

Four nickel carbonate-bearing minerals from Australia have been investigated to study the effect of Ni for Mg substitution. The spectra of nullaginite, zaratite, widgiemoolthalite and takovite show three main features in the range of 26,720���25,855 cm���1 (��1-band), 15,230���14,740 cm���1 (��2-band) and 9,200���9,145 cm���1 (��3-band) which are characteristic of divalent nickel in six-fold coordination. The Crystal Field Stabilization Energy (CFSE) of Ni2+ in the four carbonates is calculated from the observed 3A2g(3F) ��� 3T2g(3F) transition. CFSE is dependent on mineralogy, crystallinity and chemical composition (Al/Mg-content). The splitting of the ��1- and ��3-bands and non-Gaussian shape of ��3-band in the minerals are the effects of Ni-site distortion from regular octahedral. The effect of structural cation substitutions (Mg2+, Ni2+, Fe2+ and trivalent cations, Al3+, Fe3+) in the carbonate minerals is noticed on band shifts. Thus, electronic bands in the UV���Vis���NIR spectra and the overtones and combination bands of OH and carbonate ion in NIR show shifts to higher wavenumbers, particularly for widgiemoolthalite and takovite.

Synthesis and vibrational spectroscopy of halotrichite and bilinite

Near infrared (NIR), infrared (IR) spectroscopy and X-ray diffraction (XRD) have been applied to halotrichites of the formula FeAl2(SO4)4���22H2O and Fe2+Fe23+(SO4)4���22H2O. Comparison of the halotrichites and their starting materials has been used to give a better understanding of the bonding involved in these types of minerals. The vibrational spectroscopy data has shown that Fe2+ oxidises during the formation of halotrichite, no preventative measures were implemented to prevent oxidation, and this has been clearly shown by the position and broadness of electronic bands of transition metals in the NIR spectra (12500 to 7500 cm-1). It is apparent from this region that Fe3+ substitutes for Al3+ in the synthesis of halotrichite. Due to the oxidation of Fe2+ to Fe3+ the halotrichite sample contains a small portion of bilinite. This has been confirmed by XRD, peaks at 9 and 14�� 2�� were observed in the halotrichite sample and are identical to the XRD pattern obtained for bilinite. Substitution of aluminium for Fe3+ has resulted in significant changes in the overall infrared and NIR spectral profiles. However, the lower wavenumber regions of the NIR spectra have very similar spectral profiles, which indicate a similar structure to halotrichite has formed for bilinite. This work has shown that iron halotrichites can be synthesised and characterised by infrared and NIR spectroscopy.

Vibrational spectroscopic study of the mineral tsumebite Pb2Cu(PO4,SO4) (OH)

The mineral tsumebite Pb2Cu(PO4)(SO4)(OH), a copper phosphate-sulfate hydroxide of the brackebuschite group has been characterised by Raman and infrared spectroscopy. The brackebuschite mineral group are a series of monoclinic arsenates, phosphates and vanadates of the general formula A2B(XO4)(OH,H2O), where A may be Ba, Ca, Pb, Sr, while B may be Al, Cu2+,Fe2+, Fe3+, Mn2+, Mn3+, Zn and XO4 may be AsO4, PO4, SO4,VO4. Bands are assigned to the stretching and bending modes of PO43- and HOPO3 units. Hydrogen bond distances are calculated based upon the position of the OH stretching vibrations and range from 2.759 �� to 3.205 ��. This range of hydrogen bonding contributes to the stability of the mineral.

A Raman spectroscopic study of bukovsk��ite Fe2(AsO4)(SO4)(OH)���7H2O-a mineral phase with a significant role in arsenic migration

The Raman spectrum of bukovsk��ite, Fe3+2(OH)(SO4)(AsO4)���7H2O has been studied and compared with the Raman spectrum of an amorphous gel containing specifically Fe, As and S elements and is understood as an intermediate product in the formation of bukovsk��ite. Observed bands are assigned to the stretching and bending vibrations of (SO4)2- and (AsO4)3- units, stretching and bending vibrations and librational modes of hydrogen bonded water molecules, stretching and bending vibrations of hydrogen bonded (OH)- ions and Fe3+-(O,OH) units. Approximate range of O-H...O hydrogen bond lengths is inferred from the Raman spectra. Raman spectra of crystalline bukovsk��ite and of the amorphous gel differ in that the bukovsk��ite spectrum is more complex, observed bands are sharp, the degenerate bands of (SO4)2- and (AsO4)3- are split and more intense. Lower wavenumbers of ��� H2O bending vibration in the spectrum of the amorphous gel may indicate the presence of weaker hydrogen bonds compared with those in bukovsk��ite.

Vibrational spectroscopy of the multi anion mineral zykaite Fe4(AsO4)(SO4)(OH)���15H2O ��� implications for arsenate removal

Some minerals are colloidal and are poorly diffracting . Vibrational spectroscopy offers one of the few methods for the assessment of the structure of these types of minerals. Among this group of minerals is zykaite with formula Fe4(AsO4)(SO4)(OH)���15H2O. The objective of this research is to determine the molecular structure of the mineral zykaite using vibrational spectroscopy. Raman and infrared bands are attributed to the AsO43-, SO42- and water stretching vibrations. The sharp band at 3515 cm-1 is assigned to the stretching vibration of the OH units. This mineral offers a mechanism for the formation of more crystalline minerals such as scorodite and bukovskyite. Arsenate ions can be removed from aqueous systems through the addition of ferric compounds such as ferric chloride. This results in the formation of minerals such as zykaite and pitticite (Fe3+,AsO4,SO4,H2O).

Raman spectroscopy of the multi anion mineral arsentsumebite Pb2Cu(AsO4)(SO4)(OH) and in comparison with tsumebite Pb2Cu(PO4)(SO4)(OH)

The mineral arsentsumebite Pb2Cu(AsO4)(SO4)(OH), a copper arsenate-sulfate hydroxide of the brackebuschite group has been characterised by Raman spectroscopy. The brackebuschite mineral group are a series of monoclinic arsenates, phosphates and vanadates of the general formula A2B(XO4)(OH,H2O), where A may be Ba, Ca, Pb, Sr, while B may be Al, Cu2+,Fe2+, Fe3+, Mn2+, Mn3+, Zn and XO4 may be AsO4, PO4, SO4,VO4. Bands are assigned to the stretching and bending modes of SO42- AsO43- and HOAsO3 units. Raman spectroscopy readily distinguishes between the two minerals arsentsumebite and tsumebite. Raman bands attributed to arsenate are not observed in the Raman spectrum of tsumebite. Phosphate bands found in the Raman spectrum of tsumebite are not found in the Raman spectrum of arsentsumebite. Raman spectroscopy readily distinguishes the two minerals tsumebite and arsentsumebite.

Determination of coastal ground and surface water processes and character by use of hydrochemistry and stable isotopes, Fraser Coast, Queensland

This study was part of an integrated project developed in response to concerns regarding current and future land practices affecting water quality within coastal catchments and adjacent marine environments. Two forested coastal catchments on the Fraser Coast, Australia, were chosen as examples of low-modification areas with similar geomorphological and land-use characteristics to many other coastal zones in southeast Queensland. For this component of the overall project, organic , physico-chemical (Eh, pH and DO), ionic (Fe2+, Fe3+), and isotopic (��13CDIC, ��15NDIN ��34SSO4) data were used to characterise waters and identify sources and processes contributing to concentrations and form of dissolved Fe, C, N and S within the ground and surface waters of these coastal catchments. Three sites with elevated Fe concentrations are discussed in detail. These included a shallow pool with intermittent interaction with the surface water drainage system, a monitoring well within a semi-confined alluvial aquifer, and a monitoring well within the fresh/saline water mixing zone adjacent to an estuary. Conceptual models of processes occurring in these environments are presented. The primary factors influencing Fe transport were; microbial reduction of Fe3+ oxyhydroxides in groundwaters and in the hyporheic zone of surface drainage systems, organic input available for microbial reduction and Fe3+ complexation, bacterial activity for reduction and oxidation, iron curtain effects where saline/fresh water mixing occurs, and variation in redox conditions with depth in ground and surface water columns. Data indicated that groundwater seepage appears a more likely source of Fe to coastal waters (during periods of low rainfall) via tidal flux. The drainage system is ephemeral and contributes little discharge to marine waters. However, data collected during a high rainfall event indicated considerable Fe loads can be transported to the estuary mouth from the catchment.

Vibrational spectroscopy of the multianion mineral gartrellite from the Anticline Deposit, Ashburton Downs, Western Australia

The multianion mineral gartrellite PbCu(Fe3+,Cu)(AsO4)2(OH,H2O)2 has been studied by a combination of Raman and infrared spectroscopy. The molecular structure of gartrellite is assessed. Gartrellite is one of the tsumcorite mineral group based upon arsenate and/or sulphate anions. Crystal symmetry is either triclinic in the case of an ordered occupation of two cationic sites, triclinic due to ordering of the H bonds in the case of species with two water molecules per formula unit, or monoclinic in the other cases. Characteristic Raman spectra of the mineral gartrellite enable the assignment of the bands to specific vibrational modes. These spectra are related to the structure of gartrellite. The position of the hydroxyl and water stretching vibrations are related to the strength of the hydrogen bond formed between the OH unit and the AsO3/4 anion.

Synthesis and spectroscopic characterization of copper zinc aluminum nanoferrite particles

Copper doped zinc aluminium ferrites are synthesized by the solid-state reaction route is cubic crystalline with unit cell parameter varying from 8.39 to 8.89 ��. TEM pictures clearly indicating that fundamental unit is composed of octahedral and tetrahedral blocks and joined strongly shown in (a). EPR spectra is compositional dependent at lower Al/Cu concentration EPR spectra is due to Fe3+ and at a higher content of Al/Cu the EPR spectra is due to Cu2+. Absence of EPR spectra at room temperature indicates that the sample is perfectly ferromagnetic. EPR results at low temperature indicate that the sample is paramagnetic, and that copper is placed in the tetragonal elongation (B) site with magnetically non-equivalent ions in the unit cell having strong exchange coupling between them. This is shown in (b). (a) TEM image of ferrite with x = 0.15. (b) EPR spectrum of ferrite with x = 0.75.

Characterisation of red mud and seawater neutralised red mud using vibrational spectroscopic techniques

Bauxite refinery residues are derived from the Bayer process by the digestion of crushed bauxite in concentrated caustic at elevated temperatures. Chemically, it comprises, in varying amounts (depending upon the composition of the starting bauxite), oxides of iron and titanium, residual alumina, sodalite, silica, and minor quantities of other metal oxides. Bauxite residues are being neutralised by seawater in recent years to reduce the alkalinity in bauxite residue, through the precipitation of hydrotalcite-like compounds and some other Mg, Ca, and Al hydroxide and carbonate minerals. A combination of X-ray diffraction (XRD) and vibrational spectroscopy techniques, including mid-infrared (IR), Raman, near-infrared (NIR), and UV-Visible, have been used to characterise bauxite residue and seawater neutralised bauxite residue. Both the ferrous (Fe2+) and ferric (Fe3+) ions within bauxite residue can be identified by their characteristic NIR bands, where ferrous ions produce a strong absorption band at around 9000 cm-1, while ferric ions produce two strong bands at 25000 and 14300 cm-1. The presence of adsorbed carbonate and hydroxide anions can be identified at around 5200 and 7000 cm-1, respectively, attributed to the 2nd overtone of the 1st fundamental overtones observed in the mid-IR spectra. The complex bands in the Raman and mid-IR spectra around 3500 cm-1 are assigned to the OH stretching vibrations of the various oxides present in bauxite residue, and water. The combination of carbonate and hydroxyl units and their fundamental overtones give rise to many of the features of the NIR spectra.

A reduction of diffusion in PVA Fricke hydrogels

A modification to the PVA-FX hydrogel whereby the chelating agent, xylenol orange, was partially bonded to the gelling agent, poly-vinyl alcohol, resulted in an 8% reduction in the post irradiation Fe3+ diffusion, adding approximately 1 hour to the useful timespan between irradiation and readout. This xylenol orange functionalised poly-vinyl alcohol hydrogel had an OD dose sensitivity of 0.014 Gy���1 and a diffusion rate of 0.133 mm2 h���1. As this partial bond yields only incremental improvement, it is proposed that more efficient methods of bonding xylenol orange to poly-vinyl alcohol be investigated to further reduce the diffusion in Fricke gels.