Separation of Natural Food Pigments in Saponified and Un-Saponified Paprika Oleoresin by Ultra High Performance Supercritical Fluid Chromatography (UHPSFC)

The natural pigments in paprika were rapidly and efficiently separated by ultra high performance supercritical fluid chromatography. The separation of both un-saponified and saponified mixtures of paprika oleoresin were optimized, with run times of 10.6 min. Three different C18 columns, a cyano, silica and diol column, all 3 × 100 mm, with 1.8 μm particles were compared. The best separation for the un-saponified sample was found with an SB-C18 column, while the saponified samples were best separated on a bare silica, RX-Sil column. A SB-CN column allowed near optimum separation of both the unsaponified, and saponified samples, with similar run times. The best mobile phase was carbon dioxide (CO₂) modified with isopropyl alcohol (IPA), with a composition gradient. Fingerprints of several commercial pepper products indicated that one appeared to be colored with artificial dyes, while the color of a chili powder may have been enhanced with a paprika extract. Spectra, using CO₂ with IPA as modifier, produced a single maximum at 453 nm, which appears to represent up to a 30 nm solvatochromic shift from the maxima in most organic solvents. Acetonitrile (ACN) as modifier produced spectra with two maxima and a similar solvatochromic shift. These results appear to be the first on saponified paprika oleoresin samples using SFC. It is also the first detailed report on the separation of un-saponified samples. The results are up to six times faster than comparable results by HPLC. It appears that SFC is a viable, superior alternative to HPLC for the analysis of this important commercial product, without using ACN, or chlorinated solvents.

     

Rapid, Direct Quantitation of the Preservatives Benzoic and Sorbic Acid (and Salts) Plus Caffeine in Foods and Aqueous Beverages Using Supercritical Fluid Chromatography

The preservatives benzoate and sorbate, plus caffeine were rapidly separated and quantified, in just over 2 min, in a wide range of beverages and foods, using supercritical fluid chromatography (SFC). Fifteen beverages and 10 semi-liquid foods were evaluated. The benzoate and sorbate were originally present in the samples as the acid, or the sodium, or potassium salt. The aqueous samples were diluted 3:1 with acidified methanol, to insure the acids were protonated, then directly injected. The solutes were isocratically eluted from a 4 × 250 mm, 5 μm Diol column with 3.5 mL min^?1 of 8.5 % methanol containing 0.3 % acetic acid at 50 °C and a column outlet pressure of 150 bar. The real samples exhibited remarkably little interference. All the beverages were accurately labeled. However, many of the foods, such as salad dressings, mustard, etc., were mislabeled. The method was linear over a wide range with correlation coefficients for all three solutes >0.999. RSD’s were generally less than 1 %. The results agreed with the caffeine content on the labels within a few percent. Surprisingly, this appears to be the first published separation of benzoic and sorbic acid preservatives in food, and beverages using SFC, and one of a very few SFC applications where aqueous samples were simply diluted and injected. Compared to published references, the SFC method was found to be up to 7 times faster than HPLC, and eliminated the use of acetonitrile.     

Scalable synthesis of palladium nanoparticle catalysts by atomic layer deposition

Potential applications in drug delivery from nanostructures composed of two oppositely charged polymethacrylates, eudragit^? L100 (EL) and eudragit^? EPO (EE), loaded with three model basic drugs (D), atenolol, propranolol, and metroclopramide were evaluated. The self-organized nanoparticles based on drug-interpolyelectrolyte complexes (DIPEC), (EL-D₅₀)?CEE_X, were obtained by mixing the aqueous dispersions of both polyelectrolytes at room temperature in an ultrasound bath. Dispersions of (EL-D₅₀) neutralized with increasing proportions of EE exhibited a rise of turbidity, particle sizes in the range of 150?C400?nm, and high negative zeta potential. The sign of zeta potential was shifted from negative to positive by changes in composition of DIPEC. Freeze dried DIPEC were easily redispersed in water yielding nearly the same parameters of fresh dispersions. In vitro release experiments using Franz cells showed that DIPEC systems behave as a drug reservoir that slowly releases the drug as water is placed in the receptor compartment. The release rate was raised by ionic exchange with counterions present in simulated physiological fluids placed in the receptor media. Delivery of D from DIPEC exhibited a remarkable robustness toward simulated physiological media of different pH. The DIPEC systems exhibit interesting properties to design nanoparticulate drug delivery systems for oral and/or topical routes.     

Cycloaddition Reactions of the Metal Phosphorus Double Bonded Complexes CP(CO)2M=PR2 (M = MO,W; R = Alkyl,Aryl)

Abstract

The reaction of the metal phosphorus double bonded species Cp(CO)₂M=PR₂ (M = Mo, W; R = aryl, alkyl) (1)¹⁾ with diverse diazoalkanes, alkenes, alkines and dienes results in the facile formation of the [2+1]-, [2+2]1- and [2+4]-cycloaddition products 2a-c.     

Separation of 9 Sulfonamide Drugs in ≈4 Min by Ultra-High Performance Supercritical Fluid Chromatography (UHPSFC): with a Feasibility Study for Detection in Milk

Nine widely used veterinary sulfonamide drugs were baseline separated (R _s ≥1.5) in just over 4 min using a 3 × 100 mm, 1.8 μm RX-Sil column, with 9.2 % methanol in carbon dioxide, at 110 bar and 30 °C, with direct UV detection at 260 nm using a 3 mm, 2 μL tapered flow cell. Pressure drop was only 172 bar. Optimization was difficult due to the similarity in structures. Small changes in modifier concentration, temperature and pressure, each tended to improve the resolution of some peak pairs but degraded the resolution of others. There were four critical pairs, each responding differently to changes in conditions. Optimization was performed by plotting resolution between pairs as a function of modifier concentration first, temperature second, and outlet pressure third. Retention time was then minimized by changing flow rate. The estimated limit of quantitation (LOQ, S/N >10), for direct injections, was ≈200–400 ng/g of each, inadequate for regulatory requirements. Solid phase extraction (SPE) attempted to pre-concentrate samples spiked with sulfamethazine by ≈20:1. From water, the limit of detection (LOD) was ≈2.7 ng/mL with LOQ ≈9 ng/mL using UV at 260 nm. The LOD for milk was 6.2 ng/mL, and LOQ was 20.1 ng/mL. A better pre-concentration step or a more sensitive detector such as MS–MS is required. Even with these inadequacies, SFC was shown to be a feasible, faster, “greener” alternative to HPLC for the separation of these drugs.     

Photokinetic,Biochemical and Structural Features of Chimeric Photoactive Yellow Protein Constructs

Of the 10 photoactive yellow protein (PYPs) that have been characterized, the two from Rhodobacter species are the only ones that have an additional intermediate spectral form in the resting state (λ_max = 375 nm), compared to the prototypical Halorhodospira halophila PYP. We have constructed three chimeric PYP proteins by replacing the first 21 residues from the N‐terminus (Hyb1PYP), 10 from the β4–β5 loop (Hyb2PYP) and both (Hyb3PYP) in Hhal PYP with those from Rb. capsulatus PYP. The N‐terminal chimera behaves both spectrally and kinetically like Hhal PYP, indicating that the Rcaps N‐terminus folds against the core of Hhal PYP. A small fraction shows dimerization and slower recovery, possibly due to interaction at the N‐termini. The loop chimera has a small amount of the intermediate spectral form and a photocycle that is 20 000 times slower than Hhal PYP. The third chimera, with both regions exchanged, resembles Rcaps PYP with a significant amount of intermediate spectral form (λ_max = 380 nm), but has even slower kinetics. The effects are not strictly additive in the double chimera, suggesting that what perturbs one site, affects the other as well. These chimeras suggest that the intermediate spectral form has its origins in overall protein stability and solvent exposure.     

Z = 50 shell gap near 100Sn from intermediate-energy Coulomb excitations in even-mass 106-112Sn isotopes

Rare isotope beams of neutron-deficient 106,108,110Sn from the fragmentation of 124Xe were employed in an intermediate-energy Coulomb excitation experiment. The measured B(E2,0(1)(+)-->2(1)(+)) values for 108Sn and 110Sn and the results obtained for the 106Sn show that the transition strengths for these nuclei are larger than predicted by current state-of-the-art shell-model calculations. This discrepancy might be explained by contributions of the protons from within the Z = 50 shell to the structure of low-energy excited states in this region.