The molecular structure of the vanadate mineral mottramite [PbCu(VO4)(OH)] from Tsumeb, Namibia – a vibrational spectroscopic study

We have studied a mineral sample of mottramite PbCu(VO4)(OH) from Tsumeb, Namibia using a combination of scanning electron microscopy with EDX, Raman and infrared spectroscopy. Chemical analysis shows principally the elements V, Pb and Cu. Ca occurs as partial substitution of Pb as well as P and As in substitution to V. Minor amounts of Si and Cr were also observed. The Raman band of mottramite at 829 cm-1, is assigned to the ν1 symmetric (VO-4) ) stretching mode. The complexity of the spectra is attributed to the chemical composition of the Tsumeb mottramite. The ν3 antisymmetric vibrational mode of mottramite is observed as very low intensity bands at 716 and 747 cm-1. The series of Raman bands at 411, 439, 451 cm-1 and probably also the band at 500 cm-1 are assigned to the (VO-4) ν2 bending mode. The series of Raman bands at 293, 333 and 366 cm-1 are attributed to the (VO-4) ) ν4 bending modes. The ν3, ν3 and ν4 regions are complex for both minerals and this is attributed to symmetry reduction of the vanadate unit from Td to Cs.

A concise approach to the polycyclic scaffold of frondosin D

Frondosins A−E, 1−5 (Figure 1), are a family of related marine sesquiterpenoids first isolated in their dextro-rotatory form from the sponge Dysidea frondosa.(1a) Additionally, levo-rotatory frondosins A and D were isolated from an unidentified Eurospongia species.(1b) Frondosins A−E are compounds of interest due to their promising interleukin-8 (IL-8) affinity and protein kinase C inhibition.(1a) IL-8 antagonists are of particular interest in view of their antiinflammatory,(2a) anti-HIV,(1b, 2b) and antitumor(2c-2f) properties. To date, frondosins A, B, and C have been synthesized.(3) Notwithstanding these successes, the frondosins have proved quite a formidable synthetic challenge, and as of yet, there has been no synthesis of frondosin D or E. In this report, we describe our approaches to the molecular scaffold of frondosins D. This work has culminated in a very effective means of producing the trimethylbicyclo[5.4.0]undecane ring system common to all frondosins (shown in bold, Figure 1).

Organo-LDH synthesized via tricalcium aluminate hydration in the present of Na-dodecylbenzenesulfate aqueous solution and subsequent investigated by near-infrared and mid-infrared

Na-dodecylbenzenesulfate (SDBS), a natural anionic surfactant, has been successfully intercalated into a Ca based LDH host structure during tricalcium aluminate hydration in the presence of SDBS aqueous solution (CaAl-SDBS-LDH). The resulting product was characterized by powder X-ray diffraction (XRD), mid-infrared (MIR) spectroscopy combined with near-infrared (NIR) spectroscopy technique, thermal analysis (TG–DTA) and scan electron microscopy (SEM). The XRD results revealed that the interlayer distance of resultant product was expanded to 30.46 Å. MIR combined with NIR spectra offered an effective method to illustrate this intercalation. The NIR spectra (6000–5500 cm−1) displayed prominent bands to expound SDBS intercalated into hydration product of C3A. And the bands around 8300 cm−1 were assigned to the second overtone of the first fundamental of CH stretching vibrations of SDBS. In addition, thermal analysis showed that the dehydration and dehydroxylation took place at ca. 220 °C and 348 °C, respectively. The SEM results appeared approximately hexagonal platy crystallites morphology for CaAl-SDBS-LDH, with particle size smaller and thinner.

Entropic bounds for multi-scale and multi-physics coupling in earth sciences

The ability to understand and predict how thermal, hydrological,mechanical and chemical (THMC) processes interact is fundamental to many research initiatives and industrial applications. We present (1) a new Thermal– Hydrological–Mechanical–Chemical (THMC) coupling formulation, based on non-equilibrium thermodynamics; (2) show how THMC feedback is incorporated in the thermodynamic approach; (3) suggest a unifying thermodynamic framework for multi-scaling; and (4) formulate a new rationale for assessing upper and lower bounds of dissipation for THMC processes. The technique is based on deducing time and length scales suitable for separating processes using a macroscopic finite time thermodynamic approach. We show that if the time and length scales are suitably chosen, the calculation of entropic bounds can be used to describe three different types of material and process uncertainties: geometric uncertainties,stemming from the microstructure; process uncertainty, stemming from the correct derivation of the constitutive behavior; and uncertainties in time evolution, stemming from the path dependence of the time integration of the irreversible entropy production. Although the approach is specifically formulated here for THMC coupling we suggest that it has a much broader applicability. In a general sense it consists of finding the entropic bounds of the dissipation defined by the product of thermodynamic force times thermodynamic flux which in material sciences corresponds to generalized stress and generalized strain rates, respectively.

Raman spectroscopy of the arsenate minerals maxwellite and in comparison with tilasite

Maxwellite NaFe3+(AsO4)F is an arsenate mineral containing fluoride and forms a continuous series with tilasite CaMg(AsO4)F. Both maxwellite and tilasite form a continuous series with durangite NaAl3+(AsO4)-F. We have used the combination of scanning electron microscopy with EDS and vibrational spectroscopy to chemically analyse the mineral maxwellite and make an assessment of the molecular structure. Chemical analysis shows that maxwellite is composed of Fe, Na and Ca with minor amounts of Mn and Al. Raman bands for tilasite at 851 and 831 cm�1 are assigned to the Raman active m1 symmetric stretching vibration (A1) and the Raman active triply degenerate m3 antisymmetric stretching vibration (F2). The Raman band of maxwellite at 871 cm�1 is assigned to the m1 symmetric stretching vibration and the Raman band at 812 cm�1 is assigned to the m3 antisymmetric stretching vibration. The intense Raman band of tilasite at 467 cm�1 is assigned to the Raman active triply degenerate m4 bending vibration (F2). Raman band at 331 cm�1 for tilasite is assigned to the Raman active doubly degenerate m2 symmetric bending vibration (E). Both Raman and infrared spectroscopy do not identify any bands in the hydroxyl stretching region as is expected.

A new approach to prepare ZVI and its application in removal of Cr(VI) from aqueous solution

Zero valent iron (ZVI) was prepared by reducing natural goethite (NG-ZVI) and synthetic goethite (SG-ZVI) in hydrogen at 550 °C. XRD, TEM, FESEM/EDS and specific surface area (SSA) and pore analyser were used to characterize goethites and reduced goethites. Both NG-ZVI and SG-ZVI with a size of nanoscale to several hundreds of nanometers were obtained by reducing goethites at 550 °C. The reductive capacity of the ZVIs was assessed by removal of Cr(VI) at ambient temperature in comparison with that of commercial iron powder (CIP). The effect of contact time, initial concentration and reaction temperature on Cr(VI) removal was investigated. Furthermore, the uptake mechanism was discussed according to isotherms, thermodynamic analysis and the results of XPS. The results showed that SG-ZVI had the best reductive capacity to Cr(VI) and reduced Cr(VI) to Cr(III). The results suggest that hydrogen reduction is a good approach to prepare ZVI and this type of ZVI is potentially useful in remediating heavy metals as a material of permeable reaction barrier.

A vibrational spectroscopic study of a hydrated hydroxy-phosphate mineral fluellite, Al2(PO4)F2(OH)·7H2O

Raman and infrared spectra of two well-defined fluellite samples, Al2(PO4)F2(OH)�7H2O, from the Krásno near Horní Slavkov (Czech Republic) and Kapunda, South Australia (Australia) were studied and tentatively interpreted. Observed bands were assigned to the stretching and bending vibrations of phosphate tetrahedra, aluminum oxide/hydroxide/fluoride octahedra, water molecules and hydroxyl ions. Approximate O–H���O hydrogen bond lengths were inferred from the Raman and infrared spectra.

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 Å. 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.

A vibrational spectroscopic study of the phosphate mineral lulzacite Sr2Fe2+(Fe2+,Mg)2Al4(PO4)4(OH)10

The mineral lulzacite from Saint-Aubin des Chateaux mine, France, with theoretical formula Sr2Fe2+(Fe2+,Mg)2Al4(PO4)4(OH)10 has been studied using a combination of electron microscopy with EDX and vibrational spectroscopic techniques. Chemical analysis shows a Sr, Fe, Al phosphate with minor amounts of Ga, Ba and Mg. Raman spectroscopy identifies an intense band at 990 cm�1 with an additional band at 1011 cm�1. These bands are attributed to the PO3� 4 m1 symmetric stretching mode. The m3 antisymmetric stretching modes are observed by a large number of Raman bands. The Raman bands at 1034, 1051, 1058, 1069 and 1084 together with the Raman bands at 1098, 1116, 1133, 1155 and 1174 cm�1 are assigned to the m3 antisymmetric stretching vibrations of PO3� 4 and the HOPO2� 3 units. The observation of these multiple Raman bands in the symmetric and antisymmetric stretching region gives credence to the concept that both phosphate and hydrogen phosphate units exist in the structure of lulzacite. The series of Raman bands at 567, 582, 601, 644, 661, 673 and 687 cm�1 are assigned to the PO3� 4 m2 bending modes. The series of Raman bands at 437, 468, 478, 491, 503 cm�1 are attributed to the PO3� 4 and HOPO2� 3 m4 bending modes. No Raman bands of lulzacite which could be attributed to the hydroxyl stretching unit were observed. Infrared bands at 3511 and 3359 cm�1 are ascribed to the OH stretching vibration of the OH units. Very broad bands at 3022 and 3299 cm�1 are attributed to the OH stretching vibrations of water. Vibrational spectroscopy offers insights into the molecular structure of the phosphate mineral lulzacite.

Vibrational spectroscopic study of the sulphate mineral glaucocerinite (Zn,Cu)10Al6(SO4)3(OH)32⋅18H2O – a natural layered double hydroxide

We have studied the molecular structure of the mineral glaucocerinite (Zn,Cu)5Al3(SO4)1.5(OH)16�9(H2O) using a combination of Raman and infrared spectroscopy. The mineral is one of the hydrotalcite supergroup of natural layered double hydroxides. The Raman spectrum is characterised by an intense Raman band at 982 cm�1 with a low intensity band at 1083 cm�1. These bands are attributed to the sulphate symmetric and antisymmetric stretching mode. The infrared spectrum is quite broad with a peak at 1020 cm�1. A series of Raman bands at 546, 584, 602, 625 and 651 cm�1 are assigned to the m4 (SO4)2� bending modes. The observation of multiple bands provides evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 762 cm�1 is attributed to a hydroxyl deformation mode associated with AlOH units. Vibrational spectroscopy enables aspects of the molecular structure of glaucocerinite to be determined.

A vibrational spectroscopic study of the phosphate mineral churchite (REE)(PO4)⋅2H2O

Vibrational spectroscopy has been used to study the rare earth mineral churchite of formula (REE)(PO4)-⋅2H2O. The mineral contains a range of rare earth metals including yttrium depending on the locality. The Raman spectra of churchite-(REE) are characterized by an intense sharp band at 984 cm-1 assigned to the v1 (PO¾-) symmetric stretching mode. A lower intensity band observed at around 1067 cm-1 is attributed to the v3 (PO¾-) antisymmetric stretching mode. The (PO¾-) bending modes are observed at 497 cm-1 (v2) and 565 cm-1(v4). Raman bands at 649 and 681 cm-1 are assigned to water librational modes. Vibrational spectroscopy enables aspects of the structure of churchite to be ascertained.

A vibrational spectroscopic study of the silicate mineral inesite Ca2(Mn,Fe)₇Si10O28(OH)⋅5H2O

We have studied the hydrated hydroxyl silicate mineral inesite of formula Ca2(Mn,Fe)7Si10O28(OH)⋅5H2O using a combination of scanning electron microscopy with EDX and Raman and infrared spectroscopy. SEM analysis shows the mineral to be a pure monomineral with no impurities. Semiquantitative analysis shows a homogeneous phase, composed by Ca, Mn2+, Si and P, with minor amounts of Mg and Fe. Raman spectrum shows well resolved component bands at 997, 1031, 1051, and 1067 cm-1 attributed to a range of SiO symmetric stretching vibrations of [Si10O28] units. Infrared bands found at 896, 928, 959 and 985 cm-1 are attributed to the OSiO antisymmetric stretching vibrations. An intense broad band at 653 cm-1 with shoulder bands at 608, 631 and 684 cm-1 are associated with the bending modes of the OSiO units of the 6- and 8-membered rings of the [Si10O28] units. The sharp band at 3642 cm-1 with shoulder bands at 3612 and 3662 cm-1 are assigned to the OH stretching vibrations of the hydroxyl units. The broad Raman band at 3420 cm-1 with shoulder bands at 3362 and 3496 cm-1 are assigned to the water stretching vibrations. The application of vibrational spectroscopy has enabled an assessment of the molecular structure of inesite to be undertaken.

The molecular structure of the phosphate mineral beraunite Fe2+Fe⅗+(PO4)4(OH)5⋅4H2O– A vibrational spectroscopic study

The mineral beraunite from Boca Rica pegmatite in Minas Gerais with theoretical formula Fe2+Fe5 3+(PO4)4(OH)5⋅4H2O has been studied using a combination of electron microscopy with EDX and vibrational spectroscopic techniques. Raman spectroscopy identifies an intense band at 990 cm-1 and 1011 cm-1. These bands are attributed to the PO4 3- v, symmetric stretching mode. The m3 antisymmetric stretching modes are observed by a large number of Raman bands. The Raman bands at 1034, 1051, 1058, 1069 and 1084 together with the Raman bands at 1098, 1116, 1133, 1155 and 1174 cm-1 are assigned to the m3 antisymmetric stretching vibrations of PO4 3- and the HOPO3 2- units. The observation of these multiple Raman bands in the symmetric and antisymmetric stretching region gives credence to the concept that both phosphate and hydrogen phosphate units exist in the structure of beraunite. The series of Raman bands at 567, 582,601, 644, 661, 673, and 687 cm-1 are assigned to the PO4 3- v2 bending modes. The series of Raman bands at 437, 468, 478, 491, 503 cm-1 are attributed to the PO4 3- and OPO3 2- v4 bending modes. No Raman bands of beraunite which could be attributed to the hydroxyl stretching unit were observed. Infrared bands at 3511 and 3359 cm-1 are ascribed to the OH stretching vibration of the OH units. Very broad bands at 3022 and 3299 cm-1 are attributed to the OH stretching vibrations of water. Vibrational spectroscopy offers insights into the molecular structure of the phosphate mineral beraunite.

Multimedia : a necessary step in the evolution of research funding applications

Multimedia communication capabilities are rapidly expanding, and visual information is easily shared electronically, yet funding bodies still rely on paper grant proposal submissions. Incorporating modern technologies will streamline the granting process by increasing the fidelity of grant communication, improving the efficiency of review, and reducing the cost of the process.