Near infrared spectroscopic imaging assessment of cartilage composition: Validation with mid infrared imaging spectroscopy

Disease or injury to articular cartilage results in loss of extracellular matrix components which can lead to the development of osteoarthritis (OA). To better understand the process of disease development, there is a need for evaluation of changes in cartilage composition without the requirement of extensive sample preparation. Near infrared (NIR) spectroscopy is a chemical investigative technique based on molecular vibrations that is increasingly used as an assessment tool for studying cartilage composition. However, the assignment of specific molecular vibrations to absorbance bands in the NIR spectrum of cartilage, which arise from overtones and combinations of primary absorbances in the mid infrared (MIR) spectral region, has been challenging. In contrast, MIR spectroscopic assessment of cartilage is well-established, with many studies validating the assignment of specific bands present in MIR spectra to specific molecular vibrations. In the current study, NIR imaging spectroscopic data were obtained for compositional analysis of tissues that served as an in vitro model of OA. MIR spectroscopic data obtained from the identical tissue regions were used as the gold-standard for collagen and proteoglycan (PG) content. MIR spectroscopy in transmittance mode typically requires a much shorter pathlength through the sample (≤10 microns thick) compared to NIR spectroscopy (millimeters). Thus, this study first addressed the linearity of small absorbance bands in the MIR region with increasing tissue thickness, suitable for obtaining a signal in both the MIR and NIR regions. It was found that the linearity of specific, small MIR absorbance bands attributable to the collagen and PG components of cartilage (at 1336 and 856 cm⁻¹, respectively) are maintained through a thickness of 60 μm, which was also suitable for NIR data collection. MIR and NIR spectral data were then collected from 60 μm thick samples of cartilage degraded with chondroitinase ABC as a model of OA. Partial least squares (PLS) regression using NIR spectra as input predicted the MIR-determined compositional parameters of PG/collagen within 6% of actual values. These results indicate that NIR spectral data can be used to assess molecular changes that occur with cartilage degradation, and further, the data provide a foundation for future clinical studies where NIR fiber optic probes can be used to assess the progression of cartilage degradation.     

Synthesis and crystal structure of the dinuclear copper(II) Schiff base complex μ‐hydroxido‐μ‐chlorido‐bis{[bis(trans‐2‐nitrocinnamaldehyde)ethylenediamine]chloridocopper(II)} dichloromethane sesquisolvate

Transition metal complexes of Schiff base ligands have been shown to have particular application in catalysis and magnetism. The chemistry of copper complexes is of interest owing to their importance in biological and industrial processes. The reaction of copper(I) chloride with the bidentate Schiff base N,N′‐bis(trans‐2‐nitrocinnamaldehyde)ethylenediamine {Nca₂en, systematic name: (1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]} in a 1:1 molar ratio in dichloromethane without exclusion of air or moisture resulted in the formation of the title complex μ‐chlorido‐μ‐hydroxido‐bis(chlorido{(1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]‐κ²N,N′}copper(II)) dichloromethane sesquisolvate, [Cu₂Cl₃(OH)(C₂₀H₁₈N₄O₄)₂]·1.5CH₂Cl₂. The dinuclear complex has a folded four‐membered ring in an unsymmetrical Cu₂OCl₃ core in which the approximate trigonal bipyramidal coordination displays different angular distortions in the equatorial planes of the two Cu^II atoms; the chloride bridge is asymmetric, but the hydroxide bridge is symmetric. The chelate rings of the two Nca₂en ligands have different conformations, leading to a more marked bowing of one of the ligands compared with the other. This is the first reported dinuclear complex, and the first five‐coordinate complex, of the Nca₂en Schiff base ligand. Molecules of the dimer are associated in pairs by ring‐stacking interactions supported by C—H…Cl interactions with solvent molecules; a further ring‐stacking interaction exists between the two Schiff base ligands of each molecule.     

Oligodeoxynucleotides incorporating structurally simple 5-alkynyl-2'-deoxyuridines fluorometrically respond to hybridization

Selected 5-ethynyl derivatives of 2'-deoxyuridine are shown to fluorometrically respond to hybridization and selectively base-pair to adenine whilst maintaining duplex stability.     

Nonrigid group theory for 1,3,5‐trimethylbenzene

Using nonrigid group theory, the full nonrigid (f‐NRG) group of 1,3,5‐trimethylbenzene (TMB) is shown to be isomorphic to the group S₃[C₃] = C₃ S₃ of order 162, where denotes the wreath product of groups, and C₃ is the cyclic group of order three and S₃ is the symmetric group of order six on three letters. This group has 22 conjugacy classes and irreducible representations. The character table of the full nonrigid TMB is then derived for the first time. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

A framework for synthetic validation of 3D echocardiographic particle image velocimetry

Particle image velocimetry (PIV) has been significantly advanced since its conception in early 1990s. With the advancement of imaging modalities, applications of 2D PIV have far expanded into biology and medicine. One example is echocardiographic particle image velocimetry that is used for in vivo mapping of the flow inside the heart chambers with opaque boundaries. Velocimetry methods can help better understanding the biomechanical problems. The current trend is to develop three-dimensional velocimetry techniques that take advantage of modern medical imaging tools. This study provides a novel framework for validation of velocimetry methods that are inherently three dimensional such as but not limited to those acquired by 3D echocardiography machines. This framework creates 3D synthetic fields based on a known 3D velocity field \({\mathbf{V}}\) and a given 3D brightness field \({\mathbf{B}}\). The method begins with computing the inverse flow \({\mathbf{V}}^{\varvec{*}} \) based on the velocity field \({\mathbf{V}}\). Then the transformation of \({\mathbf{B}}\), imposed by \({\mathbf{V}}\), is calculated using the computed inverse flow according to \({\mathbf{B}}^{\varvec{*}} \left( {\mathbf{x}} \right) = {\mathbf{B}}\left( {{\mathbf{x}} + {\mathbf{V}}^{\varvec{*}} \left( {\mathbf{x}} \right)} \right)\), where x is the coordinates of voxels in \({\mathbf{B}}^{\varvec{*}} \), with a 3D weighted average interpolation, which provides high accuracy, low memory requirement, and low computational time. To check the validity of the framework, we generate pairs of 3D brightness fields by employing Hill’s spherical vortex velocity field. \({\mathbf{B}}\) and the generated \({\mathbf{B}}^{\varvec{*}} \) are then processed by our in-house 3D particle image velocimetry software to obtain the interrelated velocity field. The results indicates that the computed and imposed velocity fields are in agreement.     

A Novel Catalytic Method for the Oxidation of Sulfides to Sulfoxides with Silica Sulfuric Acid and Sodium Nitrite in the Presence of KBr and/or NaBr as Catalyst

Highly efficient selective oxidation of sulfides to sulfoxides by NaNO₂ and silica sulfuric acid catalyzed with KBr or NaBr has been reported. This oxidation was carried out in the presence of wet SiO₂ (50% w/w) in acetonitrile at room temperature with good to excellent yields.     

The synthesis of 3,3‐dimethyl‐2‐(1‐aryl‐1h‐pyrazol‐4‐yl)‐3h‐indoles

2,3,3‐Trimethylindolenine and 5‐chloro‐2,3,3‐trimethylindolenine were converted into β‐diformyl compounds by the action of the Vilsmeier reagent at 50°C. The dialdehydes reacted with various arylhydrazines and 2‐pyridylhydrazine to produce mono‐hydrazones as mixtures of cis and trans isomers. Heating the hydrazones in refluxing ethanol produced 3,3‐dimethyl‐2‐(1‐aryl‐1H‐pyrazol‐4‐yl)‐3H‐indoles in excellent yields. Reaction of the β‐diformyl compounds with hydrazine itself led directly to 3,3‐dimethyl‐2‐(pyrazol‐4‐yl)‐3H‐indoles.     

Compatibility Equations of Nonlinear Elasticity for Non-Simply-Connected Bodies

Compatibility equations of elasticity are almost 150 years old. Interestingly, they do not seem to have been rigorously studied, to date, for non-simply-connected bodies. In this paper we derive necessary and sufficient compatibility equations of nonlinear elasticity for arbitrary non-simply-connected bodies when the ambient space is Euclidean. For a non-simply-connected body, a measure of strain may not be compatible, even if the standard compatibility equations (“bulk” compatibility equations) are satisfied. It turns out that there may be topological obstructions to compatibility; this paper aims to understand them for both deformation gradient F and the right Cauchy-Green strain C = F ^T F. We show that the necessary and sufficient conditions for compatibility of deformation gradient F are the vanishing of its exterior derivative and all its periods, that is, its integral over generators of the first homology group of the material manifold. We will show that not every non-null-homotopic path requires supplementary compatibility equations for F and linearized strain e. We then find both necessary and sufficient compatibility conditions for the right Cauchy-Green strain tensor C for arbitrary non-simply-connected bodies when the material and ambient space manifolds have the same dimensions. We discuss the well-known necessary compatibility equations in the linearized setting and the Cesàro-Volterra path integral. We then obtain the sufficient conditions of compatibility for the linearized strain when the body is not simply-connected. To summarize, the question of compatibility reduces to two issues: i) an integrability condition, which is d(F dX) = 0 for the deformation gradient and a curvature vanishing condition for C, and ii) a topological condition. For F dx this is a homological condition because the equation one is trying to solve takes the form dφ = F dX. For C, however, parallel transport is involved, which means that one needs to solve an equation of the form dR/ ds = RK, where R takes values in the orthogonal group. This is, therefore, a question about an orthogonal representation of the fundamental group, which, as the orthogonal group is not commutative, cannot, in general, be reduced to a homological question.