Raman spectroscopic study of the mixed anion sulphate-arsenate mineral parnauite Cu9[(OH)10|SO4|(AsO4)2].7H2O

The mixed anion mineral parnauite Cu9[(OH)10|SO4|(AsO4)2].7H2O has been studied by Raman spectroscopy. Characteristic bands associated with arsenate, sulphate, hydroxyl units are identified. Broad bands are observed and are resolved into component bands. Two intense bands at 859 and 830 cm-1 are assigned to the 1 (AsO4)3- symmetric stretching and 3 (AsO4)3- antisymmetric stretching modes. The comparatively sharp band at 976 cm-1 is assigned to the ν1 (SO4)2- symmetric stretching mode and a broad spectral profile centered upon 1097 cm-1 is attributed to the ν3 (SO4)2- antisymmetric stretching mode. A comparison of the Raman spectra is made with other arsenate bearing minerals such as carminite, clinotyrolite, kankite, tilasite and pharmacosiderite.

Raman spectroscopic study of the uranyl sulphate mineral jáchymovite (UO2)8(SO4)(OH)14•13H2O

Raman spectra of jáchymovite, (UO2)8(SO4)(OH)14•13H2O, were studied, complemented with infrared spectra, and compared with published Raman and infrared spectra of uranopilite, [(UO2)6(SO4)O2(OH)6(H2O)6] •6H2O. Bands related to the stretching and bending vibrations of (UO2)2+, (SO4)2-, (OH)- and water molecules were assigned. U-O bond lengths in uranyl and O-H…O hydrogen bond lengths were calculated from the Raman and infrared spectra.

Volcanic sulphate and Arctic dust plumes over the North Atlantic Ocean

High time resolution aerosol mass spectrometry measurements were conducted during a field campaign at Mace Head Research Station, Ireland, in June 2007. Observations on one particular day of the campaign clearly indicated advection of aerosol from volcanoes and desert plains in Iceland which could be traced with NOAA Hysplit air mass back trajectories and satellite images. In conjunction with this event, elevated levels of sulphate and light absorbing particles were encountered at Mace Head. While sulphate concentration was continuously increasing, nitrate levels remained low indicating no significant contribution from anthropogenic pollutants. Sulphate concentration increased about 3.8 g/m3 in comparison with the background conditions. Corresponding sulphur flux from volcanic emissions was estimated to about 0.3 TgS/yr, suggesting that a large amount of sulphur released from Icelandic volcanoes may be distributed over distances larger than 1000 km. Overall, our results corroborate that transport of volcanogenic sulphate and dust particles can significantly change the chemical composition, size distribution, and optical properties of aerosol over the North Atlantic Ocean and should be considered accordingly by regional climate models.

Structure of selected basic copper (II) sulphate minerals based upon spectroscopy : implications for hydrogen bonding

The application of near-infrared and infrared spectroscopy has been used for identification and distinction of basic Cu-sulphates that include devilline, chalcoalumite and caledonite. Near-infrared spectra of copper sulphate minerals confirm copper in divalent state. Jahn-Teller effect is more significant in chalcoalumite where 2B1g ® 2B2g transition band shows a larger splitting (490 cm-1) confirming more distorted octahedral coordination of Cu2+ ion. One symmetrical band at 5145 cm-1 with shoulder band 5715 cm-1 result from the absorbed molecular water in the copper complexes are the combinations of OH vibrations of H2O. One sharp band at around 3400 cm-1 in IR common to the three complexes is evidenced by Cu-OH vibrations. The strong absorptions observed at 1685 and 1620 cm-1 for water bending modes in two species confirm strong hydrogen bonding in devilline and chalcoalumite. The multiple bands in v3 and v4(SO4)2- stretching regions are attributed to the reduction of symmetry to the sulphate ion from Td to C2V. Chalcoalumite, the excellent IR absorber over the range 3800-500 cm-1 is treated as most efficient heat insulator among the Cu-sulphate complexes.

Efficacy of a progressive walking program and glucosamine sulphate supplementation on osteoarthritic symptoms of the hip and knee: a feasibility trial

Introduction: Management of osteoarthritis (OA) includes the use of non-pharmacological and pharmacological therapies. Although walking is commonly recommended for reducing pain and increasing physical function in people with OA, glucosamine sulphate has also been used to alleviate pain and slow the progression of OA. This study evaluated the effects of a progressive walking program and glucosamine sulphate intake on OA symptoms and physical activity participation in people with mild to moderate hip or knee OA. Methods: Thirty-six low active participants (aged 42 to 73 years) were provided with 1500 mg glucosamine sulphate per day for 6 weeks, after which they began a 12-week progressive walking program, while continuing to take glucosamine. They were randomized to walk 3 or 5 days per week and given a pedometer to monitor step counts. For both groups, step level of walking was gradually increased to 3000 steps/day during the first 6 weeks of walking, and to 6000 steps/day for the next 6 weeks. Primary outcomes included physical activity levels, physical function (self-paced step test), and the WOMAC Osteoarthritis Index for pain, stiffness and physical function. Assessments were conducted at baseline and at 6-, 12-, 18-, and 24-week follow-ups. The Mann Whitney Test was used to examine differences in outcome measures between groups at each assessment, and the Wilcoxon Signed Ranks Test was used to examine differences in outcome measures between assessments. Results: During the first 6 weeks of the study (glucosamine supplementation only), physical activity levels, physical function, and total WOMAC scores improved (P<0.05). Between the start of the walking program (Week 6) and the final follow-up (Week 24), further improvements were seen in these outcomes (P<0.05) although most improvements were seen between Weeks 6 and 12. No significant differences were found between walking groups. Conclusions: In people with hip or knee OA, walking a minimum of 3000 steps (~30 minutes), at least 3 days/week, in combination with glucosamine sulphate, may reduce OA symptoms. A more robust study with a larger sample is needed to support these preliminary findings. Trial Registration: Australian Clinical Trials Registry ACTRN012607000159459.

Effects of magnesium stearate on the efficient dispersion of salbutamol sulphate from carrier-based dry powder inhaler formulations

Dry powder inhaler (DPI) formulations is one of the most useful aerosol preparations in which drugs may be formulated as carrier-based interactive mixtures with micronised drug particles (<5 μm) adhered onto the surface of large inert carriers (lactose powders). The addition of magnesium stearate (MgSt) (1-3), was found to increase dispersion of various drugs from DPI formulations. Recently, some active compounds coated with 5% (wt/wt) MgSt using the mechanofusion method showed significant improvements in aerosolization behavior due to the reduction in intrinsic cohesion force (4). Application of MgSt in powder formulations is not new; however, no studies demonstrated the minimum threshold level for this excipient in efficient aerosolization of drug powders from the interactive mixtures. Therefore, this study investigated the role of MgSt concentration on the efficient dispersion of salbutamol sulphate (SS) from DPI formulations.

Infrared and Raman spectroscopic characterisation of the sulphate mineral creedite – Ca3Al2SO4(F,OH)·2H2O – and in comparison with the alums

The mineral creedite is a fluorinated hydroxy hydrated sulphate of aluminium and calcium of formula Ca3Al2SO4(F,OH)·2H2O. The mineral has been studied by a combination of electron probe analysis to determine the molecular formula of the mineral and the structure assessed by vibrational spectroscopy. The spectroscopy of creedite may be compared with that of the alums. The Raman spectrum of creedite is characterised by an intense sharp band at 986 cm−1 assigned to the View the MathML source ν1 (Ag) symmetric stretching mode. Multiple bands of creedite in the antisymmetric stretching region support the concept of a reduction in symmetry of the sulphate anion. Multiple bands are also observed in the bending region with the three bands at 601, 629 and 663 cm−1 assigned to the View the MathML source ν4 (Ag) bending modes. The observation of multiple bands at 440, 457 and 483 cm−1 attributed to the View the MathML source ν2 (Bg) bending modes supports the concept that the symmetry of the sulphate is reduced by coordination to the water bonded to the Al3+ in the creedite structure. The splitting of the ν2, ν3 and ν4 modes is attributed to the reduction of symmetry of the SO4 and it is proposed that the sulphate coordinates to water in the hydrated aluminium in bidentate chelation.

Characterization of the sulphate mineral amarantite Fe3 2 3+ (SO4)O 7H2O using infrared, Raman spectroscopy and thermogravimetry

The mineral amarantite Fe23+(SO4)O∙7H2O has been studied using a combination of techniques including thermogravimetry, electron probe analyses and vibrational spectroscopy. Thermal analysis shows decomposition steps at 77.63, 192.2, 550 and 641.4°C. The Raman spectrum of amarantite is dominated by an intense band at 1017 cm-1 assigned to the SO42- ν1 symmetric stretching mode. Raman bands at 1039, 1054, 1098, 1131, 1195 and 1233 cm-1 are attributed to the SO42- ν3 antisymmetric stretching modes. Very intense Raman band is observed at 409 cm-1 with shoulder bands at 399, 451 and 491 cm-1 are assigned to the v2 bending modes. A series of low intensity Raman bands are found at 543, 602, 622 and 650 cm-1 are assigned to the v4 bending modes. A very sharp Raman band at 3529 cm-1 is assigned to the stretching vibration of OH units. A series of Raman bands observed at 3025, 3089, 3227, 3340, 3401 and 3480 cm-1 are assigned to water bands. Vibrational spectroscopy enables aspects of the molecular structure of the mineral amarantite to be ascertained.

Vibrational spectroscopic characterization of the sulphate mineral khademite Al(SO4)F⋅5(H2O)

Vibrational spectroscopy has been used to characterize the sulphate mineral khademite Al(SO4)F∙5(H2O). Raman band at 991 cm-1 with a shoulder at 975 cm-1 is assigned to the ν1 (SO4)2- symmetric stretching mode. The observation of two symmetric stretching modes suggests that the sulphate units are not equivalent. Two low intensity Raman bands at 1104 and 1132 cm-1 are assigned to the ν3 (SO4)2- antisymmetric stretching mode. The broad Raman band at 618 cm-1 is assigned to the v4 (SO4)2- bending modes. Raman bands at 455, 505 and 534 cm-1 are attributable to the doubly degenerate v2 (SO4)2- bending modes. Raman bands at 2991, 3146 and 3380 cm-1 are assigned to the OH stretching bands of water. Five infrared bands are noted at 2458, 2896, 3203, 3348 and 3489 cm-1 are also due to water stretching bands. The observation of multiple water stretching vibrations gives credence to the non-equivalence of water units in the khademite structure. Vibrational spectroscopy enables an assessment of the structure of khademite.

The spectroscopic characterization of the sulphate mineral ettringite from Kuruman manganese deposits, South Africa

The mineral ettringite has been studied using a number of techniques, including XRD, SEM with EDX, thermogravimetry and vibrational spectroscopy. The mineral proved to be composed of 53% of ettringite and 47% of thaumasite in a solid solution. Thermogravimetry shows a mass loss of 46.2% up to 1000 °C. Raman spectroscopy identifies multiple sulphate symmetric stretching modes in line with the three sulphate crystallographically different sites. Raman spectroscopy also identifies a band at 1072 cm−1 attributed to a carbonate symmetric stretching mode, confirming the presence of thaumasite. The observation of multiple bands in the ν4 spectral region between 700 and 550 cm−1 offers evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 3629 cm−1 is assigned to the OH unit stretching vibration and the broad feature at around 3487 cm−1 to water stretching bands. Vibrational spectroscopy enables an assessment of the molecular structure of natural ettringite to be made.

A vibrational spectroscopic study of the sulphate mineral glauberite

The mineral glauberite is one of many minerals formed in evaporite deposits. The mineral glauberite has been studied using a combination of scanning electron microscopy with energy dispersive X-ray analysis and infrared and Raman spectroscopy. Qualitative chemical analysis shows a homogeneous phase, composed by sulphur, calcium and sodium. Glauberite is characterized by a very intense Raman band at 1002 cm-1 with Raman bands observed at 1107, 1141, 1156 and 1169 cm-1 attributed to the sulphate ν3 antisymmetric stretching vibration. Raman bands at 619, 636, 645 and 651 cm-1 are assigned to the ν4 sulphate bending modes. Raman bands at 454, 472 and 486 cm-1 are ascribed to the ν2 sulphate bending modes. The observation of multiple bands is attributed to the loss of symmetry of the sulphate anion. Raman spectroscopy is superior to infrared spectroscopy for the determination of glauberite.

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.

Vibrational spectroscopic characterization of the sulphate mineral leightonite K2Ca2Cu(SO4)4⋅2H2O – Implications for the molecular structure

The mineral leightonite, a rare sulphate mineral of formula K2Ca2Cu(SO4)4.2H2O, has been studied using a combination of electron probe and vibrational spectroscopy. The mineral is characterized by an intense Raman band at 991 cm-1 attributed to the SO2- 4 m1 symmetric stretching mode. A series of Raman bands at 1047, 1120, 1137, 1163 and 1177 cm-1 assigned to the SO2- 4 m3 antisymmetric stretching modes. The observation of multiple bands shows that the symmetry of the sulphate anion is reduced. Multiple Raman and infrared bands in the OH stretching region shows that water in the structure of leightonite is in a range of molecular environments.