Near infrared (NIR) absorption spectra correlates with subchondral bone micro-CT parameters in osteoarthritic rat models

Determining the properties and integrity of subchondral bone in the developmental stages of osteoarthritis, especially in a form that can facilitate real-time characterization for diagnostic and decision-making purposes, is still a matter for research and development. This paper presents relationships between near infrared absorption spectra and properties of subchondral bone obtained from 3 models of osteoarthritic degeneration induced in laboratory rats via: (i) menisectomy (MSX); (ii) anterior cruciate ligament transaction (ACL); and (iii) intra-articular injection of mono-ido-acetate (1 mg) (MIA), in the right knee joint, with 12 rats per model group (N = 36). After 8 weeks, the animals were sacrificed and knee joints were collected. A custom-made diffuse reflectance NIR probe of diameter 5 mm was placed on the tibial surface and spectral data were acquired from each specimen in the wavenumber range 4000–12 500 cm− 1. After spectral acquisition, micro computed tomography (micro-CT) was performed on the samples and subchondral bone parameters namely: bone volume (BV) and bone mineral density (BMD) were extracted from the micro-CT data. Statistical correlation was then conducted between these parameters and regions of the near infrared spectra using multivariate techniques including principal component analysis (PCA), discriminant analysis (DA), and partial least squares (PLS) regression. Statistically significant linear correlations were found between the near infrared absorption spectra and subchondral bone BMD (R2 = 98.84%) and BV (R2 = 97.87%). In conclusion, near infrared spectroscopic probing can be used to detect, qualify and quantify changes in the composition of the subchondral bone, and could potentially assist in distinguishing healthy from OA bone as demonstrated with our laboratory rat models.

Thermogravimetric analysis, PXRD, EDX and XPS study of chrysocolla (Cu,Al)2H2Si2O5(OH)4·nH2O : structural implications

Selected chrysocolla mineral samples from different origins have been studied by using PXRD, SEM, EDX and XPS. The XRD patterns show that the chrysocolla mineral samples are non-diffracting and no other phases are present in the minerals, thus showing the chrysocolla samples are pure. SEM analyses show the chrysocolla surfaces are featureless. EDX analyses enable the formulae of the chrysocolla samples to be calculated. The thermal decomposition of the mineral chrysocolla has been studied using a combination of thermogravimetric analysis and derivative thermogravimetric analysis. Five thermal decomposition mass loss steps are observed for the chrysocolla from Arizona (a) at 125 ◦C with the loss of water, (b) at 340 ◦C with the loss of hydroxyl units, (c) at 468.5 ◦C with a further loss of hydroxyls, (d) at 821 ◦C with oxygen loss and (e) at 895 ◦C with a further loss of oxygen. The thermal analysis of the chrysocolla from Congo shows mass losses at 125, 275.3, 805.6 and 877.4 ◦C and for the Nevada chrysocolla, mass loss steps at 268, 333, 463, 786.0 and 817.7 ◦C are observed. The thermal analysis of spertiniite is very different from that of chrysocolla and thermally decomposes at around 160 ◦C. XPS shows that there are two different copper species present, one which is bonded to oxygen and one to a hydroxyl unit. The O 1s is broad and very symmetrical suggesting two O species of equal number. The bond energy of 102.9 eV for the Si 2p suggests that it is in the form of a silicate. The bond energy is much higher for silicas around ∼103.5 eV. The reported value for silica gel has Si 2p at 103.4 eV. The combination of TG, PXRD, EDX and XPS adds to our fundamental knowledge of the structure of chrysocolla.

A novel testing system for a Cycloidal drive

At present, for mechanical power transmission, Cycloidal drives are most preferred - for compact, high transmission ratio speed reduction, especially for robot joints and manipulator applications. Research on drive-train dynamics of Cycloidal drives is not well-established. This paper presents a testing rig for Cycloidal drives, which would produce data for development of mathematical models and investigation of drive-train dynamics, further aiding in optimising its design

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.

Load-unloading response of intact and artificially degraded articular cartilage correlated with near infrared (NIR) absorption spectra

The conventional mechanical properties of articular cartilage, such as compressive stiffness, have been demonstrated to be limited in their capacity to distinguish intact (visually normal) from degraded cartilage samples. In this paper, we explore the correlation between a new mechanical parameter, namely the reswelling of articular cartilage following unloading from a given compressive load, and the near infrared (NIR) spectrum. The capacity to distinguish mechanically intact from proteoglycan-depleted tissue relative to the "reswelling" characteristic was first established, and the result was subsequently correlated with the NIR spectral data of the respective tissue samples. To achieve this, normal intact and enzymatically degraded samples were subjected to both NIR probing and mechanical compression based on a load-unload-reswelling protocol. The parameter δ(r), characteristic of the osmotic "reswelling" of the matrix after unloading to a constant small load in the order of the osmotic pressure of cartilage, was obtained for the different sample types. Multivariate statistics was employed to determine the degree of correlation between δ(r) and the NIR absorption spectrum of relevant specimens using Partial Least Squared (PLS) regression. The results show a strong relationship (R(2)=95.89%, p<0.0001) between the spectral data and δ(r). This correlation of δ(r) with NIR spectral data suggests the potential for determining the reswelling characteristics non-destructively. It was also observed that δ(r) values bear a significant relationship with the cartilage matrix integrity, indicated by its proteoglycan content, and can therefore differentiate between normal and artificially degraded proteoglycan-depleted cartilage samples. It is therefore argued that the reswelling of cartilage, which is both biochemical (osmotic) and mechanical (hydrostatic pressure) in origin, could be a strong candidate for characterizing the tissue, especially in regions surrounding focal cartilage defects in joints.

Translating vision research into policy and practice to improve visibility, and hence safety, of road workers at night

This case study report describes the stages involved in the translation of research on night-time visibility into standards for the safety clothing worn by roadworkers. Vision research demonstrates that when lights are placed on the moveable joints of the body and the person moves in a dark setting, the phenomenon known as “biological motion or biomotion” occurs, enabling rapid and accurate recognition of the human form although only the lights can be seen. QUT was successful in gaining funding from the Australian Research Council for a Linkage grant due to the support of the predecessors of the Queensland Department of Transport and Main Roads (TMR) to research the biomotion effect in on-road settings using materials that feature in roadworker clothing. Although positive results were gained, the process of translating the research results into policy, practices and standards relied strongly on the supportive efforts of TMR staff engaged in the review and promulgation of national standards. The ultimate result was the incorporation of biomotion marking into AS/NZS 4602.1 2011. The experiences gained in this case provide insights into the processes involved in translating research into practice.

Oriented graphitic carbon films for hydrogen gas sensors

An oriented graphitic nanostructured carbon film has been employed as a conductometric hydrogen gas sensor. The carbon film was energetically deposited using a filtered cathodic vacuum arc with a -75 V bias applied to a stainless steel grid placed 1cm from the surface of the Si substrate. The substrate was heated to 400°C prior to deposition. Electron microscopy showed evidence that the film consisted largely of vertically oriented graphitic sheets and had a density of 2.06 g/cm3. 76% of the atoms were bonded in sp2 or graphitic configurations. A change in the device resistance of >; 1.5% was exhibited upon exposure to 1 % hydrogen gas (in synthetic, zero humidity air) at 100°C. The time for the sensor resistance to increase by 1.5 % under these conditions was approximately 60 s and the baseline (zero hydrogen exposure) resistance remained constant to within 0.01% during and after the hydrogen exposures.

An FE investigation simulating intra-operative corrective forces applied to correct scoliosis deformity

Background: Adolescent idiopathic scoliosis (AIS) is a deformity of the spine, which may 34 require surgical correction by attaching a rod to the patient’s spine using screws 35 implanted in the vertebral bodies. Surgeons achieve an intra-operative reduction in the 36 deformity by applying compressive forces across the intervertebral disc spaces while 37 they secure the rod to the vertebra. We were interested to understand how the 38 deformity correction is influenced by increasing magnitudes of surgical corrective forces 39 and what tissue level stresses are predicted at the vertebral endplates due to the 40 surgical correction. 41 Methods: Patient-specific finite element models of the osseoligamentous spine and 42 ribcage of eight AIS patients who underwent single rod anterior scoliosis surgery were 43 created using pre-operative computed tomography (CT) scans. The surgically altered 44 spine, including titanium rod and vertebral screws, was simulated. The models were 45 analysed using data for intra-operatively measured compressive forces – three load 46 profiles representing the mean and upper and lower standard deviation of this data 47 were analysed. Data for the clinically observed deformity correction (Cobb angle) were 48 compared with the model-predicted correction and the model results investigated to 49 better understand the influence of increased compressive forces on the biomechanics of 50 the instrumented joints. 51 Results: The predicted corrected Cobb angle for seven of the eight FE models were 52 within the 5° clinical Cobb measurement variability for at least one of the force profiles. 53 The largest portion of overall correction was predicted at or near the apical 54 intervertebral disc for all load profiles. Model predictions for four of the eight patients 55 showed endplate-to-endplate contact was occurring on adjacent endplates of one or 56 more intervertebral disc spaces in the instrumented curve following the surgical loading 57 steps. 58 Conclusion: This study demonstrated there is a direct relationship between intra-59 operative joint compressive forces and the degree of deformity correction achieved. The 60 majority of the deformity correction will occur at or in adjacent spinal levels to the apex 61 of the deformity. This study highlighted the importance of the intervertebral disc space 62 anatomy in governing the coronal plane deformity correction and the limit of this 63 correction will be when bone-to-bone contact of the opposing vertebral endplates 64 occurs.

A finite element model of seat cushion indentation with a soft tissue human occupant model

Effective digital human model (DHM) simulation of automotive driver packaging ergonomics, safety and comfort depends on accurate modelling of occupant posture, which is strongly related to the mechanical interaction between human body soft tissue and flexible seat components. This paper presents a finite-element study simulating the deflection of seat cushion foam and supportive seat structures, as well as human buttock and thigh soft tissue when seated. The three-dimensional data used for modelling thigh and buttock geometry were taken on one 95th percentile male subject, representing the bivariate percentiles of the combined hip breadth (seated) and buttock-to-knee length distributions of a selected Australian and US population. A thigh-buttock surface shell based on this data was generated for the analytic model. A 6mm neoprene layer was offset from the shell to account for the compression of body tissue expected through sitting in a seat. The thigh-buttock model is therefore made of two layers, covering thin to moderate thigh and buttock proportions, but not more fleshy sizes. To replicate the effects of skin and fat, the neoprene rubber layer was modelled as a hyperelastic material with viscoelastic behaviour in a Neo-Hookean material model. Finite element (FE) analysis was performed in ANSYS V13 WB (Canonsburg, USA). It is hypothesized that the presented FE simulation delivers a valid result, compared to a standard SAE physical test and the real phenomenon of human-seat indentation. The analytical model is based on the CAD assembly of a Ford Territory seat. The optimized seat frame, suspension and foam pad CAD data were transformed and meshed into FE models and indented by the two layer, soft surface human FE model. Converging results with the least computational effort were achieved for a bonded connection between cushion and seat base as well as cushion and suspension, no separation between neoprene and indenter shell and a frictional connection between cushion pad and neoprene. The result is compared to a previous simulation of an indentation with a hard shell human finite-element model of equal geometry, and to the physical indentation result, which is approached with very high fidelity. We conclude that (a) SAE composite buttock form indentation of a suspended seat cushion can be validly simulated in a FE model of merely similar geometry, but using a two-layer hard/soft structure. (b) Human-seat indentation of a suspended seat cushion can be validly simulated with a simplified human buttock-thigh model for a selected anthropomorphism.

Hydrogen bonding in two ammonium salts of 5-sulfosalicylic acid : ammonium 3-carboxy-4-hydroxybenzenesulfonate monohydrate and triammonium 3-carboxy-4-hydroxybenzenesulfonate 3-carboxylato-4-hydroxybenzenesulfonate

The structures of two ammonium salts of 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid, 5-SSA) have been determined at 200 K. In the 1:1 hydrated salt, ammonium 3-carboxy-4-hydroxybenzenesulfonate monohydrate, NH4+·C7H5O6S-·H2O, (I), the 5-SSA- monoanions give two types of head-to-tail laterally linked cyclic hydrogen-bonding associations, both with graph-set R44(20). The first involves both carboxylic acid O-HOwater and water O-HOsulfonate hydrogen bonds at one end, and ammonium N-HOsulfonate and N-HOcarboxy hydrogen bonds at the other. The second association is centrosymmetric, with end linkages through water O-HOsulfonate hydrogen bonds. These conjoined units form stacks down c and are extended into a three-dimensional framework structure through N-HO and water O-HO hydrogen bonds to sulfonate O-atom acceptors. Anhydrous triammonium 3-carboxy-4-hydroxybenzenesulfonate 3-carboxylato-4-hydroxybenzenesulfonate, 3NH4+·C7H4O6S2-·C7H5O6S-, (II), is unusual, having both dianionic 5-SSA2- and monoanionic 5-SSA- species. These are linked by a carboxylic acid O-HO hydrogen bond and, together with the three ammonium cations (two on general sites and the third comprising two independent half-cations lying on crystallographic twofold rotation axes), give a pseudo-centrosymmetric asymmetric unit. Cation-anion hydrogen bonding within this layered unit involves a cyclic R33(8) association which, together with extensive peripheral N-HO hydrogen bonding involving both sulfonate and carboxy/carboxylate acceptors, gives a three-dimensional framework structure. This work further demonstrates the utility of the 5-SSA- monoanion for the generation of stable hydrogen-bonded crystalline materials, and provides the structure of a dianionic 5-SSA2- species of which there are only a few examples in the crystallographic literature.

Segmental torso masses and coronal plane joint torques in the adolescent scoliotic spine

Introduction. Calculating segmental (vertebral level-by-level) torso masses in Adolescent Idiopathic Scoliosis (AIS) patients allows the gravitational loading on the scoliotic spine during relaxed standing to be determined. This study used CT scans of AIS patients to measure segmental torso masses and explores how joint moments in the coronal plane are affected by changes in the position of the intervertebral joint’s axis of rotation; particularly at the apex of a scoliotic major curve. Methods. Existing low dose CT data from the Paediatric Spine Research Group was used to calculate vertebral level-by-level torso masses and joint torques occurring in the spine for a group of 20 female AIS patients (mean age 15.0 ± 2.7 years, mean Cobb angle 53 ± 7.1°). Image processing software, ImageJ (v1.45 NIH USA) was used to threshold the T1 to L5 CT images and calculate the segmental torso volume and mass corresponding to each vertebral level. Body segment masses for the head, neck and arms were taken from published anthropometric data. Intervertebral (IV) joint torques at each vertebral level were found using principles of static equilibrium together with the segmental body mass data. Summing the torque contributions for each level above the required joint, allowed the cumulative joint torque at a particular level to be found. Since there is some uncertainty in the position of the coronal plane Instantaneous Axis of Rotation (IAR) for scoliosis patients, it was assumed the IAR was located in the centre of the IV disc. A sensitivity analysis was performed to see what effect the IAR had on the joint torques by moving it laterally 10mm in both directions. Results. The magnitude of the torso masses from T1-L5 increased inferiorly, with a 150% increase in mean segmental torso mass from 0.6kg at T1 to 1.5kg at L5. The magnitudes of the calculated coronal plane joint torques during relaxed standing were typically 5-7 Nm at the apex of the curve, with the highest apex joint torque of 7Nm being found in patient 13. Shifting the assumed IAR by 10mm towards the convexity of the spine, increased the joint torque at that level by a mean 9.0%, showing that calculated joint torques were moderately sensitive to the assumed IAR location. When the IAR midline position was moved 10mm away from the convexity of the spine, the joint torque reduced by a mean 8.9%. Conclusion. Coronal plane joint torques as high as 7Nm can occur during relaxed standing in scoliosis patients, which may help to explain the mechanics of AIS progression. This study provides new anthropometric reference data on vertebral level-by-level torso mass in AIS patients which will be useful for biomechanical models of scoliosis progression and treatment. However, the CT scans were performed in supine (no gravitational load on spine) and curve magnitudes are known to be smaller than those measured in standing.

Growth of C36-films on diamond surface through molecular dynamics simulation

In this paper, the initial stage of films assembled by energetic C36 fullerenes on diamond (001)–(2 × 1) surface at low-temperature was investigated by molecular dynamics simulation using the Brenner potential. The incident energy was first uniformly distributed within an energy interval 20–50 eV, which was known to be the optimum energy range for chemisorption of single C36 on diamond (001) surface. More than one hundred C36 cages were impacted one after the other onto the diamond surface by randomly selecting their orientation as well as the impact position relative to the surface. The growth of films was found to be in three-dimensional island mode, where the deposited C36 acted as building blocks. The study of film morphology shows that it retains the structure of a free C36 cage, which is consistent with Low Energy Cluster Beam Deposition (LECBD) experiments. The adlayer is composed of many C36-monomers as well as the covalently bonded C36 dimers and trimers which is quite different from that of C20 fullerene-assembled film, where a big polymerlike chain was observed due to the stronger interaction between C20 cages. In addition, the chemisorption probability of C36 fullerenes is decreased with increasing coverage because the interaction between these clusters is weaker than that between the cluster and the surface. When the incident energy is increased to 40–65 eV, the chemisorption probability is found to increased and more dimers and trimers as well as polymerlike-C36 were observed on the deposited films. Furthermore, C36 film also showed high thermal stability even when the temperature was raised to 1500 K.

Thermal analysis and vibrational spectroscopic characterization of the boro silicate mineral datolite – CaBSiO4(OH)

The objective of this work is to determine the thermal stability and vibrational spectra of datolite CaBSiO4(OH) and relate these properties to the structure of the mineral. The thermal analysis of datolite shows a mass loss of 5.83% over a 700–775 °C temperature range. This mass loss corresponds to 1 water (H2O) molecules pfu. A quantitative chemical analysis using electron probe was undertaken. The Raman spectrum of datolite is characterized by bands at 917 and 1077 cm−1 assigned to the symmetric stretching modes of BO and SiO tetrahedra. A very intense Raman band is observed at 3498 cm−1 assigned to the stretching vibration of the OH units in the structure of datolite. BOH out-of-plane vibrations are characterized by the infrared band at 782 cm−1. The vibrational spectra are based upon the structure of datolite based on sheets of four- and eight-membered rings of alternating SiO4 and BO3(OH) tetrahedra with the sheets bonded together by calcium atoms.

Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces. Part 3. -- Fourier-transform infrared study of methyl formate adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

FTIR spectra are reported of methyl formate adsorbed at 295 K on ZnO/SiO2, reduced Cu/ZnO/SiO2 and on Cu/ZnO/SiO2 which had been preoxidised by exposure to nitrous oxide. Methyl formate on ZnO/SiO2 gave adsorbed zinc formate species and strongly physisorbed molecular methanol on silica. The comparable reaction of methyl formate with reduced Cu/ZnO/SiO2 catalyst produced bridging formate species on copper and a diminished quantity of zinc formate relative to that formed on ZnO/SiO2 catalyst. This effect is explained in terms of site blockage on the ZnO surface by small copper clusters. Addition of methyl formate to a reoxidised Cu/ZnO/SiO2 catalyst produced a considerably greater amount of formate species on zinc oxide and methoxy groups on copper were detected. The increase in concentration of zinc formate species was rationalised in terms of rearrangement of unidentate copper formate species to become bonded to copper and zinc oxide sites located at the interface between these two components.

Comprehensive study of surface chemistry of MCM-41 using 29Si CP/MAS NMR, FTIR, pyridine-TPD, and TGA

A comprehensive study was conducted on mesoporous MCM-41. Spectroscopic examinations demonstrated that three types of silanol groups, i.e., single, (SiO)3Si-OH, hydrogen-bonded, (SiO)3Si-OH-OH-Si(SiO)3, and geminal, (SiO)2Si(OH)2, can be observed. The number of silanol groups/nm2, ?OH, as determined by NMR, varies between 2.5 and 3.0 depending on the template-removal methods. All these silanol groups were found to be the active sites for adsorption of pyridine with desorption energies of 91.4 and 52.2 kJ mol-1, respectively. However, only free silanol groups (involving single and geminal silanols) are highly accessible to the silylating agent, chlorotrimethylsilane. Silylation can modify both the physical and chemical properties of MCM-41.