Rapid characterization of edible oils by direct matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis using triacylglycerols

Direct matrix-assisted laser desorption/ionization time-of-flight mass spectrometric (MALDI-TOFMS) analysis of solutions of edible fats/oils yielded spectra useful for their rapid differentiation and classification. Results also reflected the individual fatty acid components and their degree of unsaturation. After dissolution in hexane, MALDI-MS analysis revealed spectra showing characteristic triacylglycerols (TAGs), the main fat/oil components, as sodium adduct ions. The Euclidean distances calculated using the mass and intensity values for 20 TAGs were used to evaluate and compare spectra. With cluster analysis, animal fats grouped together differently than vegetable oils and the individual oils grouped together by type. The ion abundances for the individual TAGs and their presumed compositions were used to approximate the overall fatty acid composition of canola, soybean, corn, olive and peanut oil, as well as lard. Using this approach the calculated fatty acid compositions and degree of unsaturation generally fell within about 4% of literature values. When the degree of saturation was compared with values calculated from the package labeling the differences were about 7%.     

Guided-ion beam and theoretical study of the potential energy surface for activation of methane by W+

A guided-ion beam tandem mass spectrometer is used to study the reactions, W(+) + CH(4) (CD(4)) and [W,C,2H](+) + H(2) (D(2)), to probe the [W,C,4H](+) potential energy surface. The reaction W(+) + CH(4) produces [W,C,2H](+) in the only low-energy process. The analogous reaction in the CD(4) system exhibits a cross section with strong differences at the lowest energies caused by zero-point energy differences, demonstrating that this reaction is slightly exothermic for CH(4) and slightly endothermic for CD(4). The [W,C,2H](+) product ion reacts further at thermal energies with CH(4) to produce W(CH(2))(x)(+) (x = 2-4). At higher energies, the W(+) + CH(4) reaction forms WH(+) as the dominant ionic product with smaller amounts of WCH(3)(+), WCH(+), and WC(+) also formed. The energy dependent cross sections for endothermic formation of the various products are analyzed and allow the determination of D(0)(W(+)-CH(3)) approximately 2.31 +/- 0.10 eV, D(0)(W(+)-CH(2)) = 4.74 +/- 0.03 eV, D(0)(W(+)-CH) = 6.01 +/- 0.28 eV, and D(0)(W(+)-C) = 4.96 +/- 0.22 eV. We also examine the reverse reaction, [W,C,2H](+) + H(2) (D(2)) --> W(+) + CH(4) (CH(2)D(2)). Combining the cross sections for the forward and reverse processes yields an equilibrium constant from which D(0)(W(+)-CH(2)) = 4.72 +/- 0.04 eV is derived. Theoretical calculations performed at the B3LYP/HW+/6-311++G(3df,3p) level yield thermochemistry in reasonable agreement with experiment. These calculations help identify the structures and electronic states of the species involved and characterize the potential energy surface for the [W,C,4H](+) system.     

Efficient and robust tests for semiparametric models

In this paper, we investigate a hypothesis testing problem in regular semiparametric models using the Hellinger distance approach. Specifically, given a sample from a semiparametric family of \(\nu \)-densities of the form \(\{f_{\theta ,\eta }:\theta \in \Theta ,\eta \in \Gamma \},\) we consider the problem of testing a null hypothesis \(H_{0}:\theta \in \Theta _{0}\) against an alternative hypothesis \(H_{1}:\theta \in \Theta _{1},\) where \(\eta \) is a nuisance parameter (possibly of infinite dimensional), \(\nu \) is a \(\sigma \)-finite measure, \(\Theta \) is a bounded open subset of \(\mathbb {R}^{p}\), and \(\Gamma \) is a subset of some Banach or Hilbert space. We employ the Hellinger distance to construct a test statistic. The proposed method results in an explicit form of the test statistic. We show that the proposed test is asymptotically optimal (i.e., locally uniformly most powerful) and has some desirable robustness properties, such as resistance to deviations from the postulated model and in the presence of outliers.     

Influence of yttrium doping on the photocatalytic activity of bismuth oxybromide for ciprofloxacin degradation using indoor fluorescent light illumination

Research on Chemical Intermediates - In this work, a series of Y-doped BiOBr photocatalysts with different yttrium contents were successfully synthesized through a facile ethylene glycol-assisted...     

DEM investigation of mixing indices in a ribbon mixer

Mixing index is an important parameter to understand and assess the mixing state in various mixers including ribbon mixers,the typical food processing devices.M...     

Biochar derived from Salvadora persica branches biomass as low-cost adsorbent for removal of uranium(VI) and thorium(IV) from water

Journal of Radioanalytical and Nuclear Chemistry - In recent years, biochar based adsorbents have been given more attention for organic and inorganic pollutants removal. Therefore, in this study, a...     

Factors influencing the mechanism of surfactant catalyzed reaction of vitamin C-ferric chloride hexahydrate system

The kinetics of vitamin C by ferric chloride hexahydrate has been investigated in the aqueous ethanol solution of basic surfactant viz. octadecylamine (ODA) under pseudo-first order conditions. The critical micelle concentration (CMC) of surfactant was determined by surface tension measurement. The effect of pH (2.5–4.5) and temperature (15–35°C) in the presence and absence of surfactant were investigated. Activation parameters, ΔE _a, ΔH ^#, ΔS ^#, ΔG ^≠, for the reaction were calculated by using Arrhenius and Eyring plot. Surface excess concentration (Γ_max), minimum area per surfactant molecule (A _min), average area occupied by each molecule of surfactant (a), surface pressure at the CMC (Π_max), Gibb’s energy of micellization (ΔG _M°), Gibb’s energy of adsorption (ΔG _ad°), were calculated. It was found that the reaction in the presence of surfactant showed faster oxidation rate than the aqueous ethanol solution. Reaction mechanism has been deduced in the presence and absence of surfactant.     

Trapping of wide range mass-to-charge ions and dependence on matrix amount in internal source MALDI-FTMS

Internal ionization source MALDI-FTMS shows clear variation of number average molecular weight (M(n)) for an equimolar mixture of four PEG polymers (PEG 2000, PEG 4000, PEG 6000, PEG 8000) when the 2,5-dihydroxy benzoic acid (DHB) matrix to PEG ratio is varied or the laser power is changed. As the matrix to analyte ratio is increased, the analyte signal of higher molecular mass ions increases and the signal of lower mass ions decreases. Laser power dependence studies show a similar trend. Possible explanations for these observations are discussed.     

Synthesis of Au/Al2O3 Nanocatalyst and its Application in the Reduction of p‐Nitrophenol

Gold (Au) nanoparticles supported on alumina (Al₂O₃) were prepared at several pH levels via the deposition‐precipitation (DP) method. The effects of pH at below and above the isoelectric point (IEP) of Al₂O₃ as well as the pH adjustment before and after the addition of the support into the gold chloride solution were investigated. The results revealed the formation of cationic, clusters and metallic Au on alumina. The catalytic activity of these species was tested in the reduction of p‐nitrophenol (p‐NP) using hydrazine as a reductant. The catalytic reaction was monitored spectrophotometerically and the highest rate constant (k‐) achieved based on pseudo first order kinetic model was 12.7 × 10^‐3 s^‐1. Structural and elemental characterizations of the supported gold nanoparticles were carried out using X‐ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy‐dispersive X‐rays (EDX), atomic absorption spectrometry (AAS), and ultraviolet‐visible spectroscopy (UV‐Vis).     

Enantioselective analysis of ofloxacin and ornidazole in pharmaceutical formulations by capillary electrophoresis using single chiral selector and computational calculation of their inclusion complexes

A capillary electrophoretic method for the separation of the enantiomers of both ofloxacin and ornidazole is described. Several parameters affecting the separation were studied, including the type and concentration of chiral selector, buffer pH, voltage and temperature. Good chiral separation of the racemic mixtures was achieved in less than 16 min with resolution factors Rs = 5.45 and 6.28 for ofloxacin and ornidazole enantiomers, respectively. Separation was conducted using a bare fused-silica capillary and a background electrolyte (BGE) of 50 mM H₃PO₄-1 M tris solution; pH 1.85; containing 30 mg mL⁻¹ of sulfated-β-cyclodextrin (S-β-CD). The separation was carried out in reversed polarity mode at 25 °C, 18 kV, detection wavelength at 230 nm and using hydrodynamic injection for 15 s. Acceptable validation criteria for selectivity, linearity, precision, and accuracy were studied. The limits of detection (LOD) and limits of quantitation (LOQ) of the enantiomers (ofloxacin enantiomer 1 (OF-E1), ofloxacin enantiomer 2 (OF-E2), ornidazole enantiomer 1 (OR-E1) and ornidazole enantiomer 2 (OR-E2)) were (0.52, 0.46, 0.54, 0.89) and (1.59, 1.40, 3.07, 2.70) μg mL⁻¹, respectively. The proposed method was successfully applied to the assay of enantiomers of both ofloxacin and ornidazole in pharmaceutical formulations. The computational calculations for the enantiomeric inclusion complexes rationalized the reasons for the different migration times between the ofloxacin and ornidazole enantiomers.