Carlos Bravo-Díaz

A new method for monitoring dediazoniation reactions: Simultaneous monitoring of concentration and rates of product formation and loss of starting material for the dediazoniation ofp-methylbenzenediazonium tetrafluoroborate

We have examined the kinetics and mechanism of the dediazoniation reaction of p-methylbenzenediazonium tetrafluoroborate in the presence and absence of CuCl2 using a methodology developed by us that allows, simultaneously, and within the same experiment to identify, to quantify, and to obtain the rate constants for the formation of all dediazoniation products, and, indirectly, the rate constant for the diazonium salt decomposition. The methodology developed combines the use of coupling reactions, to form a stable azo dye, followed by analysis by HPLC.

Quantitative determination of α-tocopherol distribution in a tributyrin/Brij 30/water model food emulsion

Until recently, determining the distribution of antioxidants, AOs, between the oil, interfacial and aqueous regions of opaque emulsions has not worked well because the concentrations of AOs in interfacial regions cannot be determined separately from their concentrations in the oil and water phases. However, our novel kinetic method based on the reaction between an arenediazonium ion and vitamin E, or alpha-tocopherol, provides the first good estimates for the two partition constants that describe alpha-tocopherol distribution between the oil/interfacial and water/interfacial regions of tributyrin/Brij 30/water emulsions without physical isolation of any phase. The reaction is monitored by a new derivatization method based on trapping unreacted arenediazonium ion as an azo dye and confirmed by linear sweep voltammetry, LSV. The results by both derivatization and LSV methods are in good agreement and show that alpha-tocopherol distributes strongly in favor of the interfacial region when the oil is tributyrin, e.g., ca. 90% when the surfactant volume fraction is Phi I=0.01. The second-order rate constant for reaction in the interfacial region is also obtained from the results. Our kinetic method provides a robust approach for determining antioxidant distributions in emulsions and should help develop a quantitative interpretation of antioxidant efficiency in emulsions.

Effects of emulsifier hydrophile–lipophile balance and emulsifier concentration on the distributions of gallic acid, propyl gallate, and α-tocopherol in corn oil emulsions

We evaluated the effects of the hydrophile-lipophile balance (HLB) and emulsifier concentration on the distribution of the antioxidants gallic acid (GA), propyl gallate (PG), and α-tocopherol (TOC) between the aqueous, interfacial, and oil regions of food-grade emulsions composed of stripped corn oil, acidic water, and a mixture of the non-ionic surfactants Tween 20, 40, 80, and Span 20. The distribution of the antioxidants (AOs) is described by two partition constants, that between the oil-interfacial region, P(O)(I), and that between the aqueous and interfacial region, P(W)(I), of the emulsions. The partition constants were determined from the kinetic analyses of the variation in the observed rate constant, k(obs), for the reaction between the AOs and the hydrophobic 4-hexadecylbenzenediazonium ions, 16-ArN(2)(+), with the emulsifier volume fraction. The effects of emulsifier HLB on the second-order rate constants in the interfacial region k(I) were also evaluated for each antioxidant. Results show that an increase in emulsifier concentration promotes the incorporation of AOs to the interfacial region of the emulsions, so that at surfactant volume fractions of 0.04, more than 90% of GA and PG and more than 50% of TOC are located in that region. A decrease in the HLB favors the incorporation of PG and TOC to the interfacial region of the emulsions but has a negligible effect on the fraction of GA in that region. The %AOs in the interfacial region of the emulsions does not correlate with the polarity of the antioxidant, so that GA and PG are predominantly located in the aqueous-interfacial regions of the emulsion rather that in the oil droplet interior; meanwhile, TOC is mostly located in the oil-interfacial regions. Results should aid to understand how antioxidants are distributed in food-grade emulsions and their relative efficiency in inhibiting lipid oxidation.

Distribution of hydroxytyrosol and hydroxytyrosol acetate in olive oil emulsions and their antioxidant efficiency.

We employed a kinetic method to determine the distributions of the antioxidants hydroxytyrosol (HT) and hydroxytyrosol acetate (HTA) between the oil, aqueous, and interfacial regions of a model food emulsion composed of stripped olive oil, acidic water, and a blend of Tween 80 and Span 80 [hydrophilic–lipophilic balance (HLB) = 8.05] as an emulsifier. HT is oil-insoluble, but HTA is both oil- and water-soluble (partition constant P(O)(W) = 0.61). Results indicate that, at a given emulsifier volume fraction Φ(I), the fraction of HTA in the interfacial region is higher than that of HT. The percentage of both antioxidants increases with an increasing Φ(I), so that % HT > 40% at Φ(I) = 0.005 and % HT > 80% at Φ(I) = 0.04. HTA appears to be a better antioxidant than HT, as shown by an accelerated oxidative test (Schaal oven method). A correlation between their distribution in the emulsion and their efficiency was established.

To Model Chemical Reactivity in Heterogeneous Emulsions, Think Homogeneous Microemulsions.

Two important and unsolved problems in the food industry and also fundamental questions in colloid chemistry are how to measure molecular distributions, especially antioxidants (AOs), and how to model chemical reactivity, including AO efficiency in opaque emulsions. The key to understanding reactivity in organized surfactant media is that reaction mechanisms are consistent with a discrete structures-separate continuous regions duality. Aggregate structures in emulsions are determined by highly cooperative but weak organizing forces that allow reactants to diffuse at rates approaching their diffusion-controlled limit. Reactant distributions for slow thermal bimolecular reactions are in dynamic equilibrium, and their distributions are proportional to their relative solubilities in the oil, interfacial, and aqueous regions. Our chemical kinetic method is grounded in thermodynamics and combines a pseudophase model with methods for monitoring the reactions of AOs with a hydrophobic arenediazonium ion probe in opaque emulsions. We introduce (a) the logic and basic assumptions of the pseudophase model used to define the distributions of AOs among the oil, interfacial, and aqueous regions in microemulsions and emulsions and (b) the dye derivatization and linear sweep voltammetry methods for monitoring the rates of reaction in opaque emulsions. Our results show that this approach provides a unique, versatile, and robust method for obtaining quantitative estimates of AO partition coefficients or partition constants and distributions and interfacial rate constants in emulsions. The examples provided illustrate the effects of various emulsion properties on AO distributions such as oil hydrophobicity, emulsifier structure and HLB, temperature, droplet size, surfactant charge, and acidity on reactant distributions. Finally, we show that the chemical kinetic method provides a natural explanation for the cut-off effect, a maximum followed by a sharp reduction in AO efficiency with increasing alkyl chain length of a particular AO. We conclude with perspectives and prospects.

Temperature and emulsifier concentration effects on gallic acid distribution in a model food emulsion.

We determined the effects of emulsifier concentration and temperature on the distribution of gallic acid (GA) in a food-grade emulsion composed of 1:9 vol:vol stripped corn oil, acidic water and Tween 20. The distribution of GA can be defined by the partition constant between the aqueous and the interfacial regions, P(W)(I), which was determined by using a kinetic method and the pseudophase kinetic model. Once P(W)(I) is known, determining the distribution of GA is straightforward. Our results show that at least 40% of the total GA is located in the interfacial region of the emulsion at 0.005 volume fraction of Tween 20, and this percentage increases to ca. 85% of the total GA at 0.04 volume fraction of Tween 20. The variation of P(W)(I) with the temperature was used to estimate the thermodynamic parameters for the GA transfer from the aqueous to the interfacial region of the emulsion and the activation parameters for the reaction between 16-ArN(2)(+) and GA in the interfacial region. The free energy of transfer from the aqueous to the interfacial region, ΔG(T)(0,W→I), is negative, the enthalpy of transfer is small and negative, but the entropy of transfer is large and positive. Our results demonstrate that the partitioning of GA in acidic emulsions between aqueous and interfacial regions depends primarily on droplet concentration and is only slightly dependent on temperature.

Free radicals and polyphenols: The redox chemistry of neurodegenerative diseases

The oxidation of bioorganic materials by air and, particularly, the oxidative stress involved in the cell loss and other pathologies associated with neurodegenerative diseases (NDs) are of enormous social and economic importance. NDs generally involve free radical reactions, beginning with the formation of an initiating radical by some redox, thermal or photochemical process, causing nucleic acid, protein and lipid oxidations and the production of harmful oxidative products. Physically, persons afflicted by NDs suffer progressive loss of memory and thinking ability, mood swings, personality changes, and loss of independence. Therefore, the development of antioxidant strategies to retard or minimize the oxidative degradation of bioorganic materials has been, and still is, of paramount importance. While we are aware of the importance of investigating the biological and medical aspects of the diseases, elucidation of the associated chemistry is crucial to understanding their progression, heading to intelligent chemical intervention to find more efficient therapies to prevent or delay the onset of the diseases. Accordingly, this review aims to provide the reader with a chemical base to understand the behavior and properties of the reactive oxygen species involved and of typical radical scavengers such as polyphenolic antioxidants. Some discussion on the structures of the various species, their formation, chemical reactivities and lifetimes is included. The ultimate goal is to understand how, when and where they form, how far they travel prior to react, which molecules are their targets, and how we can, eventually, control their activity to minimize their impact by means of chemical methods. Recent strategies explore chemical modifications of the hydrophobicity of potent, natural antioxidants to improve their efficiency by fine-tuning their concentrations at the reaction site.

Rates and pH-dependent product distributions of the CuCl2-catalyzed dediazoniation of p-nitrobenzenediazonium ­tetrafluoroborate in aqueous acid

The rates of formation and yields of products from the dediazoniation of p-nitrobenzenediazonium tetrafluoroborate (PNBD) in aqueous solutions over a range of HCl, NaCl and CuCl 2 concentrations at 60 °C were examined. Two main products were observed: p-nitrophenol (ArOH) and p-nitrochlorobenzene (ArCl). Trace amounts of nitrobenzene (ArH) and p-nitrofluorobenzene (ArF) were detected. Added CuCl 2 speeds the reaction and both the rate of dediazoniation and ArOH yield (unlike ArCl) are very sensitive to pH. The results are completely consistent with the heterolytic dediazoniation mechanism, i.e. rate-determining formation of a highly reactive aryl cation followed by competitive formation of dediazoniation products. PNBD kinetics are first order (with respect to PNBD) in the absence of and presence of CuCl2, except at low acidity and in the presence of low to moderate CuCl2 concentrations. The non-first-order kinetics are attributed to a competing reaction between PNBD and the ArOH product. The results suggest a simple method for preparing halobenzenes in high yield. Copyright

Using the pseudophase kinetic model to interpret chemical reactivity in ionic emulsions: determining antioxidant partition constants and interfacial rate constants.

Kinetic results obtained in cationic and anionic emulsions show for the first time that pseudophase kinetic models give reasonable estimates of the partition constants of reactants, here t-butylhydroquinone (TBHQ) between the oil and interfacial region, P(O)(I), and the water and interfacial region, P(W)(I), and of the interfacial rate constant, k(I), for the reaction with an arenediazonium ion in emulsions containing a 1:1 volume ratio of a medium chain length triglyceride, MCT, and aqueous acid or buffer. The results provide: (a) an explanation for the large difference in pH, >4 pH units, required to run the reaction in CTAB (pH 1.54, added HBr) and SDS (pH 5.71, acetate buffer) emulsions; (b) reasonable estimates of PO(I) and k(I) in the CTAB emulsions; (c) a sensible interpretation of added counterion effects based on ion exchange in SDS emulsions (Na(+)/H3O(+) ion exchange in the interfacial region) and Donnan equilibrium in CTAB emulsions (Br(-) increasing the interfacial H3O(+)); and (d) the significance of the effect of the much greater solubility of TBHQ in MCT versus octane, 1000/1, as the oil. These results should aid in interpreting the effects of ionic surfactants on chemical reactivity in emulsions in general and in selecting the most efficient antioxidant for particular food applications.

Monitoring dediazoniation product formation by high-performance liquid chromatography after derivatization

A derivatization protocol that exploits the rapid reaction between arenediazonium ions and a suitable coupling agent followed by high-performance liquid chromatography analyses of the reaction mixture was employed to determine the product distribution, the rate constants for product formation and the association constant of 4-nitrobenzenediazonium, PNBD, ion with beta-cyclodextrin, beta-CD. The derivatization of PNBD with the coupling agent leads to the formation of a stable azo dye that prevents by-side reactions of PNBD with the solvents of the mobile phase, including water, or the metallic parts of the chromatographic system that would eventually lead to erroneous identification and quantification of dediazoniation products. The results show that in the presence of beta-CD, nitrobenzene is formed at the expense of 4-nitrophenol, which is the major product in its absence. The observed rate constants for the interaction between PNBD and beta-CD increase upon increasing [beta-CD] showing a saturation profile indicative of the formation of an inclusion complex between PNBD and beta-CD. By fitting the experimental data to a simplified Lineaweaver-Burk equation, the corresponding association constant and the maximum acceleration rate of beta-CD towards PNBD were estimated. The protocol is applicable under a variety of experimental conditions provided that the rate of the coupling reaction is much faster than that of dediazoniation.