Mössbauer study of archaeological ceramics from Valle del Alto Sinu (Colombia)

A physico-chemical characterization of ceramic samples from the arachaeological sites of El Cabrero, El Gallo, and El Frasquillo (Valle del Alto Sinú) is presented. Extensive use of Mössbauer spectroscopy data reveals that the currently used typological classification scheme of Dolmatoff is related to the production technology of the different artifacts. In addition, a model for firing conditions for “Rojo Sencillo”, “Tierra Impresa”, “Tierra Incisa”, and “Blanco” types of ceramics is proposed.     

Studies on crude oil‐water biphasic mixtures by low‐field NMR

Low‐field ¹H NMR was used in this work for the analysis of mixtures involving crude oils and water. CPMG experiments were performed to determine the transverse relaxation time (T₂) distribution curves, which were computed by the inverse Laplace transform of the echo decay data. The instrument's ability of quantifying water and petroleum in biphasic mixtures following different methodologies was tested. For mixtures between deionized water and petroleum, one achieved excellent results, with root mean squared error of cross‐validation (RMSECV) of 0.8% for a regression between the water content (wt %) and the relative area of the water peak in the T₂ distribution curve, or a standard deviation of 0.9% for the relationship between the water content and the relative water peak area, corrected by the relative hydrogen index of the crude. In the case of biphasic mixtures of Mn²⁺‐doped water and crude oils, the best result of RMSECV = 1.6% was achieved by using the raw magnetization decay data for a partial least squares regression. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and characterization of nanostructured iron compounds prepared from the decomposition of iron pentacarbonyl dispersed into carbon materials with varying porosities

This work describes the production and characterization of carbon-iron nanocomposites obtained from the decomposition of iron pentacarbonyl (Fe(CO)₅) mixed with different carbon materials: a high surface area activated carbon (AC), powdered graphite (G), milled graphite (MG), and carbon black (CB). The nanocomposites were prepared either under argon or in ambient atmosphere, with a fixed ratio of Fe(CO)₅ (4.0 mL) to carbon precursor (2.0 g). The images of scanning electron microscopy and the analysis of textural properties indicated the presence of nanostructured Fe compounds homogeneously dispersed into the different classes of pores of the carbon matrices. The elemental Fe content was always larger for samples prepared in ambient atmosphere, reaching values in the range of 20–32 wt%. On the other hand, samples prepared under argon showed reduced Fe content, with values in the range 5–10 wt% for samples prepared from precursors with low surface area (G, MG, and CB) and a much higher value (~19 wt%) for samples prepared from the precursor of high surface area (AC). Mössbauer spectroscopy and X-ray diffractometry showed that the nanoparticles were mostly composed of iron oxides in the case of the samples prepared in oxygen-rich ambient atmosphere and also for the AC-derived nanocomposite prepared under argon, which is consistent with the large oxygen content of this precursor. For the other precursors, with reduced or no oxygen content, metallic iron and iron carbides were found to be the dominant phases in samples prepared under oxygen-free atmosphere. The samples prepared in ambient atmosphere and the AC-derived sample prepared under argon exhibited superparamagnetic behavior at room temperature, as revealed by temperature-dependent magnetization curves and Mössbauer spectroscopy.     

Solid-state natural abundance 25Mg NMR studies of Na2MgEDTA x 4 H2O--a possible new reference compound for 25Mg NMR spectroscopy

Natural abundance solid-state (25)Mg NMR measurements were made of the disodium salt of magnesium ethylenediaminetetraacetate tetrahydrate (Na(2)MgEDTA x 4 H(2)O). Both magic angle spinning (MAS) and static experiments were employed to determine the quadrupole coupling constant (C(q)) and the asymmetry parameter (eta(q)) of the electric field gradient (EFG) tensor associated with (25)Mg in this compound, giving the values C(q) = 1.675(5) MHz and eta(q) = 0.15(1). The isotropic chemical shift was determined to be delta(iso) = 0.25(10) ppm (relative to 11 M MgCl(2) aqueous solution) and a small chemical shift anisotropy (CSA) contribution (approximately -13 ppm) was detected, one of the first CSA reports in (25)Mg NMR. This compound exhibited remarkably good (25)Mg NMR sensitivity, due to its fast spin-lattice relaxation and modest quadrupole coupling, which allowed its use as a secondary shift reference and as a test sample for the implementation and optimisation of signal-enhancement methods in (25)Mg NMR spectroscopy, such as double frequency sweeps (DFS) and the use of adiabatic hyperbolic secant (HS) and WURST pulses.     

The delay effect on reaction–diffusion equations

In this work we study a reaction–diffusion problem with delay and we make an analysis of the stability of solutions by means of bifurcation theory. We take the delay constant as a parameter. Special conditions on the vector field assure existence of a spatially nonconstant positive equilibrium U_k , which is stable for small values of the delay. An increase of the delay destabilizes the equilibrium of U_k and leads to super or subcritical Hopf bifurcation.     

Calorimetric and computational study of 3-buten-1-ol and 3-butyn-1-ol. Estimation of the enthalpies of formation of 1-alkenols and 1-alkynols

The enthalpies of combustion and vaporization of 3-buten-1-ol and 3-butyn-1-ol have been measured by static bomb combustion calorimetry and correlation gas chromatography techniques, respectively, and the gas-phase enthalpies of formation, Delta(f)H degrees (m)(g), have been determined, the values being -147.3 +/- 1.8 and 16.7 +/- 1.6 kJ mol(-1), for 3-buten-1-ol and 3-butyn-1-ol, respectively. High level calculations at the G2 and G3 levels have also been carried out. Relationships between the enthalpies of formation of 1-alkanols, 1-alkenols and 1-alkynols and with the corresponding hydrocarbons have been discussed. From the calculated contributions to Delta(f)H degrees (m)(g) for the substitutions of CH(3) by CH(2)OH, CH(3)CH(2) by CH(2)=CH and CH(3)CH(2) by CH triple bond C, we have estimated the Delta(f)H degrees (m)(g) values for 3-buten-1-ol and 3-butyn-1-ol, in excellent agreement with the experimental ones. Delta(f)H degrees (m)(g) values for 1-alkenols and 1-alkynols up to 10 carbon atoms have also been estimated.     

Could cell membranes produce acoustic streaming? Making the case for Synechococcus self-propulsion

Sir James Lighthill proposed in 1992 that acoustic streaming (AS) within the mammalian cochlea could play a role in the transmission of acoustic signals to the auditory sensory cells. Microelectromechanical devices for mixing and pumping, based on the acoustic streaming effect were introduced in the mid 1990s. Nature may have preceded this invention by 2.7 Gyr. We believe that acoustic streaming produced by nanometer scale membrane vibrations is widespread in cell biology. Flows generated by acoustic streaming could be produced along the “raphes” (central channels) of silica coated diatoms. Other possible instances are yeast cells and erythrocytes whose membranes generate nanoscale vibrations. We hypothesize that some of the most ancient organisms use acoustic streaming not only for self-propulsion but also to enhance their nutrient uptake. In this paper we focus on a motile strain of Synechococcus, a cyanobacterium whose mechanism for self-propulsion is not known. The calculations presented here show that a traveling surface acoustic wave (SAW) could account for the observed velocities. These SAWs would also produce a non-negligible Stokes layer surrounding the cell, motion within this region being essentially chaotic. Therefore, an AS mechanism would be biologically advantageous, enhancing localized diffusion processes and consequently, chemical reactions. Finally, we discuss possible experiments to support (or rule out) the AS model vs. other contending explanations for Synechococcus locomotion.     

Micro-swimming without flagella: Propulsion by internal structures

Since a first proof-of-concept for an autonomous micro-swimming device appeared in 2005 a strong interest on the subject ensued. The most common configuration consists of a cell driven by an external propeller, bio-inspired by bacteria such as E.coli. It is natural to investigate whether micro-robots powered by internal mechanisms could be competitive. We compute the translational and rotational velocity of a spheroid that produces a helical wave on its surface, as has been suggested for the rod-shaped cyanobacterium Synechococcus. This organisms swims up to ten body lengths per second without external flagella. For the mathematical analysis we employ the tangent plane approximation method, which is adequate for amplitudes, frequencies and wave lengths considered here. We also present a qualitative discussion about the efficiency of a device driven by an internal rotating structure.