Numerical simulations of confocal Raman spectroscopic depth profiles of materials: a photon scattering approach

We present a simple model that uses a novel photon scattering approach to predict the depth profile response obtained when confocal Raman spectroscopy is applied both to silicon and to a number of related polymeric materials of varying optical clarity. This paper first provides an overview of the models proposed to date to demonstrate the evolution in understanding of the confocal Raman response of semi‐transparent materials, based upon geometrical optics. A new model is then described that is based upon the twin notions of a permanent extended Raman illuminated volume and the degree of extinction of the incident and Raman scattered photons from the whole of the illuminated volume as it is gradually moved further into, or defocused above, the sample. The model's predictions are compared with empirical data from previous studies of a range of semi‐crystalline polymers with different scattering properties and, by means of contrast, with that of a silicon sample. We show that, despite its inherent simplicity, the physics this model utilizes is able successfully to predict the form of the depth profile for each material, something that has not been achieved by any model previously proposed, and that the parameters used in the model scale with independent physical measurements. Finally the model is used to account for the fact that useful Raman spectra can be obtained when the laser is focused as much as 40 µm above the sample surface. Copyright © 2007 John Wiley & Sons, Ltd.     

Modal analysis of lightweight graphite reinforced silica/polymer matrix composite plates

In this paper we describe how finite element and experimental modal analyses can be used to characterize the dynamic behavior of plates made from a new class of graphite reinforced silica/polymer matrix composite (GRSPMC) materials. An agreement is obtained between both methods, and the results show that GRSPMC materials can be modeled and tested using tools similar to those applied to the study of classical composite laminates.     

Fibrin Matrices as (Injectable) Biomaterials: Formation,Clinical Use,and Molecular Engineering

This review focuses on fibrin, starting from biological mechanisms (its production from fibrinogen and its enzymatic degradation), through its use as a medical device and as a biomaterial, and finally discussing the techniques used to add biological functions and/or improve its mechanical performance through its molecular engineering. Fibrin is a material of biological (human, and even patient's own) origin, injectable, adhesive, and remodellable by cells; further, it is nature's most common choice for an in situ forming, provisional matrix. Its widespread use in the clinic and in research is therefore completely unsurprising. There are, however, areas where its biomedical performance can be improved, namely achieving a better control over mechanical properties (and possibly higher modulus), slowing down degradation or incorporating cell‐instructive functions (e.g., controlled delivery of growth factors). The authors here specifically review the efforts made in the last 20 years to achieve these aims via biomimetic reactions or self‐assembly, as much via formation of hybrid materials.     

Modeling of solute transport into sub-aqueous sediments

A model for investigating the solute transport into a sub-aqueous sediment bed, under an imposed standing water surface wave, is developed. Under the assumption of Darcy flow in the bed, a model based on a two-dimensional, unsteady advection–diffusion equation is derived; the relative roles of the advective and diffusive transport are characterized by a Peclet number, Pe. Two solutions for the equation are developed. The first is a basic control volume method using the power-law scheme. The second is a smear-free, modified upwind solution for the special case of Pe → ∞. Results, at a given time step, are reported in terms of a laterally averaged solute verse depth profile. The main result of the paper is to demonstrate that the one-dimensional solute concentration verse depth profile is essentially independent of any numerical dissipation present in the solute field predictions. This demonstration is achieved by (i) using an extensive grid refinement study, and (ii) by comparing Pe → ∞ predictions obtained with the basic and smear-free solutions.     

Fe3O4(111) termination of α-Fe2O3(0001)

Scanning tunnelling microscopy (STM) has been used to investigate the structure formed on an α-Fe₂O₃(0001) substrate after argon ion bombardment and annealing in 1 × 10⁻⁶ mbar of O₂ at 1000 K. The STM images recorded at positive sample bias reveal an hexagonal array, with a distance between (Fe) atoms of 6.0 ± 0.1 rA and steps in multiples of 4.8 Å. These results are consistent with formation of an Fe₃O₄(111) epitaxial layer terminating in a monolayer of Fe atoms.     

Acoustic sounder monitoring of windshear within the atmospheric boundary layer over Ile-Ife, Nigeria

Summary A tri-axial acoustic sounder with Doppler wind measuring capability has been used to measure boundary layer winds from which windshear fields have been evaluated over Ile-Ife (7.29° N, 4.34° E) Nigeria between April and June, 1988. The correlation between SODAR-derived windshear profile and a radiosonde-derived temperature profile is examined. Associated Richardson numbers have been used to categorize atmospheric layers into various stability types. A case study of wind fields and derived windshear zones associated with a rain event has been made. The authors of this paper have agreed to not receive the proofs for correction.     

Algebras associated to intermediate subfactors

The Temperley-Lieb algebras are the fundamental symmetry associated to any inclusion of factors with finite index. We analyze in this paper the situation when there is an intermediate subfactor of . The additional symmetry is captured by a tower of certain algebras associated to . These algebras form a Popa system (or standard lattice) and thus, by a theorem of Popa, arise as higher relative commutants of a subfactor. This subfactor gives a free composition (or minimal product) of an and an subfactor. We determine the Bratteli diagram describing their inclusions. This is done by studying a hierarchy of colored generalizations of the Temperley-Lieb algebras, using a diagrammatic approach, à la Kauffman, that is independent of the subfactor context. The Fuss-Catalan numbers appear as the dimensions of our algebras. We give a presentation of the and calculate their structure in the semisimple case employing a diagrammatic method. The principal part of the Bratteli diagram describing the inclusions of the algebras is the Fibonacci graph. Our algebras have a natural trace and we compute the trace weights explicitly as products of Temperley-Lieb traces. If all indices are , we prove that the algebras and coincide. If one of the indices is , is a quotient of and we compute the Bratteli diagram of the tower . Our results generalize to a chain of intermediate subfactors. Oblatum 1-XII-1995 & 1-VII-1996     

Crystallization behavior of a propylene/ethylene copolymer: Nucleation and a clarifying additive

The isothermal crystallization behavior of a propylene/ethylene copolymer containing a clarifying additive has been studied in detail and compared with the equivalent unclarified grade. Differential scanning calorimetry was used to obtain crystallization exotherms for both the unclarified system and the clarified analogue. Avrami analysis of these data was then performed, using both linear and nonlinear data‐fitting techniques. Linear analysis revealed a change from a primary to a secondary crystallization process in the clarified system at about 50% relative crystallinity. Nonlinear techniques, however, led to more reliable estimates of the Avrami parameters and provided estimates of crystallization‐induction times. By combining the preceding with isothermal crystal‐growth‐rate data, the nucleation density in each material was obtained as a function of crystallization temperature. In the unclarified case, this fell exponentially with temperature. The nucleation density in the sorbitol‐clarified copolymer was 10³–10⁶ times greater than in the unclarified material, but decreased only slowly with increasing crystallization temperature throughout the temperature range investigated here. This final result appears entirely contradictory to previous morphological work in which a distinct morphological transition was observed at 128 °C and associated with a marked reduction in the nucleating efficiency of the sorbitol. Possible explanations for this apparent contradiction are considered. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2178–2189, 2002     

Strontium isotope ratios (87Sr/86Sr) of tooth enamel: a comparison of solution and laser ablation multicollector inductively coupled plasma mass spectrometry methods

Strontium isotope ratios (87Sr/86Sr) in tooth enamel provide a means to investigate migration and landscape use in humans and other animals. Established methods for measuring (87)Sr/(86)Sr in teeth use bulk sampling (5-20 mg) and labor-intensive elemental purification procedures before analysis by either thermal ionization mass spectrometry (TIMS) or multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). Another method for measuring 87Sr/86Sr is laser ablation MC-ICP-MS, but concerns have been expressed about its accuracy for measuring tooth enamel. In this study we test the precision and accuracy of the technique by analyzing 30 modern rodent teeth from the Sterkfontein Valley, South Africa by laser ablation MC-ICP-MS and solution MC-ICP-MS. The results show a mean difference in 87Sr/86Sr measured by laser ablation and by solution of 0.0003 +/- 0.0002. This degree of precision is well within the margin necessary for investigating the potential geographic origins of humans or animals in many areas of the world. Because laser ablation is faster, less expensive, and less destructive than bulk sampling solution methods, it opens the possibility for conducting 87Sr/86Sr analyses of intra-tooth samples and small and/or rare specimens such as micromammal and fossil teeth.     

Aqueous photochemistry of methyl-benzoquinone

Chemical trapping studies combined with optical and electron paramagnetic resonance measurements were employed to examine the mechanisms of the aqueous photochemistry of methyl-benzoquinone (mBQ) at both low and high quinone concentrations. At low [mBQ], dimethylsulfoxide (DMSO) reacted with a photogenerated intermediate to form a methyl radical, but methane did not, thereby unequivocally excluding the hydroxyl radical. DMSO at concentrations between 50 mM and 2 M completely suppressed the formation of the hydroxylated quinone, while only slowing the formation of the hydroquinone, suggesting reaction with either the triplet state or an intermediate arising from the triplet. Addition of Cl-, a putative physical quencher of the triplet, inhibited the DMSO reaction both noncompetitively and competitively in a fashion similar to that observed previously with nitrite, formate, and salicylic acid, thus providing further evidence for a reactive intermediate distinct from the triplet. This intermediate is attributed to a water-quinone exciplex. The relative yield of the methyl radical from the DMSO reaction decreased with increasing [mBQ], suggesting that at high concentrations, a bimolecular reaction of the triplet with the ground-state quinone outcompetes the formation of the quinone-water exciplex.