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.

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 borate mineral rhodizite (K, Cs)Al4Be4(B, Be)12O28 – A vibrational spectroscopic study

We have studied the borate mineral rhodizite (K, Cs)Al4Be4(B, Be)12O28 using a combination of DEM with EDX and vibrational spectroscopic techniques. The mineral occurs as colorless, gray, yellow to white crystals in the triclinic crystal system. The studied sample is from the Antandrokomby Mine, Sahatany valley, Madagascar. The mineral is prized as a semi-precious jewel. Semi-quantitative chemical composition shows a Al, Ca, borate with minor amounts of K, Mg and Cs. The mineral has a characteristic borate Raman spectrum and bands are assigned to the stretching and bending modes of B, Be and Al. No Raman bands in the OH stretching region were observed.

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.

Gas sensing of ruthenium implanted tungsten oxide thin films

Different amounts of Ru were implanted into thermally evaporated WO3 thin films by ion implantation. The films were subsequently annealed at 600oC for 2 hours in air to remove defects generated during the ion implantation. The Ru concentrations of four samples have been quantified by Rutherford Backscattering Spectrometry as 0.8, 5.5, 9 and 11.5 at%. The un-implanted WO3 films were highly porous but the porosity decreased significantly after ion implantation as observed by Transmission Electron Microscopy and Scanning Electron Microscopy. The thickness of the films also decreased with increasing Ru-ion dose, which is mainly due to densification of the porous films during ion implantation. From Raman spectroscopy two peaks at 408 and 451 cm-1 (in addition to the typical vibrational peaks of the monoclinic WO3 phase) associated with Ru were observed. Their intensity increased with increasing Ru concentration. X-Ray Photoelectron Spectroscopy showed a metallic state of Ru with binding energy of Ru 3d5/2 at 280.1 eV. This peak position remained almost unchanged with increasing Ru concentration. The resistances of the Ru-implanted films were found to increase in the presence of NO2 and NO with higher sensor response to NO2. The effect of Ru concentration on the sensing performance of the films was not explicitly observed due to reduced film thickness and porosity with increasing Ru concentration. However, the results indicate that the implantation of Ru into WO3 films with sufficient film porosity and film thickness can be beneficial for NO2 sensing at temperatures in the range of 250°C to 350°C.

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.

Molecular structural studies of the amorphous mineral pitticite Fe, AsO4, SO4, H2O

Some minerals are colloidal and show no X-ray diffraction patterns. Vibrational spectroscopy offers one of the few methods for the assessment of the structure of these types of mineral. Among this group of minerals is pitticite simply described as Fe, AsO4, SO4, H2O. The objective of this research is to determine the molecular structure of the mineral pitticite using vibrational spectroscopy. Raman microscopy offers a useful method for the analysis of such colloidal minerals. Raman and infrared bands are attributed to the , and water stretching vibrations. The Raman spectrum is dominated by a very intense sharp band at 983 cm−1 assigned to the symmetric stretching mode. A strong Raman band at 1041 cm−1 is observed and is assigned to the antisymmetric stretching mode. Low intensity Raman bands at 757 and 808 cm−1 may be assigned to the antisymmetric and symmetric stretching modes. Raman bands observed at 432 and 465 cm−1 are attributable to the doubly degenerate ν2(SO4)2- bending mode.

Label-free SERS for natural product provenance

Introduction Natural product provenance is important in the food, beverage and pharmaceutical industries, for consumer confidence and with health implications. Raman spectroscopy has powerful molecular fingerprint abilities. Surface Enhanced Raman Spectroscopy’s (SERS) sharp peaks allow distinction between minimally different molecules, so it should be suitable for this purpose. Methods Naturally caffeinated beverages with Guarana extract, coffee and Red Bull energy drink as a synthetic caffeinated beverage for comparison (20 µL ea.) were reacted 1:1 with Gold nanoparticles functionalised with anti-caffeine antibody (ab15221) (10 minutes), air dried and analysed in a micro-Raman instrument. The spectral data was processed using Principle Component Analysis (PCA). Results The PCA showed Guarana sourced caffeine varied significantly from synthetic caffeine (Red Bull) on component 1 (containing 76.4% of the variance in the data). See figure 1. The coffee containing beverages, and in particular Robert Timms (instant coffee) were very similar on component 1, but the barista espresso showed minor variance on component 1. Both coffee sourced caffeine samples varied with red Bull on component 2, (20% of variance). ************************************************************ Figure 1 PCA comparing a naturally caffeinated beverage containing Guarana with coffee. ************************************************************ Discussion PCA is an unsupervised multivariate statistical method that determines patterns within data. Figure 1 shows Caffeine in Guarana is notably different to synthetic caffeine. Other researchers have revealed that caffeine in Guarana plants is complexed with tannins. Naturally sourced/ lightly processed caffeine (Monster Energy, Espresso) are more inherently different than synthetic (Red Bull) /highly processed (Robert Timms) caffeine, in figure 1, which is consistent with this finding and demonstrates this technique’s applicability. Guarana provenance is important because it is still largely hand produced and its demand is escalating with recognition of its benefits. This could be a powerful technique for Guarana provenance, and may extend to other industries where provenance / authentication are required, e.g. the wine or natural pharmaceuticals industries.

Self assembly of plasmonic core-satellite nano-assemblies mediated by hyperbranched polymer linkers

The morphology of plasmonic nano-assemblies has a direct influence on optical properties, such as localised surface plasmon resonance (LSPR) and surface enhanced Raman scattering (SERS) intensity. Assemblies with core-satellite morphologies are of particular interest, because this morphology has a high density of hot-spots, while constraining the overall size. Herein, a simple method is reported for the self-assembly of gold NPs nano-assemblies with a core-satellite morphology, which was mediated by hyperbranched polymer (HBP) linkers. The HBP linkers have repeat units that do not interact strongly with gold NPs, but have multiple end-groups that specifically interact with the gold NPs and act as anchoring points resulting in nano-assemblies with a large (~48 nm) core surrounded by smaller (~15 nm) satellites. It was possible to control the number of satellites in an assembly which allowed optical parameters such as SPR maxima and the SERS intensity to be tuned. These results were found to be consistent with finite-difference time domain (FDTD) simulations. Furthermore, the multiplexing of the nano-assemblies with a series of Raman tag molecules was demonstrated, without an observable signal arising from the HBP linker after tagging. Such plasmonic nano-assemblies could potentially serve as efficient SERS based diagnostics or biomedical imaging agents in nanomedicine.

Thermal stability and decomposition kinetics of styrene-butadiene rubber nanocomposites filled with different particle sized kaolinites

A series of styrene-butadiene rubber (SBR) nanocomposites filledwith different particle sized kaolinites are prepared via a latex blending method. The thermal stabilities of these clay polymer nanocomposites (CPN) are characterized by a range of techniques including thermogravimetry (TG), digital photos, scanning electron microscopy (SEM) and Raman spectroscopy. These CPN show some remarkable improvement in thermal stability compared to that of the pure SBR. With the increase of kaolinite particle size, the residual char content and the average activation energy of kaolinite SBR nanocomposites all decrease; the pyrolysis residues become porous; the crystal carbon in the pyrolysis residues decrease significantly from 58.23% to 44.41%. The above results prove that the increase of kaolinite particle size is not beneficial in improving the thermal stability of kaolinite SBR nanocomposites.

Insight into morphology and structure of different particle sized kaolinites with same origin

The particle size, morphology, crystallinity order and structural defects of four kaolinite samples are characterized by the techniques including particle size analysis, scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). The particle size of four kaolinite samples gradually increases. Four samples all belong to the ordered kaolinite and show a decrease in structural order with the increase of kaolinite particle size. The changes of structural defect are proved by the increase of the band splitting in Raman spectroscopy, the decrease of the intensity of absorption bands in infrared spectroscopy, and the decrease of equivalent silicon atom and the increase of nonequivalent aluminum atom in MAS NMR spectroscopy. The differences in morphology and structural defect are attributed to the broken bonds of Al–O–Si, Al–O–Al and Si–O–Si and the Al substitution for Si in tetrahedral sheets.

A vibrational spectroscopic study of the phosphate mineral rimkorolgite (Mg,Mn2+)5(Ba, Sr)(PO4)4·8H2O from Kovdor massif, Kola Peninsula, Russia

We have studied aspect of the molecular structure of the phosphate mineral rimkorolgite from Zheleznyi iron mine, Kovdor massif, Kola Peninsula, Russia, using SEM with EDX and vibrational spectroscopy. Qualitative chemical analysis shows a homogeneous phase, composed by P, Mg, Ba, Mn and Ca. Small amounts of Si were also observed. An intense Raman peak at 975 cm−1 is assigned to the PO43− ν1 symmetric stretching mode. The Raman band at 964 cm−1 is attributed to the HPO42− ν1 symmetric stretching vibration. Raman bands observed at 1016, 1035, 1052, 1073, 1105 and 1135 cm−1 are attributed to the ν3 antisymmetric stretching vibrations of the HPO42− and PO43− units. Complexity in the spectra of the phosphate bending region is observed. The broad Raman band at 3272 cm−1 is assigned to the water stretching vibration. Vibrational spectroscopy enables aspects on the molecular structure of rimkorolgite to be undertaken.