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.

Continuum mechanics modelling of microfilament networks with different architectures based on molecular investigation of single F-actin

The actin microfilament plays a critical role in many cellular processes including embryonic development, wound healing, immune response, and tissue development. It is commonly organized in the form of networks whose mechanical properties change with changes in their architecture due to cell evolution processes. This paper presents a new nonlinear continuum mechanics model of single filamentous actin (F-actin) that is based on nanoscale molecular simulations. Following this continuum model of the single F-actin, mechanical properties of differently architected lamellipodia are studied. The results provide insight that can contribute to the understanding of the cell edge motions of living cells.

Ruthenium(II) dichloro or dithiocyanato complexes with 4,4′:2′,2″:4″,4‴-quaterpyridinium ligands : towards photosensitisers with enhanced low-energy absorption properties

Fourteen new complexes of the form cis-\[RuIIX2(R2qpy2+)2]4+ (R2qpy2+ = a 4,4′:2′,2″:4″,4‴-quaterpyridinium ligand, X = Cl− or NCS−) have been prepared and isolated as their PF6− salts. Characterisation involved various techniques including 1H NMR spectroscopy and +electrospray or MALDI mass spectrometry. The UV–Vis spectra display intense intraligand π → π∗ absorptions, and also metal-to-ligand charge-transfer (MLCT) bands with two resolved maxima in the visible region. Red-shifts in the MLCT bands occur as the electron-withdrawing strength of the pyridinium groups increases, while replacing Cl− with NCS− causes blue-shifts. Cyclic voltammograms show quasi-reversible or reversible RuIII/II oxidation waves, and several ligand-based reductions that are irreversible. The variations in the redox potentials correlate with changes in the MLCT energies. A single-crystal X-ray structure has been obtained for a protonated form of a proligand salt, \[(4-(CO2H)Ph)2qpyH3+]\[HSO4]3·3H2O. Time-dependent density functional theory calculations give adequate correlations with the experimental UV–Vis spectra for the two carboxylic acid-functionalised complexes in DMSO. Despite their attractive electronic absorption spectra, these dyes are relatively inefficient photosensitisers on electrodes coated with TiO2 or ZnO. These observations are attributed primarily to weak electronic coupling with the surfaces, since the DFT-derived LUMOs include no electron density near the carboxylic acid anchors.

Molecular dynamics investigation on edge stress and shape transition in graphene nanoribbons

Graphene nanoribbon (GNR) with free edges demonstrates unique pre-existing edge energy and edge stress, leading to non-flat morphologies. Using molecular dynamics (MD) methods, we evaluated edge energies as well as edge stresses for four different edge types, including regular edges (armchair and zigzag), armchair edge terminated with hydrogen and reconstructed armchair. The results showed that compressive stress exists in the regular and hydrogen-terminated edges along the edge direction. In contrast, the reconstructed armchair edge is generally subject to tension. Furthermore, we also investigated shape transition between flat and rippled configurations of GNRs with different free edges. It was found that the pre-existing stress at free edges can greatly influence the initial energy state and the shape transition.

A vibrational spectroscopic study of philipsbornite PbAl3(AsO4)2(OH)5⋅H2O-molecular structural implications and relationship to the crandallite subgroup arsenates

The presence of arsenic in the environment is a hazard. The accumulation of arsenate by a range of cations in the formation of minerals provides a mechanism for the remediation of arsenate contamination. The formation of the crandallite group of minerals provides a mechanism for arsenate accumulation. Among the crandallite minerals are philipsbornite, arsenocrandallite and arsenogoyazite. Raman spectroscopy complimented with infrared spectroscopy has enabled aspects of the structure of philipsbornite to be studied. The Raman spectrum of philipsbornite displays an intense band at around 840 cm−1 attributed to the overlap of the symmetric and antisymmetric stretching modes. Raman bands observed at 325, 336, 347, 357, 376 and 399 cm−1 are assigned to the ν2 (AsO4)3− symmetric bending vibration (E) and to the ν4 bending vibration (F2). The observation of multiple bending modes supports the concept of a reduction in symmetry of the arsenate anion in philipsbornite. Evidence for phosphate in the mineral is provided. By using an empirical formula, hydrogen bond distances for the OH units in philipsbornite of 2.8648 Å, 2.7864 Å, 2.6896 Å cm−1 and 2.6220 were calculated.

The molecular structure of matioliite – NaMgAl5(PO4)4(OH)6·2(H2O) : a pegmatite mineral from Minas Gerais, Brazil

Detailed spectroscopic and chemical investigation of matioliite, including infrared and Raman spectroscopy, scanning electron microscopy and electron probe microanalysis has been carried out on homogeneous samples from the Gentil pegmatite, Mendes Pimentel, Minas Gerais, Brazil. The chemical composition is (wt.%): FeO 2.20, CaO 0.05, Na2O 1.28, MnO 0.06, Al2O3 39.82, P2O5 42.7, MgO 4.68, F 0.02 and H2O 9.19; total 100.00. The mineral crystallize in the monoclinic crystal system, C2/c space group, with a = 25.075(1) Å, b = 5.0470(3) Å, c = 13.4370(7) Å, β = 110.97(3)°, V = 1587.9(4) Å3, Z = 4. Raman spectroscopy coupled with infrared spectroscopy supports the concept of phosphate, hydrogen phosphate and dihydrogen phosphate units in the structure of matioliite. Infrared and Raman bands attributed to water and hydroxyl stretching modes are identified. Vibrational spectroscopy adds useful information to the molecular structure of matioliite.

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.

Hydrogen spillover mechanism on a pd-doped mg surface as revealed by ab initio density functional calculation

The hydrogenation kinetics of Mg is slow, impeding its application for mobile hydrogen storage. We demonstrate by ab initio density functional theory (DFT) calculations that the reaction path can be greatly modified by adding transition metal catalysts. Contrasting with Ti doping, a Pd dopant will result in a very small activation barrier for both dissociation of molecular hydrogen and diffusion of atomic H on the Mg surface. This new computational finding supports for the first time by ab initio simulationthe proposed hydrogen spillover mechanism for rationalizing experimentally observed fast hydrogenation kinetics for Pd-capped Mg materials.

The molecular structure of the phosphate mineral chalcosiderite – a vibrational spectroscopic study

The mineral chalcosiderite with formula CuFe6(PO4)4(OH)8⋅4H2O has been studied by Raman spectroscopy and by infrared spectroscopy. A comparison of the chalcosiderite spectra is made with the spectra of turquoise. The spectra of the mineral samples are very similar in the 1200–900 cm−1 region but strong differences are observed in the 900–100 cm−1 region. The effect of substitution of Fe for Al in chalcosiderite shifts the bands to lower wave numbers. Factor group analysis (FGA) implies four OH stretching vibrations for both the water and hydroxyl units. Two bands ascribed to water are observed at 3276 and 3072 cm−1. Three hydroxyl stretching vibrations are observed. Calculations using a Libowitzky type formula show that the hydrogen bond distances of the water molecules are 2.745 and 2.812 Å which are considerably shorter than the values for the hydroxyl units 2.896, 2.917 and 2.978 Å. Two phosphate stretching vibrations at 1042 and 1062 cm−1 in line with the two independent phosphate units in the structure of chalcosiderite. Three bands are observed at 1102, 1159 and 1194 cm−1 assigned to the phosphate antisymmetric stretching vibrations. FGA predicts six bands but only three are observed due to accidental degeneracy. Both the ν2 and ν4 bending regions are complex. Four Raman bands observed at 536, 580, 598 and 636 cm−1 are assigned to the ν4 bending modes. Raman bands at 415, 420, 475 and 484 cm−1are assigned to the phosphate ν2 bending modes. Vibrational spectroscopy enables aspects of the molecular structure of chalcosiderite to be assessed.

Molecular dynamics simulation of fracture strength and morphology of defective graphene

Different types of defects can be introduced into graphene during material synthesis, and significantly influence the properties of graphene. In this work, we investigated the effects of structural defects, edge functionalisation and reconstruction on the fracture strength and morphology of graphene by molecular dynamics simulations. The minimum energy path analysis was conducted to investigate the formation of Stone-Wales defects. We also employed out-of-plane perturbation and energy minimization principle to study the possi-ble morphology of graphene nanoribbons with edge-termination. Our numerical results show that the fracture strength of graphene is dependent on defects and environmental temperature. However, pre-existing defects may be healed, resulting in strength recovery. Edge functionalization can induce compressive stress and ripples in the edge areas of gra-phene nanoribbons. On the other hand, edge reconstruction contributed to the tensile stress and curved shape in the graphene nanoribbons.

Insights into the nature of the coupling interactions between uracil corrosion inhibitors and copper : a DFT and molecular dynamics study

In this study, the nature of the coupling interactions between copper and uracil as well as its several derivatives has been systematically investigated employing the atoms in molecules (AIM) theory and energy decomposition analyses. The whole interaction process has been investigated through the analyses of the radial distribution functions of the Cu⋯X (X = S and O) contact on the basis of the ab initio molecular dynamics. No direct relationship between the adsorption strengths and inhibition efficiencies of the inhibitors has been observed. Additionally, the possibility of the methyl-substituted dithiouracil species to act as copper corrosion inhibitors has been tested.

Water absorption, permeability, and resistance to chloride-ion penetration of lightweight aggregate concrete

This paper presents an experimental study to evaluate effect of cumulative lightweight aggregate (LWA) content (including lightweight sand) in concrete [water/cement ratio (w/c) = 0.38] on its water absorption, water permeability, and resistance to chloride-ion penetration. Rapid chloride penetrability test (ASTM C 1202), rapid migration test (NT Build 492), and salt ponding test (AASHTO T 259) were conducted to evaluate the concrete resistance to chloride-ion penetration. The results were compared with those of a cement paste and a control normal weight aggregate concrete (NWAC) with the same w/c and a NWAC (w/c = 0.54) with 28-day compressive strength similar to some of the lightweight aggregate concrete (LWAC). Results indicate that although the total charge passed, migration coefficient, and diffusion coefficient of the LWAC were not significantly different from those of NWAC with the same w/c of 0.38, resistance of the LWAC to chloride penetration decreased with increase in the cumulative LWA content in the concretes. The water penetration depth under pressure and water sorptivity showed, in general, similar trends. The LWAC with only coarse LWA had similar water sorptivity, water permeability coefficient, and resistance to chloride-ion penetration compared to NWAC with similar w/c. The LWAC had lower water sorptivity, water permeability and higher resistance to chloride-ion penetration than the NWAC with similar 28-day strength but higher w/c. Both the NWAC and LWAC had lower sorptivity and higher resistance to chloride-ion penetration than the cement paste with similar w/c.

The molecular structure of the phosphate mineral väyrynenite : a vibrational spectroscopic study

We have studied the mineral väyrynenite from the Viitaniemi pegmatite, located in the Eräjärvi area, Finland using a combination of electron microscopy electron microprobe and vibrational spectroscopic techniques. Chemical analysis shows the formula of the mineral to be (Mn0.88,Fe0.08,Mg0.01)∑0.97Be1.02(PO4)1.00(OH)1.02. Vibrational spectroscopy enables an assessment of the molecular structure of väyrynenite to be assessed. An intense Raman band at 1004 cm−1 is to the ν1 symmetric stretching mode. The observation of multiple bands in the phosphate stretching region, offers support for the concept of different phosphate units in the väyrynenite structure. Infrared spectroscopy confirms this multiplicity of vibrational bands. Multiple bands are observed in the phosphate bending region.

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.

The molecular structure of the phosphate mineral senegalite Al2(PO4)(OH)3⋅3H2O – A vibrational spectroscopic study

We have studied the mineral senagalite, a hydrated hydroxy phosphate of aluminium with formula Al2(PO4)(OH)3⋅3H2O using a combination of electron microscopy and vibrational spectroscopy. Senegalite crystal aggregates shows tabular to prismatic habitus and orthorhombic form. The Raman spectrum is dominated by an intense band at 1029 cm−1 assigned to the PO43- ν1 symmetric stretching mode. Intense Raman bands are found at 1071 and 1154 cm−1 with bands of lesser intensity at 1110, 1179 and 1206 cm−1 and are attributed to the PO43- ν3 antisymmetric stretching vibrations. The infrared spectrum shows complexity with a series overlapping bands. A comparison is made with spectra of other aluminium containing phosphate minerals such as augelite and turquoise. Multiple bands are observed for the phosphate bending modes giving support for the reduction of symmetry of the phosphate anion. Vibrational spectroscopy offers a means for the assessment of the structure of senagalite.