Infrared and Raman spectroscopic characterization of the carbonate mineral weloganite – Sr3Na2Zr(CO3)6·3H2O and in comparison with selected carbonates

The mineral weloganite Na2Sr3Zr(CO3)6·3H2O has been studied by using vibrational spectroscopy and a comparison is made with the spectra of weloganite with other carbonate minerals. Weloganite is member of the mckelveyite group that includes donnayite-(Y) and mckelveyite-(Y). The Raman spectrum of weloganite is characterized by an intense band at 1082 cm−1 with shoulder bands at 1061 and 1073 cm−1, attributed to the View the MathML source symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of View the MathML source symmetric stretching vibration varies with mineral composition. The Raman bands at 1350, 1371, 1385, 1417, 1526, 1546, and 1563 cm−1 are assigned to the ν3 (CO3)2− antisymmetric stretching mode. The observation of additional Raman bands for the ν3 modes for weloganite is significant in that it shows distortion of the carbonate anion in the mineral structure. The Raman band observed at 870 cm−1 is assigned to the (CO3)2− ν2 bending mode. Raman bands observed for weloganite at 679, 682, 696, 728, 736, 749, and 762 cm−1 are assigned to the (CO3)2− ν4 bending modes. A comparison of the vibrational spectra is made with that of the rare earth carbonates decrespignyite, bastnasite, hydroxybastnasite, parisite, and northupite.

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.

Infrared and Raman spectroscopic characterization of the phosphate mineral leucophosphite - K(Fe3+)2(PO4)2(OH)·2(H2O)

The phosphate mineral leucophosphite K(Fe2)3þ(PO4)2(OH) · 2H2O has been characterized by SEM-EDS, Raman, and infrared spectro- scopic measurements. The mineral is predominantly a K and Fe phosphate with some minor substitution of Al in the Fe3þ site. Raman bands at 994 and 1058 cm-1 are assigned to the symmetric stretching modes of PO3- and HPO2- units. The Raman bands at 1104, 1135, and 1177 cm-1 are assigned to the PO3- and HPO2- antisymmetric stretching modes. Raman and infrared spectra in the 2600–3800 cm-1 region show a complex set of overlapping bands, which may be resolved into the component bands. The Raman bands observed at 3325, 3355, and 3456 cm-1 are attributed to water stretching vibrations, and in the infrared spectrum, bands at 3237, 3317, and 3453 cm-1 are assigned to water stretching bands.

Infrared and Raman spectroscopic characterization of the silicate-carbonate mineral carletonite – KNa4Ca4Si8O18(CO3)4(OH,F) H2O

Abstract An assessment of the molecular structure of carletonite a rare phyllosilicate mineral with general chemical formula given as KNa4Ca4Si8O18(CO3)4(OH,F)·H2O has been undertaken using vibrational spectroscopy. Carletonite has a complex layered structure. Within one period of c, it contains a silicate layer of composition NaKSi8O18·H2O, a carbonate layer of composition NaCO3·0.5H2O and two carbonate layers of composition NaCa2CO3(F,OH)0.5. Raman bands are observed at 1066, 1075 and 1086 cm−1. Whether these bands are due to the CO32- ν1 symmetric stretching mode or to an SiO stretching vibration is open to question. Multiple bands are observed in the 300–800 cm−1 spectral region, making the attribution of these bands difficult. Multiple water stretching and bending modes are observed showing that there is much variation in hydrogen bonding between water and the silicate and carbonate surfaces.

Ultra-trace detection of diagnostically important biomarkers using functionalised-Surface Enhanced Raman Spectroscopy (SERS)

Here we report an ultrasensitive method for detecting bio-active compounds in biological samples by means of functionalised nanoparticles interrogated by surface enhanced Raman spectroscopy (SERS). This method is applicable to the recovery and detection of many diagnostically important peptidyl analytes such as insulin, human growth hormone, growth factors (IGFs) and erythropoietin (EPO), as well as many small molecule analytes and metabolites. Our method, developed to detect EPO, demonstrates its utility in a complex yet well defined biological system. Recombinant human EPO (rhEPO) and EPO analogues have successfully been used to treat anaemia in end-stage renal failure, chronic disorders and infections, cancer and AIDS. Current methods for EPO testing are lengthy, laborious and relatively insensitive to low concentrations. In our rapid screening methodology, gold nanoparticles were functionalised with anti-EPO antibodies to provide very high selectivity towards the EPO protein in urine. These “smart sensor” nanoparticles interact with and trap EPO. Subsequent SERS screening allows for the detection and quantisation of ultra trace amounts (<<10-15 M) of EPO in urine samples with minimal sample preparation. We present data showing that the SERS spectrum differentiates between human endogenous EPO and rhEPO in unpurified urine, and potentially distinguishes between purified EPO isoforms. The elimination of sample preparation and direct screening in biological fluids significantly reduces the time required by current methods. Antibody recognition against a variety of biological targets and the availability of portable commercial SERS analysers for rapid onsite testing suggest broad diagnostic applicability in a flexible analytical platform.

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.

Raman spectroscopic study of the mineral qingheiite Na2(Mn2+,Mg,Fe2+)2(Al,Fe3+)(PO4)3, a pegmatite phosphate mineral from Santa Ana pegmatite, Argentina

The pegmatite mineral qingheiite Na2(Mn2+,Mg,Fe2+)2(Al,Fe3+)(PO4)3 has been studied by a combination of SEM and EMP, Raman and infrared spectroscopy. The studied sample was collected from the Santa Ana pegmatite, Argentina. The mineral occurs as a primary mineral in lithium bearing pegmatite, in association with beausite and lithiophilite. The Raman spectrum is characterized by a very sharp intense Raman band at 980 cm�1 assigned to the PO3�4 symmetric stretching mode. Multiple Raman bands are observed in the PO3�4 antisymmetric stretching region, providing evidence for the existence of more than one phosphate unit in the structure of qingheiite and evidence for the reduction in symmetry of the phosphate units. This concept is affirmed by the number of bands in the m4 and m2 bending regions. No intensity was observed in the OH stretching region in the Raman spectrum but significant intensity is found in the infrared spectrum. Infrared bands are observed at 2917, 3195, 3414 and 3498 cm�1 are assigned to water stretching vibrations. It is suggested that some water is coordinating the metal cations in the structure of qingheiite.

Deep Raman Spectroscopy in the analytical forensic investigation of concealed substances

Deep Raman Spectroscopy is a domain within Raman spectroscopy consisting of techniques that facilitate the depth profiling of diffusely scattering media. Such variants include Time-Resolved Raman Spectroscopy (TRRS) and Spatially-Offset Raman Spectroscopy (SORS). A recent study has also demonstrated the integration of TRRS and SORS in the development of Time-Resolved Spatially-Offset Raman Spectroscopy (TR-SORS). This research demonstrates the application of specific deep Raman spectroscopic techniques to concealed samples commonly encountered in forensic and homeland security at various working distances. Additionally, the concepts behind these techniques are discussed at depth and prospective improvements to the individual techniques are investigated. Qualitative and quantitative analysis of samples based on spectral data acquired from SORS is performed with the aid of multivariate statistical techniques. By the end of this study, an objective comparison is made among the techniques within Deep Raman Spectroscopy based on their capabilities. The efficiency and quality of these techniques are determined based on the results procured which facilitates the understanding of the degree of selectivity for the deeper layer exhibited by the individual techniques relative to each other. TR-SORS was shown to exhibit an enhanced selectivity for the deeper layer relative to TRRS and SORS whilst providing spectral results with good signal-to-noise ratio. Conclusive results indicate that TR-SORS is a prospective deep Raman technique that offers higher selectivity towards deep layers and therefore enhances the non-invasive analysis of concealed substances from close range as well as standoff distances.

Infrared and Raman spectroscopic characterization of the borate mineral colemanite – CaB3O4(OH)3·H2O – implications for the molecular structure

Colemanite CaB3O4(OH)3 H2O is a secondary borate mineral formed from borax and ulexite in evaporate deposits of alkaline lacustrine sediments. The basic structure of colemanite contains endless chains of interlocking BO2(OH) triangles and BO3(OH) tetrahedrons with the calcium, water and extra hydroxide units interspersed between these chains. The Raman spectra of colemanite is characterized by an intense band at 3605 cm-1 assigned to the stretching vibration of OH units and a series of bands at 3182, 3300, 3389 and 3534 cm-1 assigned to water stretching vibrations. Infrared bands are observed in similar positions. The BO stretching vibrations of the trigonal and tetrahedral boron are characterized by Raman bands at 876, 1065 and 1084 cm-1. The OBO bending mode is defined by the Raman band at 611 cm-1. It is important to characterize the very wide range of borate minerals including colemanite because of the very wide range of applications of boron containing minerals.

Infrared and Raman spectroscopic characterization of the phosphate mineral fairfieldite – Ca2(Mn2+,Fe2+)2(PO4)2·2(H2O)

Raman spectroscopy complimented with infrared spectroscopy has been used to determine the molecular structure of the phosphate mineral fairfieldite. The Raman phosphate (PO4)3- stretching region shows strong differences between the fairfieldite phosphate minerals which is attributed to the cation substitution for calcium in the structure. In the infrared spectra complexity exists with multiple (PO4)2- antisymmetric stretching vibrations observed, indicating a reduction of the tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong Raman bands around 600 cm-1 are assigned to v4 phosphate bending modes. Multiple bands in the 400–450 cm-1 region assigned to m2 phosphate bending modes provide further evidence of symmetry reduction of the phosphate anion. Three broadbands for fairfieldite are found at 3040, 3139 and 3271 cm-1 and are assigned to OH stretching bands. By using a Libowitzky empirical equation hydrogen bond distances of 2.658 and 2.730 A are estimated. Vibrational spectroscopy enables aspects of the molecular structure of the fairfieldite to be ascertained.

Investigation of ultra trace detection in functionalised-surface enhanced Raman spectroscopy (SERS)

We have developed an explanation for ultra trace detection found when using Au/Ag SERS nanoparticles linked to biochemical affinity tags, e.g. antibodies. The nanoparticle structure is not as usually assumed and the aggregated nanoparticles constitute hot spots that are indispensable for these very low levels of analyte detection, even more so when using a direct detection method.

Raman and infrared spectroscopic study of the mineral goyazite SrAl3(PO4)2(OH)5·H2O

We have studied the mineral goyazite using Raman and infrared spectroscopy. Goyazite is a member of the crandallite subgroup of the alunite supergroup. The crystal structure is of the alunite-type and consists of sheets of corner-sharing AlO6 octahedra parallel to (0001). The octahedrally coordinated Sr2+ cations occupy cavities between pairs of octahedral sheets and are surrounded by six oxygen atoms from the (Al3+)O6 octahedra. The very intense sharp band at 983 cm-1 is assigned to the ν1 PO43- symmetric stretching mode. The observation of a single band supports the concept that all the phosphate units are equivalent in the structure of goyazite. Raman bands observed at 1029 cm-1 and 1037 cm-1 are assigned to the to the ν3 PO43- antisymmetric stretching vibrations. Two Raman bands at 895 and 927 cm-1 are attributed to the stretching vibrations of H2PO4; thus indicating some hydrogen phosphate units in the structure of goyazite. Raman bands at 556, 581, 596 and 612 cm-1 are assigned to the ν4 PO43- bending modes, suggesting a reduction of symmetry of phosphate units. Two sharp Raman bands at 3609 and 3631 cm-1 are attributed to OH stretching vibrations from the goyazite hydroxyl units. Broad Raman bands at 2924, 3043, 3210, 3429 and 3511 cm-1 are assigned to water stretching vibrations. Vibrational spectroscopy enables subtle details of the molecular structure of goyazite to be determined.

A combined environmental scanning electron microscopy and Raman microscopy study of methanol oxidation on silver(I) oxide

The techniques of environmental scanning electron microscopy (ESEM) and Raman microscopy have been used to respectively elucidate the morphological changes and nature of the adsorbed species on silver(I) oxide powder, during methanol oxidation conditions. Heating Ag2O in either water vapour or oxygen resulted firstly in the decomposition of silver(I) oxide to polycrystalline silver at 578 K followed by sintering of the particles at higher temperature. Raman spectroscopy revealed the presence of subsurface oxygen and hydroxyl species in addition to surface hydroxyl groups after interaction with water vapour. Similar species were identified following exposure to oxygen in an ambient atmosphere. This behaviour indicated that the polycrystalline silver formed from Ag2O decomposition was substantially more reactive than silver produced by electrochemical methods. The interaction of water at elevated temperatures subsequent to heating silver(I) oxide in oxygen resulted in a significantly enhanced concentration of subsurface hydroxyl species. The reaction of methanol with Ag2O at high temperatures was interesting in that an inhibition in silver grain growth was noted. Substantial structural modification of the silver(I) oxide material was induced by catalytic etching in a methanol/air mixture. In particular, "pin-hole" formation was observed to occur at temperatures in excess of 773 K, and it was also recorded that these "pin- holes" coalesced to form large-scale defects under typical industrial reaction conditions. Raman spectroscopy revealed that the working surface consisted mainly of subsurface oxygen and surface Ag=O species. The relative lack of sub-surface hydroxyl species suggested that it was the desorption of such moieties which was the cause of the "pin-hole" formation.

In situ Raman studies of the selective oxidation of methanol to formaldehyde and ethene to ethylene oxide on a polycrystalline silver catalyst

The combined techniques of in situ Raman microscopy and scanning electron microscopy (SEM) have been used to study the selective oxidation of methanol to formaldehyde and the ethene epoxidation reaction over polycrystalline silver catalysts. The nature of the oxygen species formed on silver was found to depend critically upon the exact morphology of the catalyst studied. Bands at 640, 780 and 960 cm-1 were identified only on silver catalysts containing a significant proportion of defects. These peaks were assigned to subsurface oxygen species situated in the vicinity of surface dislocations, AgIII=O sites formed on silver atoms modified by the presence of subsurface oxygen and O2 - species stabilized on subsurface oxygen-modified silver sites, respectively. The selective oxidation of methanol to formaldehyde was determined to occur at defect sites, where reaction of methanol with subsurface oxygen initially produced subsurface OH species (451 cm-1) and adsorbed methoxy species. Two distinct forms of adsorbed ethene were identified on oxidised silver sites. One of these was created on silver sites modified by the interaction of subsurface oxygen species, and the other on silver crystal planes containing a surface coverage of atomic oxygen species. The selective oxidation of ethene to ethylene oxide was achieved by the reaction between ethene adsorbed on modified silver sites and electrophilic AgIII=O species, whereas the combustion reaction was perceived to take place by the reaction of adsorbed ethene with nucleophilic surface atomic oxygen species. Defects were determined to play a critical role in the epoxidation reaction, as these sites allowed the rapid diffusion of oxygen into subsurface positions, and consequently facilitated the formation of the catalytically active AgIII=O sites.

trans-Polyacetylene on sodium and cesium mordenites: a resonance Raman spectroscopic study

Sodium and cesium mordenite (denoted NaM and CsM, respectively) were investigated as potential catalysts for the synthesis of polyacetylene ((CH) x). Both were successful in initiating polymerization of purified gaseous acetylene at room temperature as evidenced by Raman spectroscopic studies. The polyacetylene synthesised in this way exhibited resonance enhancement of the polyene skeletal vibrations. trans-Polyacetylene, but no cis-(CH) x, was detected. As no apparent coloration of the NaM and CsM substrates accompanied the formation of trans-(CH) x it was concluded that only small quantities of the polymer were present. The number of conjugated double bonds was estimated from the frequencies of the Raman active C-C and C=C stretching vibrations, and it was shown that the trans-(CH) x formed on CsM has a distribution of conjugation lengths ranging from less than 6 to at least 30 double bonds. The polyacetylene formed on NaM was significantly shorter and was produced in lower yields than that synthesized on CsM. "Sliced" resonance excitation profiles of polyacetylene formed on CsM were obtained using nearly 40 different excitation wavelengths and these confirmed that the adsorbed trans-(CH) x was composed of segments having a distribution of conjugated lengths. The architecture of the mordenite pore system permitted only a single polymer molecule per channel, thereby preventing cross-linking. Raman spectroscopic studies of the effects of exposure to air revealed that progressive oxidative degradation occurred with a reduction in the number of conjugated double bond