A comparative study of calibration transfer methods for determination of gasoline quality parameters in three different near infrared spectrometers

This work presents a comparative study of calibration transfer among three near infrared spectrometers for determination of naphthenes and RON (Research Octane Number) in gasoline. Seven transfer methods are compared: direct standardization (DS), piecewise direct standardization (PDS), orthogonal signal correction (OSC), reverse standardization (RS), piecewise reverse standardization (PRS), slope and bias correction (SBC) and model updating (MU). Two pre-treatment procedures, namely standard normal variate (SNV) and multiplicative scatter correction (MSC), are also investigated. The choice of an appropriate number of transfer samples for each technique, as well as the effect of window size in PDS/PRS and OSC components, are discussed. A broad set of gasoline samples representative of the Northeastern states of Brazil is employed in the investigation. The results show that the use of calibration transfer yields prediction errors comparable to those obtained with complete recalibration of the secondary instrument. Overall, the results point to RS as the best method for the analytical problem under consideration. When storage and/or physical transportation of transfer samples are impractical, MU is more appropriate. The comprehensive investigation carried out in the present work will be of value for practitioners involved in networks of fuel monitoring.     

Electrospray ionization mass spectrometry and partial least squares discriminant analysis applied to the quality control of olive oil

Direct infusion electrospray ionization mass spectrometry in the positive ion mode [ESI(+)‐MS] is used to obtain fingerprints of aqueous–methanolic extracts of two types of olive oils, extra virgin (EV) and ordinary (OR), as well as of samples of EV olive oil adulterated by the addition of OR olive oil and other edible oils: corn (CO), sunflower (SF), soybean (SO) and canola (CA). The MS data is treated by the partial least squares discriminant analysis (PLS‐DA) protocol aiming at discriminating the above‐mentioned classes formed by the genuine olive oils, EV (1) and OR (2), as well as the EV adulterated samples, i.e. EV/SO (3), EV/CO (4), EV/SF (5), EV/CA (6) and EV/OR (7). The PLS‐DA model employed is built with 190 and 70 samples for the training and test sets, respectively. For all classes (1–7), EV and OR olive oils as well as the adulterated samples (in a proportion varying from 0.5 to 20.0% w/w) are properly classified. The developed methodology required no ions identification and demonstrated to be fast, as each measurement lasted about 3 min including the extraction step and MS analysis, and reliable, because high sensitivities (rate of true positives) and specificities (rate of true negatives) were achieved. Finally, it can be envisaged that this approach has potential to be applied in quality control of EV olive oils. Copyright © 2013 John Wiley & Sons, Ltd.     

An approach to control the spurious currents in a multiphase lattice Boltzmann method and to improve the implementation of initial condition

Multiphase lattice Boltzmann methods are known to generate spurious or parasitic currents at the fluid–fluid interfaces. This nonphysical phenomenon has to be avoided, or at least controlled, in order to achieve reliable solutions. In this article, a method to control these fictitious velocities via lattice refinement is proposed, which is based on interface thickness control for which both the spurious currents and the physical fluid–fluid interface thickness vanishes as the spatial resolution increases. It has been found that a proper interface thickness adjustment is required as the lattice refinement is applied, or an increase in spurious currents, instead of a reduction, can occur. By combining the new method with an appropriate multiphase flow initialization, the overall stability for high density O(1000) and viscosity O(100) ratios is greatly improved. Although this research has been conducted with a Rothman and Keller type lattice Boltzmann model, it is believed that other types of multiphase lattice Boltzmann models could benefit from the basic ideas underlying this research. Copyright © 2015 John Wiley & Sons, Ltd.     

Interaction of Candida parapsilosis isolates with human hair and nail surfaces revealed by scanning electron microscopy analysis

Candida parapsilosis is found frequently as commensal organism on epithelial tissues, and is also an increasing cause of nosocomial infection. Scanning electron microscope (SEM) observations were used to analyse the capability of C. parapsilosis cells to adhere and grow as biofilm on human natural substrates and to compare the adherence pattern of isolates exhibiting distinct phenotypes. Cells from the crepe phenotype are predominantly elongated and form pseudohyphae whereas cells from the smooth phenotype are yeast-shaped, either in liquid cultures or on human nail and hair surfaces. The electron micrographs revealed that C. parapsilosis cells from the smooth phenotype adhered in higher number to both surfaces compared to the observed for the crepe phenotype. SEM analysis of human hair surface revealed that cells from the smooth phenotype appear as clumped blastoconidia of uniform morphology embedded in a flocculent extracellular material forming biofilm. The extracellular material and biofilm were seeing in a less extension in the crepe phenotype. A distinct adherence pattern was observed when human nail was used as substrate. Here C. parapsilosis cells seem to be linked to surface structures of human nail plate. Fibrillar extracellular material was observed connecting neighbouring cells as well as nail surface.     

CaII Binding Regulates and Dominates the Reactivity of a Transition‐Metal‐Ion‐Dependent Diesterase from Mycobacterium tuberculosis

The diesterase Rv0805 from Mycobacterium tuberculosis is a dinuclear metallohydrolase that plays an important role in signal transduction by controlling the intracellular levels of cyclic nucleotides. As Rv0805 is essential for mycobacterial growth it is a promising new target for the development of chemotherapeutics to treat tuberculosis. The in vivo metal‐ion composition of Rv0805 is subject to debate. Here, we demonstrate that the active site accommodates two divalent transition metal ions with binding affinities ranging from approximately 50 nm for Mn^II to about 600 nm for Zn^II. In contrast, the enzyme GpdQ from Enterobacter aerogenes, despite having a coordination sphere identical to that of Rv0805, binds only one metal ion in the absence of substrate, thus demonstrating the significance of the outer sphere to modulate metal‐ion binding and enzymatic reactivity. Ca^II also binds tightly to Rv0805 (K_d≈40 nm ), but kinetic, calorimetric, and spectroscopic data indicate that two Ca^II ions bind at a site different from the dinuclear transition‐metal‐ion binding site. Ca^II acts as an activator of the enzymatic activity but is able to promote the hydrolysis of substrates even in the absence of transition‐metal ions, thus providing an effective strategy for the regulation of the enzymatic activity.     

A cyclic hexacopper(II) fluoro complex that encapsulates two fluoride anions

The complex [[Cu3(HpztBu)4(mu-pztBu)2(mu-F)2(mu 3-F)]2]F2 (HpztBu = 3[5]-tert-butylpyrazole) has a cyclic, C2v-symmetric hexacopper core. The two non-coordinated F- anions are encapsulated within cavities formed by three HpztBu ligands.     

Phase-object analysis with a speckle interferometer

We describe the characteristics of a double-exposure specklegram obtained through a double-aperture system, by introduction of a wedge in front of one aperture in one exposure. It is assumed that a uniform displacement of the diffuser is produced between exposures. The average intensity distribution and visibility of the interferometric fringes in the Fourier plane are analyzed. An alternative interferometric technique for phase-object detection is proposed.     

A correction algorithm for undersampled images using dynamic segmentation and entropy based focus criterion

A post-processing technique is presented for correcting images undersampled in k-space. The method works by taking advantage of the image's background zeros (dynamically segmented through the application of a threshold) to extrapolate the missing k-space samples. The algorithm can produce good quality images from a small set of k-space frequencies with only a few iterations of simple matrix operations, using the image entropy as the focus criterion. It does not require any special patient preparation, extra pulse sequences, complex gradient programming or specialized hardware. This makes it a good candidate for any application that requires short scan times or where only few frequencies can be sampled.