Numerical developments for short-pulsed Near Infra-Red laser spectroscopy. Part I: direct treatment

This two part study is devoted to the numerical treatment of short-pulsed laser near infra-red spectroscopy. The overall goal is to address the possibility of numerical inverse treatment based on a recently developed direct model to solve the transient radiative transfer equation. This model has been constructed in order to incorporate the last improvements in short-pulsed laser interaction with semi-transparent media and combine a discrete ordinates computing of the implicit source term appearing in the radiative transfer equation with an explicit treatment of the transport of the light intensity using advection schemes, a method encountered in reactive flow dynamics. The incident collimated beam is analytically solved through Bouger-Beer-Lambert extinction law.In this first part, the direct model is extended to fully non-homogeneous materials and tested with two different spatial schemes in order to be adapted to the inversion methods presented in the following second part. As a first point, fundamental methods and schemes used in the direct model are presented. Then, tests are conducted by comparison with numerical simulations given as references. In a third and last part, multi-dimensional extensions of the code are provided. This allows presentation of numerical results of short pulses propagation in 1, 2 and 3D homogeneous and non-homogeneous materials given some parametrical studies on medium properties and pulse shape. For comparison, an integral method adapted to non-homogeneous media irradiated by a pulsed laser beam is also developed for the 3D case.     

Optical tomography using the time-independent equation of radiative transfer—Part 2: inverse model

Optical tomography is a novel imaging modality that is employed to reconstruct cross-sectional images of the optical properties of highly scattering media given measurements performed on the surface of the medium. Recent advances in this field have mainly been driven by biomedical applications in which near-infrared light is used for transillumination and reflectance measurements of highly scattering biological tissues. Many of the reconstruction algorithms currently utilized for optical tomography make use of model-based iterative image reconstruction (MOBIIR) schemes. The imaging problem is formulated as an optimization problem, in which an objective function is minimized. In the simplest case the objective function is a normalized-squared error between measured and predicted data. The predicted data are obtained by using a forward model that describes light propagation in the scattering medium given a certain distribution of optical properties.In part I of this two-part study, we presented a forward model that is based on the time-independent equation of radiative transfer. Using experimental data we showed that this transport-theory-based forward model can accurately predict light propagation in highly scattering media that contain void-like inclusions. In part II we focus on the details of our image reconstruction scheme (inverse model). A crucial component of this scheme involves the efficient and accurate determination of the gradient of the objective function with respect to all optical properties. This calculation is performed using an adjoint differentiation algorithm that allows for fast calculation of this gradient. Having calculated this gradient, we minimize the objective function with a gradient-based optimization method, which results in the reconstruction of the spatial distribution of scattering and absorption coefficients inside the medium. In addition to presenting the mathematical and numerical background of our code, we present reconstruction results based on experimentally obtained data from highly scattering media that contain void-like regions. These types of media play an important role in optical tomographic imaging of the human brain and joints.     

New developments in frequency domain optical tomography. Part II: Application with a L-BFGS associated to an inexact line search

Gradient-based algorithms in optical tomography have shown efficiency and robustness due to their self-regularization effect, as they track the largest errors first, which tends to stabilize the reconstruction scheme. This second part shows the application of the presented developments in the first part for the reconstruction of optical properties in complex geometry while taking into account the collimated source direction with such an algorithm. The reconstruction scheme is based on the limited memory BFGS type associated to an inexact line search in order to avoid numerous evaluations of the objective function. Normalization of the objective function with measurements and independent scaling of its gradient are used to improve the quality of the reconstruction. The results show that the algorithm is efficient compared to other solvers with a better recovering of both the absorption and scattering coefficients.     

Doppler limited laser spectroscopy on hafnium lines. Part II: Hyperfine structure of odd-parity levels

The hyperfine structure of selected odd-parity levels of the configurations 5d6s ^26p and 5d ^26s6p of I was studied in 10 lines lying in the red spectral region. Hyperfine spectra were obtained by the method of laser induced fluorescence in the plasma of a liquid nitrogen cooled hollow cathode discharge. The observed hyperfine structure constants A and B, together with results from earlier studies were analyzed by means of a parametric method. The interpretation has been carried out based on a refined multiconfigurational fine structure calculation including the main Rydberg series configurations mutually interacting. The set of fine structure parameters as well as the leading eigenvector percentages of levels relevant for this paper are given. The following single electron hfs parameters were deduced for : , ,, for the lowest configuration. Received: 16 November 1998 / Received in final form: 5 February 1999     

Surface‐enhanced Raman spectroscopy (SERS) on silver colloids for the identification of ancient textile dyes. Part II: pomegranate and sumac

The effectiveness of surface‐enhanced Raman spectroscopy (SERS) spectrocsopy on Ag colloids has been successfully demonstrated for the identification of a yellow dye in two ancient wool threads found in the Royal Tumulus of In Aghelachem, Libyan Sahara, belonging to the Garamantian period (2nd–3rd century A.D.). High‐performance liquid chromatography (HPLC) highlighted the presence of ellagic acid in the extracts from the threads, excluding other chromophores. This result, together with the abundance of malic acid detected by gas chromatography‐mass spectrometry (GC‐MS), suggested the possible use of pomegranate rind or sumac berries as source of the yellow dye, both plants being documented in the Fezzan area during the Garamantian period. HPLC analyses and SERS spectra acquired on the extracts of the ancient threads were therefore compared with those obtained from pomegranate and sumac extracts of the corresponding fruits and reference dyed wool samples, allowing us to identify the yellow dye as deriving from pomegranate (Punica granatum L.). SERS spectra of ellagic acid and dyes extracted from pomegranate rind and sumac berries are reported here for the first time. A methodological improvement is also presented, based on the use of NaClO₄ as aggregating agent, that leads to a significant increase of the signal‐to‐noise ratio in the SERS spectra. Copyright © 2010 John Wiley & Sons, Ltd.     

Self‐assembled monolayers of mercaptosuccinic acid monolayers on silver and gold surfaces designed for protein binding. Part II: vibrational spectroscopy studies on cytochrome c immobilization

An attempt has been made for using MSA‐modified electrodes as linkage monolayers for electrostatic and covalent binding of cytochrome c (Cc). For MSA monolayers grown from an aqueous solution on Ag, attachment of Cc in its native state is proved in the case of covalent bonding. Electrostatic immobilization of Cc at pH 7 results in presence of at least some amount of Fe²⁺ high‐spin configuration and/or Fe³⁺ oxidation state. Native protein Fe²⁺ low‐spin state of Cc is observed after applying a negative potential to the Ag electrode. The influence of the solvent used for the preparation of the MSA monolayer and thiol surface coverage of the Ag surface was studied. It was shown that the key factor to obtain the native structure of Cc is the successful blocking of the metal surface by the MSA linking layer. IRRAS measurements of MSA on monocrystalline gold (111) at neutral pH confirm the successful electrostatic Cc immobilization, which preserves the Fe²⁺ oxidation state of the chromophore on this substrate. Copyright © 2007 John Wiley & Sons, Ltd.