Development and synthesis of innovative approaches to the surgical assessment of articular cartilage degeneration

This research has established, through ultrasound, near infrared spectroscopy and biomechanics experiments, parameters and parametric relationships that can form the framework for quantifying the integrity of the articular cartilage-on-bone laminate, and objectively distinguish between normal/healthy and abnormal/degenerated joint tissue, with a focus on articular cartilage. This has been achieved by: 1. using traditional experimental methods to produce new parameters for cartilage assessment; 2. using novel methodologies to develop new parameters; and 3. investigating the interrelationships between mechanical, structural and molec- ular properties to identify and select those parameters and methodologies that can be used in a future arthroscopic probe based on points 1 and 2. By combining the molecular, micro- and macro-structural characteristics of the tissue with its mechanical properties, we arrive at a set of critical benchmarking parameters for viable and early-stage non-viable cartilage. The interrelationships between these characteristics, examined using a multivariate analysis based on principal components analysis, multiple linear regression and general linear modeling, could then to deter- mine those parameters and relationships which have the potential to be developed into a future clinical device. Specifically, this research has found that the ultrasound and near infrared techniques can subsume the mechanical parameters and combine to characterise the tissue at the molecular, structural and mechanical levels over the full depth of the cartilage matrix. It is the opinion in this thesis that by enabling the determination of the precise area of in uence of a focal defect or disease in the joint, demarcating the boundaries of articular cartilage with dierent levels of degeneration around a focal defect, better surgical decisions that will advance the processes of joint management and treatment will be achieved. Providing the basis for a surgical tool, this research will contribute to the enhancement and quanti�cation of arthroscopic procedures, extending to post- treatment monitoring and as a research tool, will enable a robust method for evaluating developing (particularly focalised) treatments.

Comparison between maximal lengthening and shortening contractions for biceps brachii muscle oxygenation and hemodynamics

Eccentric contractions (ECC) require lower systemic oxygen (O2) and induce greater symptoms of muscle damage than concentric contractions (CON); however, it is not known if local muscle oxygenation is lower in ECC than CON during and following exercise. This study compared between ECC and CON for changes in biceps brachii muscle oxygenation [tissue oxygenation index (TOI)] and hemodynamics [total hemoglobin volume (tHb) = oxygenated-Hb + deoxygenated-Hb], determined by near-infrared spectroscopy over 10 sets of 6 maximal contractions of the elbow flexors of 10 healthy subjects. This study also compared between ECC and CON for changes in TOI and tHb during a 10-s sustained and 30-repeated maximal isometric contraction (MVC) task measured immediately before and after and 1–3 days following exercise. The torque integral during ECC was greater (P < 0.05) than that during CON by ∼30%, and the decrease in TOI was smaller (P < 0.05) by ∼50% during ECC than CON. Increases in tHb during the relaxation phases were smaller (P < 0.05) by ∼100% for ECC than CON; however, the decreases in tHb during the contraction phases were not significantly different between sessions. These results suggest that ECC utilizes a lower muscle O2 relative to O2 supply compared with CON. Following exercise, greater (P < 0.05) decreases in MVC strength and increases in plasma creatine kinase activity and muscle soreness were evident 1–3 days after ECC than CON. Torque integral, TOI, and tHb during the sustained and repeated MVC tasks decreased (P < 0.01) only after ECC, suggesting that muscle O2 demand relative to O2 supply during the isometric tasks was decreased after ECC. This could mainly be due to a lower maximal muscle mass activated as a consequence of muscle damage; however, an increase in O2 supply due to microcirculation dysfunction and/or inflammatory vasodilatory responses after ECC is recognized.

Optical non-destructive evaluation of articular cartilage integrity : a review

This paper reviews the current status of the application of optical non-destructive methods, particularly infrared (IR) and near infrared (NIR), in the evaluation of the physiological integrity of articular cartilage. It is concluded that a significant amount of work is still required in order to achieve specificity and clinical applicability of these methods in the assessment and treatment of dysfunctional articular joints.

Mechanism of interaction of hydrocalumites (Ca/Al-LDH) with methyl orange and acidic scarlet GR

The development of new materials for water purification is of universal importance. Among these types of materials are layered double hydroxides (LDHs). Non-ionic materials pose a significant problem as pollutants. The interaction of methyl orange (MO) and acidic scarlet GR (GR) adsorption on hydrocalumite (Ca/Al-LDH-Cl) were studied by X-ray diffraction (XRD), infrared spectroscopy (MIR), scanning electron microscope (SEM) and near-infrared spectroscopy (NIR). The XRD results revealed that the basal spacing of Ca/Al-LDH-MO was expanded to 2.45 nm, and the MO molecules were intercalated with a inter-penetrating bilayer model in the gallery of LDH, with 49o tilting angle. Yet Ca/Al-LDH-GR was kept the same d-value as Ca/Al-LDH-Cl. The NIR spectrum for Ca/Al-LDH-MO showed a prominent band around 5994 cm-1, assigned to the combination result of the N-H stretching vibrations, which was considered as a mark to assess MO- ion intercalation into Ca/Al-LDH-Cl interlayers. From SEM images, the particle morphology of Ca/Al-LDH-MO mainly changed to irregular platelets, with a “honey-comb” like structure. Yet the Ca/Al-LDH-GR maintained regular hexagons platelets, which was similar to that of Ca/Al-LDH-Cl. All results indicated that MO- ion was intercalated into Ca/Al-LDH-Cl interlayers, and acidic scarlet GR was only adsorped upon Ca/Al-LDH-Cl surfaces.

Photochemistry and chemometrics : an overview

Photochemistry has made significant contributions to our understanding of many important natural processes as well as the scientific discoveries of the man-made world. The measurements from such studies are often complex and may require advanced data interpretation with the use of multivariate or chemometrics methods. In general, such methods have been applied successfully for data display, classification, multivariate curve resolution and prediction in analytical chemistry, environmental chemistry, engineering, medical research and industry. However, in photochemistry, by comparison, applications of such multivariate approaches were found to be less frequent although a variety of methods have been used, especially with spectroscopic photochemical applications. The methods include Principal Component Analysis (PCA; data display), Partial Least Squares (PLS; prediction), Artificial Neural Networks (ANN; prediction) and several models for multivariate curve resolution related to Parallel Factor Analysis (PARAFAC; decomposition of complex responses). Applications of such methods are discussed in this overview and typical examples include photodegradation of herbicides, prediction of antibiotics in human fluids (fluorescence spectroscopy), non-destructive in- and on-line monitoring (near infrared spectroscopy) and fast-time resolution of spectroscopic signals from photochemical reactions. It is also quite clear from the literature that the scope of spectroscopic photochemistry was enhanced by the application of chemometrics. To highlight and encourage further applications of chemometrics in photochemistry, several additional chemometrics approaches are discussed using data collected by the authors. The use of a PCA biplot is illustrated with an analysis of a matrix containing data on the performance of photocatalysts developed for water splitting and hydrogen production. In addition, the applications of the Multi-Criteria Decision Making (MCDM) ranking methods and Fuzzy Clustering are demonstrated with an analysis of water quality data matrix. Other examples of topics include the application of simultaneous kinetic spectroscopic methods for prediction of pesticides, and the use of response fingerprinting approach for classification of medicinal preparations. In general, the overview endeavours to emphasise the advantages of chemometrics' interpretation of multivariate photochemical data, and an Appendix of references and summaries of common and less usual chemometrics methods noted in this work, is provided. Crown Copyright © 2010.

Vibrational spectroscopic study of the minerals nekoite Ca3Si6O15•7H2O and okenite Ca10Si18O46•18H2O : implications for the molecular structure

Nekoite Ca3Si6O15•7H2O and okenite Ca10Si18O46•18H2O are both hydrated calcium silicates found respectively in contact metamorphosed limestone and in association with zeolites from the alteration of basalts. The minerals form two-Dimensional infinite sheets with other than six-membered rings with 3-, 4-, or 5-membered rings and 8-membered rings. The two minerals have been characterised by Raman, near-infrared and infrared spectroscopy. The Raman spectrum of nekoite is characterised by two sharp peaks at 1061 and 1092 cm-1 with bands of lesser intensity at 974, 994, 1023 and 1132 cm-1. The Raman spectrum of okenite shows an intense single Raman band at 1090 cm-1 with a shoulder band at 1075 cm-1.These bands are assigned to the SiO stretching vibrations of Si2O5 units. Raman water stretching bands of nekoite are observed at 3071, 3380, 3502 and 3567 cm-1. Raman spectrum of okenite shows water stretching bands at 3029, 3284, 3417, 3531 and 3607 cm-1. NIR spectra of the two minerals are subtly different inferring water with different hydrogen bond strengths. By using a Libowitzky empirical formula, hydrogen bond distances based upon these OH stretching vibrations. Two types of hydrogen bonds are distinguished: strong hydrogen bonds associated with structural water and weaker hydrogen bonds assigned to space filling water molecules.

Inactivation and structural changes of E. Cloacae and B. Subtilis Endospores during IR laser water treatment

IR radiation has been studied for micro-organism inactivation of bacterial spores on metal substrates [1] and on metal and paper substrates [2]. A near-point near infrared laser water treatment apparatus for use in dental hand-pieces was also developed [3]. To date water sterilisation research using a mid-IR laser technique is very rare. According to the World Health Organisation [4], examinations for faecal indicator bacteria remain the most sensitive and specific way of assessing the hygienic quality of water. Bacteria that fall into this group are E. coli, other coliform bacteria (including E. cloacae) and to a lesser extent, faecal streptococci [5]. Protozoan cysts from organisms which cause giardiasis are the most frequently identified cause of waterborne diseases in developed countries [6,7]. The use of aerobic bacterial endospores to monitor the efficiency of various water treatments has been shown to provide a reliable and simple indicator of overall performance of water treatment[8,9].The efficacy of IR radiation for water disinfection compared to UV treatment has been further investigated in the present study. In addition FTIR spectroscopy in conjunction with Principle Component Analysis was used to characterise structural changes within the bacterial cells and endospores following IR laser treatment. Changes in carbohydrate content of E. cloacae following IR laser treatment were observed.

Cold-water immersion decreases cerebral oxygenation but improves recovery after intermittent-sprint exercise in the heat

This study examined the effects of post-exercise cooling on recovery of neuromuscular, physiological, and cerebral hemodynamic responses after intermittent-sprint exercise in the heat. Nine participants underwent three post-exercise recovery trials, including a control (CONT), mixed-method cooling (MIX), and cold-water immersion (10 °C; CWI). Voluntary force and activation were assessed simultaneously with cerebral oxygenation (near-infrared spectroscopy) pre- and post-exercise, post-intervention, and 1-h and 24-h post-exercise. Measures of heart rate, core temperature, skin temperature, muscle damage, and inflammation were also collected. Both cooling interventions reduced heart rate, core, and skin temperature post-intervention (P < 0.05). CWI hastened the recovery of voluntary force by 12.7 ± 11.7% (mean ± SD) and 16.3 ± 10.5% 1-h post-exercise compared to MIX and CONT, respectively (P < 0.01). Voluntary force remained elevated by 16.1 ± 20.5% 24-h post-exercise after CWI compared to CONT (P < 0.05). Central activation was increased post-intervention and 1-h post-exercise with CWI compared to CONT (P < 0.05), without differences between conditions 24-h post-exercise (P > 0.05). CWI reduced cerebral oxygenation compared to MIX and CONT post-intervention (P < 0.01). Furthermore, cooling interventions reduced cortisol 1-h post-exercise (P < 0.01), although only CWI blunted creatine kinase 24-h post-exercise compared to CONT (P < 0.05). Accordingly, improvements in neuromuscular recovery after post-exercise cooling appear to be disassociated with cerebral oxygenation, rather reflecting reductions in thermoregulatory demands to sustain force production.

A vibrational spectroscopic study of the phosphate mineral zanazziite - Ca2(MgFe2+)(MgFe2+Al)4Be4(PO4)6⋅6(H2O)

Zanazziite is the magnesium member of a complex beryllium calcium phosphate mineral group named roscherite. The studied samples were collected from the Ponte do Piauí mine, located in Itinga, Minas Gerais. The mineral was studied by electron microprobe, Raman and infrared spectroscopy. The chemical formula can be expressed as Ca2.00(Mg3.15,Fe0.78,Mn0.16,Zn0.01,Al0.26,Ca0.14)Be4.00(PO4)6.09(OH)4.00⋅5.69(H2O) and shows an intermediate member of the zanazziite–greinfeinstenite series, with predominance of zanazziite member. The molecular structure of the mineral zanazziite has been determined using a combination of Raman and infrared spectroscopy. A very intense Raman band at 970 cm−1 is assigned to the phosphate symmetric stretching mode whilst the Raman bands at 1007, 1047, 1064 and 1096 cm−1 are attributed to the phosphate antisymmetric stretching mode. The infrared spectrum is broad and the antisymmetric stretching bands are prominent. Raman bands at 559, 568, 589 cm−1 are assigned to the ν4 out of plane bending modes of the PO4 and HPO4 units. The observation of multiple bands supports the concept that the symmetry of the phosphate unit in the zanazziite structure is reduced in symmetry. Raman bands at 3437 and 3447 cm−1 are attributed to the OH stretching vibrations; Raman bands at 3098 and 3256 are attributed to water stretching vibrations. The width and complexity of the infrared spectral profile in contrast to the well resolved Raman spectra, proves that the pegmatitic phosphates are better studied with Raman spectroscopy.

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.

Microwave synthesis and spectroscopic characterization of manganese oxalate nanocrystals

The microwave synthesis of MnC2O4·2H2O nanoparticles was performed through the thermal double decomposition of oxalic acid dihydrate (C2H2O4·2H2O) and Mn(OAc)2·4H2O solutions using a CATA-2R microwave reactor. Structural characterization was performed using X-ray diffraction (XRD), particle size and shape were analyzed using transmission electron microscopy (TEM). The chemical in the structures was investigated using electron paramagnetic resonance (EPR) as well as optical absorption spectra and near-infrared (NIR) spectroscopies. The nanocrystals produced with this method were pure and had a distorted rhombic octahedral structure.

SERS based detection of barcoded gold nanoparticle assemblies from within animal tissue

We have explored the potential of deep Raman spectroscopy, specifically surface enhanced spatially offset Raman spectroscopy (SESORS), for non-invasive detection from within animal tissue, by employing SERS-barcoded nanoparticle (NP) assemblies as the diagnostic agent. This concept has been experimentally verified in a clinic-relevant backscattered Raman system with an excitation line of 785 nm under ex vivo conditions. We have shown that our SORS system, with a fixed offset of 2-3 mm, offered sensitive probing of injected QTH-barcoded NP assemblies through animal tissue containing both protein and lipid. In comparison to that of non-aggregated SERS-barcoded gold NPs, we have demonstrated that the tailored SERS-barcoded aggregated NP assemblies have significantly higher detection sensitivity. We report that these NP assemblies can be readily detected at depths of 7-8 mm from within animal proteinaceous tissue with high signal-to-noise (S/N) ratio. In addition they could also be detected from beneath 1-2 mm of animal tissue with high lipid content, which generally poses a challenge due to high absorption of lipids in the near-infrared region. We have also shown that the signal intensity and S/N ratio at a particular depth is a function of the SERS tag concentration used and that our SORS system has a QTH detection limit of 10-6 M. Higher detection depths may possibly be obtained with optimization of the NP assemblies, along with improvements in the instrumentation. Such NP assemblies offer prospects for in vivo, non-invasive detection of tumours along with scope for incorporation of drugs and their targeted and controlled release at tumour sites. These diagnostic agents combined with drug delivery systems could serve as a “theranostic agent”, an integration of diagnostics and therapeutics into a single platform.

Comparison between electrically-evoked and voluntary wrist movements on sensorimotor and prefrontal cortical activation : A multi-channel time domain fNIRS study

Neuromuscular electrical stimulation (NMES) has been consistently demonstrated to improve skeletal muscle function in neurological populations with movement disorders, such as poststroke and incomplete spinal cord injury (Vanderthommen and Duchateau, 2007). Recent research has documented that rapid, supraspinal central nervous system reorganisation/neuroplastic mechanisms are also implicated during NMES (Chipchase et al., 2011). Functional neuroimaging studies have shown NMES to activate a network of sub-cortical and cortical brain regions, including the sensorimotor (SMC) and prefrontal (PFC) cortex (Blickenstorfer et al., 2009; Han et al., 2003; Muthalib et al., 2012). A relationship between increase in SMC activation with increasing NMES current intensity up to motor threshold has been previously reported using functional MRI (Smith et al., 2003). However, since clinical neurorehabilitation programmes commonly utilise NMES current intensities above the motor threshold and up to the maximum tolerated current intensity (MTI), limited research has determined the cortical correlates of increasing NMES current intensity at or above MTI (Muthalib et al., 2012). In our previous study (Muthalib et al., 2012), we assessed contralateral PFC activation using 1-channel functional near infrared spectroscopy (fNIRS) during NMES of the elbow flexors by increasing current intensity from motor threshold to greater than MTI and showed a linear relationship between NMES current intensity and the level of PFC activation. However, the relationship between NMES current intensity and activation of the motor cortical network, including SMC and PFC, has not been clarified. Moreover, it is of scientific and clinical relevance to know how NMES affects the central nervous system, especially in comparison to voluntary (VOL) muscle activation. Therefore, the aim of this study was to utilise multi-channel time domain fNIRS to compare SMC and PFC activation between VOL and NMESevoked wrist extension movements.