Near infrared spectroscopy for non-destructive evaluation of articular cartilage

There is a need for an accurate real-time quantitative system that would enhance decision-making in the treatment of osteoarthritis. To achieve this objective, significant research is required that will enable articular cartilage properties to be measured and categorized for health and functionality without the need for laboratory tests involving biopsies for pathological evaluation. Such a system would provide the capability of access to the internal condition of the cartilage matrix and thus extend the vision-based arthroscopy that is currently used beyond the subjective evaluation of surgeons. The system required must be able to non-destructively probe the entire thickness of the cartilage and its immediate subchondral bone layer. In this thesis, near infrared spectroscopy is investigated for the purpose mentioned above. The aim is to relate it to the structure and load bearing properties of the cartilage matrix to the near infrared absorption spectrum and establish functional relationships that will provide objective, quantitative and repeatable categorization of cartilage condition outside the area of visible degradation in a joint. Based on results from traditional mechanical testing, their innovative interpretation and relationship with spectroscopic data, new parameters were developed. These were then evaluated for their consistency in discriminating between healthy viable and degraded cartilage. The mechanical and physico-chemical properties were related to specific regions of the near infrared absorption spectrum that were identified as part of the research conducted for this thesis. The relationships between the tissue's near infrared spectral response and the new parameters were modeled using multivariate statistical techniques based on partial least squares regression (PLSR). With significantly high levels of statistical correlation, the modeled relationships were demonstrated to possess considerable potential in predicting the properties of unknown tissue samples in a quick and non-destructive manner. In order to adapt near infrared spectroscopy for clinical applications, a balance between probe diameter and the number of active transmit-receive optic fibres must be optimized. This was achieved in the course of this research, resulting in an optimal probe configuration that could be adapted for joint tissue evaluation. Furthermore, as a proof-of-concept, a protocol for obtaining the new parameters from the near infrared absorption spectra of cartilage was developed and implemented in a graphical user interface (GUI)-based software, and used to assess cartilage-on-bone samples in vitro. This conceptual implementation has been demonstrated, in part by the individual parametric relationship with the near infrared absorption spectrum, the capacity of the proposed system to facilitate real-time, non-destructive evaluation of cartilage matrix integrity. In summary, the potential of the optical near infrared spectroscopy for evaluating articular cartilage and bone laminate has been demonstrated in this thesis. The approach could have a spin-off for other soft tissues and organs of the body. It builds on the earlier work of the group at QUT, enhancing the near infrared component of the ongoing research on developing a tool for cartilage evaluation that goes beyond visual and subjective methods.

Auger spectroscopy of stratospheric particles : the influence of aerosols on interplanetary dust

Particle collections from the stratosphere via either the JSC Curatorial Program or the U2 Program (NASA Ames) occur between 16km and 19km altitude and are usually part of ongoing experiments to measure parameters related to the aerosol layer. Fine-grained aerosols (<0.1µm) occur in the stratosphere up to 35km altitude and are concentrated between 15km and 25km altitude[1]. All interplanetary dust particles (IDP's) from these stratospheric collections must pass through this aerosol layer before reaching the collection altitude. The major compounds in this aerosol layer are sulfur rich particulates (<0.1µm) and gases and include H2S04, OCS, S02 and CS2 [2].In order to assess possible surface reactions of interplanetary dust particles (IDP's) with ambient aerosols in the stratosphere, we have initiated a Surface Auger Microprobe (SAM) and electron microscope study of selected particles from the JSC Cosmic Dust Collection.

Vibrational spectroscopy of the multianion mineral kemmlitzite (Sr,Ce)Al3(AsO4)(SO4)(OH)6

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 kemmlitzite (Sr,Ce)Al3(AsO4)(SO4)(OH)6. The objective of this research is to determine the molecular structure of the mineral kemmlitzite using vibrational spectroscopy. Raman microscopy offers a useful method for the analysis of such colloidal minerals. Raman and infrared bands are attributed to the AsO43- , SO42- and water stretching vibrations. The Raman spectrum is dominated by a very intense sharp band at 984 cm-1 assigned to the SO42- symmetric stretching mode. Raman bands at 690, 772 and 825 cm-1 may be assigned to the AsO43- antisymmetric and symmetric stretching modes. Raman bands observed at 432 and 465 cm-1 are attributable to the doubly degenerate 2 (SO4)2- bending mode. Vibrational spectroscopy is important in the assessment of the molecular structure of the kemmlitzite, especially when the mineral is non-diffracting or poorly diffracting.

Assessment of the molecular structure of the borate mineral sakhaite Ca12Mg4(BO3)7(CO3)4Cl(OH)2·H2O using vibrational spectroscopy

The structure of the borate mineral sakhaite Ca12Mg4(BO3)7(CO3)4Cl(OH)2·H2O, a borate–carbonate of calcium and magnesium has been assessed using vibrational spectroscopy. Assignment of bands is undertaken by comparison with the data from other published results. Intense Raman band at 1134 cm−1 with a shoulder at 1123 cm−1 is assigned to the symmetric stretching mode. The Raman spectrum displays bands at 1479, 1524 and 1560 cm−1 which are assigned to the antisymmetric stretching vibrations. The observation of multiple carbonate stretching bands supports the concept that the carbonate units are non-equivalent. The Raman band at 968 cm−1 with a shoulder at 950 cm−1 is assigned to the symmetric stretching mode of trigonal boron. Raman bands at 627 and 651 cm−1 are assigned to the out-of-plane bending modes of trigonal and tetrahedral boron. Raman spectroscopy coupled with infrared spectroscopy enables the molecular structure of the mineral sakhaite to be assessed.

Assessment of the molecular structure of the borate mineral boracite Mg3B7O13Cl using vibrational spectroscopy

Boracite is a magnesium borate mineral with formula: Mg3B7O13Cl and occurs as blue green, colorless, gray, yellow to white crystals in the orthorhombic – pyramidal crystal system. An intense Raman band at 1009 cm−1 was assigned to the BO stretching vibration of the B7O13 units. Raman bands at 1121, 1136, 1143 cm−1 are attributed to the in-plane bending vibrations of trigonal boron. Four sharp Raman bands observed at 415, 494, 621 and 671 cm−1 are simply defined as trigonal and tetrahedral borate bending modes. The Raman spectrum clearly shows intense Raman bands at 3405 and 3494 cm−1, thus indicating that some Cl anions have been replaced with OH units. The molecular structure of a natural boracite has been assessed by using vibrational spectroscopy.

Near Infrared Spectroscopy Evaluation of Articular Cartilage : Decision-Making in Arthroplasty : Real-Time Assessment of Articular Cartilage

Current diagnostic methods for assessing the severity of articular cartilage degenerative conditions, such as osteoarthritis, are inadequate. There is also a lack of techniques that can be used for real-time evaluation of the tissue during surgery to inform treatment decision and eliminate subjectivity. This book, derived from Dr Afara’s doctoral research, presents a scientific framework that is based on near infrared (NIR) spectroscopy for facilitating the non-destructive evaluation of articular cartilage health relative to its structural, functional, and mechanical properties. This development is a component of the ongoing research on advanced endoscopic diagnostic techniques in the Articular Cartilage Biomechanics Research Laboratory of Professor Adekunle Oloyede at Queensland University of Technology (QUT), Brisbane Australia.

Vibrational spectroscopy of the borate mineral henmilite Ca2Cu[B(OH)4]2(OH)4

Henmilite is a triclinic mineral with the crystal structure consisting of isolated B(OH)4 tetrahedra, planar Cu(OH)4 groups and Ca(OH)3 polyhedra. The structure can also be viewed as having dimers of Ca polyhedra connected to each other through 2B(OH) tetrahedra to form chains parallel to the C axis. The structure of the mineral has been assessed by the combination of Raman and infrared spectra. Raman bands at 902, 922, 951, and 984 cm−1 and infrared bands at 912, 955 and 998 cm−1 are assigned to stretching vibrations of tetragonal boron. The Raman band at 758 cm−1 is assigned to the symmetric stretching mode of tetrahedral boron. The series of bands in the 400–600 cm−1 region are due to the out-of-plane bending modes of tetrahedral boron. Two very sharp Raman bands are observed at 3559 and 3609 cm−1. Two infrared bands are found at 3558 and 3607 cm−1. These bands are assigned to the OH stretching vibrations of the OH units in henmilite. A series of Raman bands are observed at 3195, 3269, 3328, 3396, 3424 and 3501 cm−1 are assigned to water stretching modes. Infrared spectroscopy also identified water and OH units in the henmilite structure. It is proposed that water is involved in the structure of henmilite. Hydrogen bond distances based upon the OH stretching vibrations using a Libowitzky equation were calculated. The number and variation of water hydrogen bond distances are important for the stability off the mineral.

Vibrational spectroscopy of the borate mineral kotoite Mg3(BO3)2

Vibrational spectroscopy has been used to assess the structure of kotoite a borate mineral of magnesium which is isostructural with jimboite. The mineral is orthorhombic with point group: 2/m 2/m 2/m. The mineral has the potential as a new memory insulator material. The mineral has been characterised by a combination of Raman and infrared spectroscopy. The Raman spectrum is dominated by a very intense band at 835 cm−1, assigned to the symmetric stretching mode of tetrahedral boron. Raman bands at 919, 985 and 1015 cm−1 are attributed to the antisymmetric stretching modes of tetrahedral boron. Kotoite is strictly an hydrous borate mineral. An intense Raman band observed at 3559 cm−1 is attributed to the stretching vibration of hydroxyl units, more likely to be associated with the borate mineral hydroxyborate. The lack of observation of water bending modes proves the absence of water in the kotoite structure.

Vibrational spectroscopy of natural cave mineral monetite CaHPO4 and the synthetic analog

Monetite is a phosphate mineral formed by the reaction of the chemicals in bat guano with calcite substrates and is commonly found in caves. The analog of the mineral monetite CaHPO4 has been synthesized and the Raman and infrared spectra of the natural monetite originating from the Murra-el-elevyn Cave, Eucla, Western Australia, compared. Monetite is characterized by a complex set of phosphate bands that arise because of two sets of pairs of phosphate units in the unit cell. Raman and infrared bands are assigned to HPO4(2-), OH stretching and bending vibrations. Infrared bands at 1346 and 1402 cm−1 are assigned to POH deformation modes. Vibrational spectroscopy confirms the presence of monetite in the cave system.

Stichtite : a review

Stichtite is a naturally occurring layered double hydroxide (LDH) with the ideal chemical formula Mg6Cr2CO3(OH)16·4H2O. It has received less attention in the literature than other LDHs and is often described as a rare mineral; however, abundant deposits of the mineral do exist. In this article we aim to review a number of significant publications concerning the mineral stichtite, including papers covering the discovery, geological origin, synthesis and characterizsation of stichtite. Characterization techniques reviewed include powder X-ray diffraction (XRD), infrared spectroscopy (IR), near infrared spectroscopy (NIR), Raman spectroscopy (Raman), thermogravimetry (TG) and electron microprobe analysis.

Thermogravimetric analysis of selected layered double hydroxides

Thermogravimetric analysis (TG) and powder X-ray diffraction (PXRD) were used to study some selected Mg/Al and Zn/Al layered double hydroxides (LDHs) prepared by co-precipitation. A Mg/Al hydrotalcite was investigated before and after reformation in fluoride and nitrate solutions. Little change in the TG or PXRD patterns was observed. It was proposed that successful intercalation of nitrate anions has occurred. However, the absence of any change in the d(003) interlayer spacing suggests that fluoride anions were not intercalated between the LDH layers. Any fluoride anions that were removed from solution are most likely adsorbed onto the outer surfaces of the hydrotalcite. As fluoride removal was not quantified it is not possible to confirm that this has happened without further experimentation. Carbonate is probably intercalated into the interlayer of these hydrotalcites, as well as fluoride or nitrate. The carbonate most likely originates from either incomplete decarbonation during thermal activation or adsorption from the atmosphere or dissolved in the deionised water. Small and large scale co-precipitation syntheses of a Zn/Al LDH were also investigated to determine if there was any change in the product. While the small scale experiment produced a good quality LDH of reasonable purity; the large scale synthesis resulted in several additional phases. Imprecise measurement and difficulty in handling the large quantities of reagents appeared to be sufficient to alter the reaction conditions causing a mixture of phases to be formed.

Removal of boron species by layered double hydroxides : a review

Boron, which is an essential element for plants, is toxic to humans and animals at high concentrations. Layered double hydroxides (LDHs) and thermally activated LDHs have shown good uptake of a range of boron species in laboratory scale experiments when compared to current available methods, which are for the most part ineffective or prohibitively expensive. LDHs were able to remove anions from water by anion exchange, the reformation (or memory) effect and direct precipitation. The main mechanism of boron uptake appeared to be anion exchange, which was confirmed by powder X-ray diffraction (XRD) measurements. Solution pH appeared to have little effect on boron sorption while thermal activation did not always significantly improve boron uptake. In addition, perpetration of numerous LDHs with varying boron anions in the interlayer region by direct co-precipitation and anion exchange have been reported by a number of groups. The composition and orientation of the interlayer boron ions could be identified with reasonable certainty by applying a number of characterisation techniques including: powder XRD, nuclear magnetic resonance spectroscopy (NMR), X-ray photoelectron spectroscopy (XPS) and infrared (IR) spectroscopy. There is still considerable scope for future research on the application of LDHs for the removal of boron contaminants.

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.

Vibrational spectroscopy of the mineral meyerhofferite CaB3O3(OH)5·H2O – An assessment of the molecular structure

Meyerhofferite is a calcium hydrated borate mineral with ideal formula: CaB3O3(OH)5�H2O and occurs as white complex acicular to crude crystals with length up to �4 cm, in fibrous divergent, radiating aggregates or reticulated and is often found in sedimentary or lake-bed borate deposits. The Raman spectrum of meyerhofferite is dominated by intense sharp band at 880 cm�1 assigned to the symmetric stretching mode of trigonal boron. Broad Raman bands at 1046, 1110, 1135 and 1201 cm�1 are attributed to BOH in-plane bending modes. Raman bands in the 900–1000 cm�1 spectral region are assigned to the antisymmetric stretching of tetrahedral boron. Distinct OH stretching Raman bands are observed at 3400, 3483 and 3608 cm�1. The mineral meyerhofferite has a distinct Raman spectrum which is different from the spectrum of other borate minerals, making Raman spectroscopy a very useful tool for the detection of meyerhofferite in sedimentary and lake bed deposits.