Synchronous fluorescence spectroscopy for quantitative determination of virgin olive oil adulteration with sunflower oil

Adulteration of extra virgin olive oil with sunflower oil is a major issue for the olive oil industry. In this paper, the potential of total synchronous fluorescence (TSyF) spectra to differentiate virgin olive oil from sunflower oil and synchronous fluorescence (SyF) spectra combined with multivariate analysis to assess the adulteration of virgin olive oil are demonstrated. TSyF spectra were acquired by varying the excitation wavelength in the region 270–720 nm and the wavelength interval (Δλ) in the region from 20 to 120 nm. TSyF contour plots for sunflower, in contrast to virgin olive oil, show a fluorescence region in the excitation wavelength range 325–385 nm. Fifteen different virgin olive oil samples were adulterated with sunflower oil at varying levels (0.5–95%) resulting in one hundred and thirty six mixtures. The partial least-squares regression model was used for quantification of the adulteration using wavelength intervals of 20 and 80 nm. This technique is useful for detection of sunflower oil in virgin olive oil at levels down to 3.4% (w/v) in just two and a half minutes using an 80-nm wavelength interval.     

Local Mass Transfer Correlations for Nonaqueous Phase Liquid Pool Dissolution in Saturated Porous Media

Local mass transfer correlations are developed to describe the rate of interface mass transfer of single component nonaqueous phase liquid (NAPL) pools in saturated subsurface formations. A threedimensional solute transport model is employed to compute local mass transfer coefficients from concentration gradients at the NAPL–water interface, assuming that the aqueous phase concentration along the NAPL–water interface is constant and equal to the solubility concentration. Furthermore, it is assumed that the porous medium is homogeneous, the interstitial fluid velocity steady and the dissolved solute may undergo firstorder decay or may sorb under local equilibrium conditions. Powerlaw expressions relating the local Sherwood number to appropriate local Peclet numbers are developed for both rectangular and elliptic/circular source geometries. The proposed power law correlations are fitted to numerically generated data and the correlation coefficients are determined using nonlinear least squares regression. The estimated correlation coefficients are found to be direct functions of the interstitial fluid velocity, pool dimensions, and pool geometry.     

Note on “Electrochemical promotion of catalytic reactions”

A recent review published in this Journal of the electrochemical promotion of catalysis (EPOC or NEMCA effect) is discussed. Some key aspects of the effect’s phenomenology and physicochemical origin are reviewed and clarified and the interplay of catalytic kinetics and mass transfer limitations in EPOC studies under high vacuum is discussed.     

One-pot synthesis of novel fused pentacyclic chromenopyrimidobenzimidazolones and benzimidazolyl-chromenyl-substituted thiazolidinones

The ultrasound promoted synthesis of a number of novel fused pentacyclic chromenopyrimido[1,2-α]benzimidazolones by the one-pot reaction of 3-formylchromones with 2-aminobenzimidazole is described. Moreover, the isolated pentacyclic chromone derivatives upon microwave irradiation with 2-mercaptocarboxylic acids afforded benzimidazolyl-chromenylthiazolidinones incorporating three pharmacophoric heterocycles; the same thiazolidinones were also formed through a multicomponent reaction under microwave irradiation involving 3-formylchromones, aminobenzimidazole and 2-mercaptocarboxylic acids. The structural elucidation of the products was accomplished by 1D and 2D NMR experiments and for thiazolidinones was also confirmed by X-ray crystallographic analysis. Full assignment of all ¹H and ¹³C NMR chemical shifts has been unambiguously achieved. The proposed reaction mechanism is also discussed.     

Modeling of colloid and colloid-facilitated contaminant transport in a two-dimensional fracture with spatially variable aperture

Mathematical models are developed for two-dimensional transient transport of colloids, and cotransport of contaminant/colloids in a fracture-rock matrix system with spatially variable fracture aperture. The aperture in the fracture plane is considered as a lognormally distributed random variable with spatial fluctuations described by an exponential autocovariance function. Colloids are envisioned to irreversibly deposit onto fracture surfaces without penetrating the rock matrix; whereas, the contaminant is assumed to decay, sorb onto fracture surfaces and onto colloidal particles, as well as to diffuse into the rock matrix. The governing stochastic transport equations are solved numerically for each realization of the aperture fluctuations by a fully implicit finite difference scheme. Emphasis is given on the effects of variable aperture on colloid and colloid-facilitated contaminant transport. Simulated breakthrough curves of ensemble averages of several realizations show enhanced colloid transport and more pronounced fingering when colloids are subject to size exclusion from regions of small aperture size. Moreover, it is shown that an increase in the fracture aperture fluctuations leads to faster transport and increases dispersion. For the case of contaminant/colloids cotransport it is shown, for the conditions considered in this work, that colloids enhance contaminant mobility and increase contaminant dispersion.Nomenclature b fracture aperture, L - c contaminant concentration in the fracture, M/L³ - c _m contaminant concentration in the rock matrix, M/L³ - c _o source contaminant concentration, M/L³ - c ^* contaminant concentration adsorbed onto fracture surfaces, M/L² - c _m ^* contaminant concentration adsorbed inside the rock matrix, M/M - d _p colloidal particle diameter, L - D hydrodynamic dispersion coefficient dyadic, L²/t - D Brownian diffusion coefficient for colloids and molecular diffusion coefficient for contaminants, L²/t - D _m effective diffusion coefficient in the rock matrix, L²/t - h total head potential in the fracture, L - K _f partition coefficient for contaminant sorption onto fracture surfaces, L - K _m contaminant partition coefficient in the rock matrix, L³/M - K _n partition coefficient for contaminant sorption onto suspended colloids, L - K _n* partition coefficient for contaminant sorption onto deposited colloids, L³/M - _x fracture length in thex-direction, L - _y fracture length in they-direction, L - n colloid concentration in the liquid phase, M/L³ - n _o source colloid concentration, M/L³ - n ^* colloid concentration adsorbed onto fracture surfaces, M/L² - n _max ^* maximum deposited colloid concentration on fracture surfaces, M/L² - N ^* number of deposited colloidal particles per unit surface area of the fracture, 1/L² - N _max ^* maximum number of deposited colloidal particles per unit surface area of the fracture, 1/L² - q ^* diffusive mass flux into the rock matrix, M/L²t - R retardation factor in the fracture - R _m retardation factor in the rock matrix - s contaminant concentration adsorbed on colloids in the liquid phase, M/M - s _o source solid-phase contaminant concentration onto suspended colloids, M/M - s ^* contaminant concentration adsorbed on deposited colloids, M/M - t time, t - U interstitial velocity vector, L/t - x coordinate along the fracture length, L - y coordinate along the fracture width, L - z coordinate perpendicular to the fracture plane, L - area blocked by a deposited colloidal particle, L² - _L longitudinal dispersivity, L - _T transversal dispersivity, L - fluid specific weight, M/L²t² - fraction of the fracture surface physically covered by colloids - gz dummy integration variable - porosity of the rock matrix - colloid deposition coefficient, L - first-order decay coefficient, 1/t - fluid dynamic viscosity, M/Lt - defined in (18) - _b bulk density of the rock matrix, M/L³ - _p colloidal particle density, M/L³ - standard deviation of the lognormally distributed fluctuations of the fracture aperture     

An Exact Reformulation Algorithm for Large Nonconvex NLPs Involving Bilinear Terms

Many nonconvex nonlinear programming (NLP) problems of practical interest involve bilinear terms and linear constraints, as well as, potentially, other convex and nonconvex terms and constraints. In such cases, it may be possible to augment the formulation with additional linear constraints (a subset of Reformulation-Linearization Technique constraints) which do not affect the feasible region of the original NLP but tighten that of its convex relaxation to the extent that some bilinear terms may be dropped from the problem formulation. We present an efficient graph-theoretical algorithm for effecting such exact reformulations of large, sparse NLPs. The global solution of the reformulated problem using spatial Branch-and Bound algorithms is usually significantly faster than that of the original NLP. We illustrate this point by applying our algorithm to a set of pooling and blending global optimization problems.     

Zeolite NaY-promoted cyclization of farnesal: a short route to nanaimoal

The sesquiterpene nanaimoal was synthesized in 21% overall yield and in a biomimetic manner. As a key step, the acid-catalyzed cyclization of farnesal under zeolite NaY confinement conditions was used. The intrazeolite cyclization of farnesal affords as major product a double-bond isomer of nanaimoal, via a novel diastereoselective tandem 1,5-diene cyclization/Prins-type reaction.     

Interactive transport, subcellular relocation and enhanced phototoxicity of hypericin encapsulated in guanidinylated liposomes via molecular recognition

Abstract Hypericin (HYP), a photocytotoxic phenanthroperylenquinone was encapsulated in liposomes outfitted with guanidinium-bearing lipids to ensure efficient cell binding through molecular recognition with anionic groups resident on the plasma membrane. The uptake of HYP encapsulated in these liposomes by DU145 human prostate cancer cells, was studied employing fluorescence, versus nonguadinylated liposomes and free HYP. The subcellular localization was in all cases studied by confocal microscopy employing specific subcellular organelle probes. The photocytotoxicity of HYP was assessed, 24 h following irradiation with 15 mWcm(-2) light through a GG 495 Schott filter, by a standard tetrazolium to formazan assay (XTT). HYP uptake by DU145 cells was found to be profoundly enhanced by using guanidinylated liposomes. Also the distance of the guanidinium group from the liposomal surface was found to significantly affect HYP loading, subcellular localization and phototoxicity. The two different modes of liposome cell internalization observed, i.e. plasma membrane fusion and endocytosis, were found to greatly affect the phototoxicity of HYP. Molecular recognition was overall appraised as a promising, novel route for photodynamic therapy, profoundly enhancing its efficacy. HYP encapsulated in liposomes-bearing guanidinium groups was more efficiently taken up by cells, leading to enhanced phototoxicity, in contrast to HYP encapsulated in their nonguanidinylated counterparts.