Vibration-based elastic parameter identification of the diploë and cortical tables in dry cranial bones.

Various human skull models feature a layered cranial structure composed of homogeneous cortical tables and the inner diploë. However, there is a lack of fundamental validation work of such three-layer cranial bone models by combining high-fidelity computational modeling and rigorous experiments. Here, non-contact vibration experiments are conducted on an assortment of dry bone segments from the largest cranial bone regions (parietal, frontal, occipital, and temporal) to estimate the first handful of modal frequencies and damping ratios, as well as mode shapes, in the audio frequency regime. Numerical models that consider the cortical tables and the diploë as domains with separate isotropic material properties are constructed for each bone segment using a routine that identifies the cortical table-diploë boundaries from micro-computed tomography scan images, and reconstructs a three-dimensional geometry layer by layer. The material properties for cortical tables and diploë are obtained using a Hounsfield Unit-based mass density calculation combined with a parameter identification scheme for Young's modulus estimation. With the identified parameters, the average error between experimental and numerical modal frequencies is 1.3% and the modal assurance criterion values for most modes are above 0.90, indicating that the layered model is suitable for predicting the vibrational behavior of cranial bone. The proposed layered modeling and identified elastic parameters are also useful to support computational modeling of cranial guided waves and mode conversion in medical ultrasound. Additionally, the diploë elastic properties are rarely reported in the literature, making this work a fundamental characterization effort that can guide in the selection of material properties for human head models that consider layered cranial bone.

Determining the time of death by morphological and immunohistochemical evaluation of collagen fibers in postmortem gingival tissues.

The estimation of the post mortem interval (PMI) is still one of the most challenging variables to determine and the different approaches currently used in its estimation generally yield to large post mortem windows. In the present study we combined morphological and immunohistochemical analysis in order to reach a more detailed knowledge on tissue organization and degradation after death. Ultrastructural cellular changes and the extracellular matrix of gingival tissues, collected at different post mortem intervals, were observed by a Transmission Electron Microscopy (TEM), in combination with the immunohistochemical detection of extracellular matrix proteins (i.e. collagen type I and collagen type III) as potential post mortem biochemical markers. The final goal was to find a correlation between morphological modifications, biomarkers expression and the time of death. Samples of gingival tissues obtained from 10 cadavers at different post mortem intervals (short post mortem interval, 1-3 days; mid post mortem interval, 4-6 days; long post mortem interval, 7-9 days) were processed for light microscopy and TEM and they were also immunostained with anti-collagen type I and type III antibodies. Results showed gradual degradation of extracellular matrix in the suboral connective tissue in relation to the different time of death. Moreover PMI was related to an increase of nuclear chromatin condensation and cytoplasmic vacuolization both in epithelial and connective tissues. In conclusion, in addition to traditional forensic approaches to estimate PMI, the combined analyses of cellular morphology, ultrastructure and immunohistochemical expression of collagen proteins allow to better infer the PMI.

Computation of leaky guided waves dispersion spectrum using vibroacoustic analyses and the Matrix Pencil Method: a validation study for immersed rectangular waveguides.

The paper aims at validating a recently proposed Semi Analytical Finite Element (SAFE) formulation coupled with a 2.5D Boundary Element Method (2.5D BEM) for the extraction of dispersion data in immersed waveguides of generic cross-section. To this end, three-dimensional vibroacoustic analyses are carried out on two waveguides of square and rectangular cross-section immersed in water using the commercial Finite Element software Abaqus/Explicit. Real wavenumber and attenuation dispersive data are extracted by means of a modified Matrix Pencil Method. It is demonstrated that the results obtained using the two techniques are in very good agreement.

Dispersion analysis of leaky guided waves in fluid-loaded waveguides of generic shape.

A fully coupled 2.5D formulation is proposed to compute the dispersive parameters of waveguides with arbitrary cross-section immersed in infinite inviscid fluids. The discretization of the waveguide is performed by means of a Semi-Analytical Finite Element (SAFE) approach, whereas a 2.5D BEM formulation is used to model the impedance of the surrounding infinite fluid. The kernels of the boundary integrals contain the fundamental solutions of the space Fourier-transformed Helmholtz equation, which governs the wave propagation process in the fluid domain. Numerical difficulties related to the evaluation of singular integrals are avoided by using a regularization procedure. To improve the numerical stability of the discretized boundary integral equations for the external Helmholtz problem, the so called CHIEF method is used. The discrete wave equation results in a nonlinear eigenvalue problem in the complex axial wavenumbers that is solved at the frequencies of interest by means of a contour integral algorithm. In order to separate physical from non-physical solutions and to fulfill the requirement of holomorphicity of the dynamic stiffness matrix inside the complex wavenumber contour, the phase of the radial bulk wavenumber is uniquely defined by enforcing the Snell-Descartes law at the fluid-waveguide interface. Three numerical applications are presented. The computed dispersion curves for a circular bar immersed in oil are in agreement with those extracted using the Global Matrix Method. Novel results are presented for viscoelastic steel bars of square and L-shaped cross-section immersed in water.

A coupled SAFE-2.5D BEM approach for the dispersion analysis of damped leaky guided waves in embedded waveguides of arbitrary cross-section.

The paper presents a Semi-Analytical Finite Element (SAFE) formulation coupled with a 2.5D Boundary Element Method (BEM) for the computation of the dispersion properties of viscoelastic waveguides with arbitrary cross-section and embedded in unbounded isotropic viscoelastic media. Attenuation of guided modes is described through the imaginary component of the axial wavenumber, which accounts for material damping, introduced via linear viscoelastic constitutive relations, as well as energy loss due to radiation of bulk waves in the surrounding media. Energy radiation is accounted in the SAFE model by introducing an equivalent dynamic stiffness matrix for the surrounding medium, which is derived from a regularized 2.5D boundary element formulation. The resulting dispersive wave equation is configured as a nonlinear eigenvalue problem in the complex axial wavenumber. The eigenvalue problem is reduced to a linear one inside a chosen contour in the complex plane of the axial wavenumber by using a contour integral method. Poles of leaky and evanescent modes are obtained by choosing appropriately the phase of the wavenumbers normal to the interface in compliance with the nature of the waves in the surrounding medium. Finally, the obtained eigensolutions are post-processed to compute the energy velocity and the radiated wavefield in the surrounding domain. The reliability of the method is first validated on existing results for waveguides of circular cross sections embedded in elastic and viscoelastic media. Next, the potential of the proposed numerical framework is shown by computing the dispersion properties for a square steel bar embedded in grout and for an H-shaped steel pile embedded in soil.

Supercritical fluid simulated moving bed chromatography II. Langmuir isotherm.

The simulated moving bed (SMB) technology offers the possibility of scaling up single column, batch chromatographic separations to continuous operation. This has proved particularly effective for the separation of enantiomers, and has been applied in the liquid and gas phase, as well as using a supercritical fluid as eluent (SF-SMB). In the last case, the main performance improvements are due to the possibility of tuning the elution strength of the mobile phase, by changing the pressure in the four sections of the SMB unit. Thus a SF-SMB can be operated in two modes, i.e. the isocratic and the pressure gradient mode. In this research, design criteria for these two operating modes have been developed, which can be applied to systems described by linear as well as nonlinear Langmuir adsorption isotherms. The role and effect of an appropriate modifier in increasing solubility and reducing retention times have been investigated. The results reported allow to identify the operating conditions, including the pressure levels and the modifier concentration, which lead to optimal separation performance in terms of productivity and desorbent requirement.

On-line monitoring of enantiomer concentration in chiral simulated moving bed chromatography.

Simulated moving bed chromatography is a key technology for the pilot and production scale separation of enantiomers of chiral chemical species. Product quality control is probably the most important issue in this kind of separation at both scales, and for this it is clear that on-line monitoring of absolute enantiomer concentrations plays a major role. In this work, an on-line system consisting of a UV detector and a polarimeter in series is used to monitor the composition of the extract and raffinate streams of a laboratory SMB unit. The model system adopted is the separation of the enantiomers of the Tröger's base on microcrystalline cellulose triacetate (CTA) using ethanol as mobile phase. The technique is effective and accurate, thus providing promising perspectives for SMB process control and dynamic optimization.

Regioselective enzymatic diol esterification in batch and fixed-Bed adsorptive reactors: experiments and modeling.

The dynamic behavior of batch and fixed-bed adsorptive reactors is studied for the enzyme-catalyzed regioselective esterification of propionic acid and 2-ethyl-1,3-hexanediol in hexane. The reaction is equilibrium-limited with an apparent equilibrium constant of 0.6 +/- 0.1 at 22 degrees C. Moreover, accumulation of water produced in the reaction onto the biocatalyst causes a decrease in the catalytic activity. As a result, improvements in both reaction rate and final conversion can be achieved by operating in an adsorptive-reactor mode. Control of water in the reactor is achieved with a catalytically inert ion-exchange resin in Na-form. The resin prevents an excessive accumulation of water on the biocatalyst and reduces equilibrium limitations. The thermodynamic activity of water is identified as a key parameter for the design of such reactors. A mathematical model capable of predicting the water activity as a function of the varying concentrations of reactants and products is thus developed and found to successfully predict the experimental behavior observed in laboratory reactors. Substantial improvements in performance predicted by the model are seen experimentally in batch reactions and during the transient operation of continuous-flow fixed-bed reactors combining adsorptive and catalytic functions.

Design and optimisation of a simulated moving bed unit: role of deviations from equilibrium theory.

The design of a simulated moving bed involves thermodynamic, kinetic and hydrodynamic aspects and requires the optimisation of several variables: plant design variables, such as the column length and diameter, and operating variables, among them four independent flow-rates, the feed concentration and the switch time. In this work we develop an algorithm to design both the unit and its operating conditions, with an overall view on equilibrium properties, efficiency and hydrodynamics, using a simple equilibrium stage model. In this way we determine the parameters leading to the highest possible productivity for a given separation, only requiring the knowledge of the equilibrium isotherms, the Van Deemter equation and a correlation for pressure drop. The algorithm has been used to investigate the effect on the separation performance of some parameters, such as particle size and required product purity, which are not considered by equilibrium theory. The results have been compared with the predictions of equilibrium theory and the observed deviations have been put in evidence and discussed.

Simulated moving-bed chromatography and its application to chirotechnology.

The increased awareness of the differences in biological activity of the two enantiomers of a chiral drug has raised the demand for enantiomerically pure products, particularly in the pharmaceutical industry. Simulated moving-bed chromatography can be used for the separation of the two enantiomers of a chiral molecule, which is feasible at all production scales, from laboratory to pilot to production plant. The use of non-enantioselective synthesis of racemic mixtures and simulated moving-bed enantiomer separation might make the development process of a new chiral drug substantially shorter and cheaper.