An accurate and reproducible method for the quantitative analysis of isoflavones and their metabolites in rat plasma using liquid chromatography/mass spectrometry combined with photodiode array detection

To study the safety and potential health benefits of soy isoflavones, a rapid and simple method based on liquid chromatography combined with mass spectrometry (LC/MS) and photodiode array detector (PDA) was developed for the determination of isoflavones in rat plasma. The analytes included daidzein, genistein, glycitein, equol, 4-ethyl phenol, and biochanin A over a concentration range of 1.0-4320.0 nM using 75 microL of rat plasma. Rat plasma samples were hydrolyzed by adding an enzyme mixture from Helix pomatia containing glucuronidase and sulfatase to convert the isoflavone beta-glycosides daidzin, genistin, and glycitin to their active aglycone forms. A liquid-liquid extraction method using ethyl acetate as the extraction solvent was used to extract aglycones and the internal standards (phenolphthalein beta-D glucuronide, 4-methylumbelliferyl sulfate, and apigenin) from digested plasma samples. The extract was evaporated to dryness under a nitrogen stream, reconstituted with 0.1% formic acid in water-acetonitrile (85 + 15), and injected into a Zorbax SB-CN reversed-phase column (4.6 x 75 mm, 3.5 microm particle size). The Micromass ZQ detector was operated in the positive ion selected-ion monitoring mode. The flow rate for LC was 1.0 mL/min, with a split where 25% of the effluent was introduced into the electrospray ionization probe of the MS instrument and 75% into the PDA. The chromatographic run time was 16.0 min, with delay of 10 min/injection. The interday precision and accuracy of the standard samples were <2.6% relative standard deviation and <10% relative error, respectively. Recovery of the reported isoflavones with this method varied from 86 to 100%.     

Comparative vapour phase FTIR spectra and vibrational assignment of manganese pentacarbonyls derivatives of the type XMn(CO)5: (where X=Br, Cl, I, H, D, CH3, CD3, CF3)

The infrared spectra of pure Mn(CO)(5)X in the region 4000-400 cm(-1) has been obtained in the vapour phase. The observed spectrum has been analyzed to distinguish the fundamental frequencies, the rotational-vibrational and structure, and overtone and combination frequencies. The assignment of the observed vapour phase frequencies to the fundamental modes of vibration has been made on C(4V) symmetry. The weak peaks due to XMn(CO)(4)((13)CO) molecules have been measured and assigned for all molecules. This study provides a comprehensive comparison of these compounds, with all of these data the assignment of frequencies is reviewed and a set of quite unambiguous assignments made. The significant finding in this regards are that, it is not necessary to assume lower than C(4V) symmetry for XMn(CO)(5) as has been done in previous consideration of some infrared spectrum of these compounds.     

Preparation, structure and spasmolytic activities of some derivatives of harmine series of alkaloids

Keeping in view the interesting chemistry and pharmacological importance of harmine series of bases -- the beta-carboline alkaloids, a number of new derivatives of tetrahydroharmine and harmalol have been prepared and characterized through spectral studies. Some of these derivatives showed spasmolytic activity. It was observed that all the N-acyl tetrahydroharmine derivatives are stable, not labile and no ring opening occurs in these compounds, as reported recently.     

(Liquid + liquid) equilibria of (water + propionic acid + 2-ethyl-1-hexanol): Experimental data and correlation

(Liquid + liquid) equilibrium (LLE) data for (water + propionic acid + 2-ethyl-1-hexanol) were determined at atmospheric pressure over the temperature range of (298.15 to 308.15) K. A type-1 LLE phase diagram was obtained for this ternary system. The LLE data were correlated fairly well with UNIQUAC model, indicating the reliability of the UNIQUAC equation for this ternary system. The average root mean square deviation between the observed and calculated mole fractions was 1.57%. Distribution coefficients and separation factors were measured to evaluate the extracting capability of the solvent.     

Liquid phase equilibria of (water + phosphoric acid + 1-butanol or butyl acetate) ternary systems at T = 308.2 K

(Liquid + liquid) equilibria and tie lines for the ternary systems of (water + phosphoric acid + 1-butanol) and (water + phosphoric acid + butyl acetate) were measured at T = 308.2 K. The experimental ternary (liquid + liquid) equilibrium data were correlated with the UNIQUAC model. The reliability of the experimental tie lines was confirmed using Othmer-Tobias correlation. The average root-mean-square deviation (RMSD) values of (water + phosphoric acid + 1-butanol) and (water + phosphoric acid + butyl acetate) systems were 2.17% and 2.16%, respectively. Distribution coefficients and separation factors were measured to evaluate the extracting capability of the solvents. The results show that butyl acetate may be considered as a reliable organic solvent for the extraction of phosphoric acid from aqueous solutions.     

The role of host environment on the aggregative properties of some ionic dye materials

The aggregation of methylene blue (MB), rhodamine 6G (R6G), and rhodamine B (RB) in liquid crystalline solution (anisotropic host) was studied using polarised spectroscopy and in a guest–host system. The self-association of the ionic dyes was investigated in molecular sieves of type zeolite-β and SAPO-11 (microporous solid hosts) using diffuse reflectance spectroscopy. The aggregation of the dyes in the aqueous solution (isotropic host) was studied using absorption spectroscopy in the visible region for comparison. Therefore, the influence of host nature in the different phases on the molecular interaction of the guest molecules was investigated and compared. The nature of the interacting pairs in these dyes was discussed using the exciton theory.     

Effects of antinutritional factors on protein digestibility and amino acid availability in foods

Digestibility of protein in traditional diets from developing countries such as India, Guatemala, and Brazil is considerably lower compared to that of protein in typical North American diets (54-78 versus 88-94%). The presence of less digestible protein fractions, high levels of insoluble fiber, and high concentrations of antinutritional factors in the diets of developing countries, which are based on less refined cereals and grain legumes as major sources of protein, are responsible for poor digestibility of protein. The effects of the presence of some of the important antinutritional factors on protein and amino digestibilities of food and feed products are reviewed in this chapter. Food and feed products may contain a number of antinutritional factors that may adversely affect protein digestibility and amino acid availability. Antinutritional factors may occur naturally, such as glucosinolates in mustard and rapeseed protein products, trypsin inhibitors and hemagglutinins in legumes, tannins in legumes and cereals, phytates in cereals and oilseeds, and gossypol in cottonseed protein products. Antinutritional factors may also be formed during heat/alkaline processing of protein products, yielding Maillard compounds, oxidized forms of sulfur amino acids, D-amino acids, and lysinoalanine (LAL, an unnatural amino acid derivative). The presence of high levels of dietary trypsin inhibitors from soybeans, kidney beans, or other grain legumes can cause substantial reductions in protein and amino acid digestibilities (up to 50%) in rats and pigs. Similarly, the presence of high levels of tannins in cereals, such as sorghum, and grain legumes, such as fababean (Vicia faba L.), can result in significantly reduced protein and amino acid digestibilities (up to 23%) in rats, poultry, and pigs. Studies involving phytase supplementation of production rations for swine or poultry have provided indirect evidence that normally encountered levels of phytates in cereals and legumes can reduce protein and amino acid digestibilities by up to 10%. D-amino acids and LAL formed during alkaline/heat treatment of proteins such as casein, lactalbumin, soy protein isolate, or wheat proteins are poorly digestible (less than 40%), and their presence can reduce protein digestibility by up to 28% in rats and pigs. A comparison of the protein digestibility determination in young (5-week) versus old (20-month) rats suggests greater susceptibility to the adverse effects of antinutritional factors in old rats than in young rats. Therefore, the inclusion of protein digestibility data obtained with young rats, as the recommended animal model, in the calculation of PDCAAS (Protein Digestibility-Corrected Amino Acid Score) may overestimate protein digestibility and quality of products, especially those containing antinutritional factors, for the elderly. For products specifically intended for the elderly, protein digestibility should be determined using more mature rats.     

Evidence for metal-like electronic contribution in low-temperature heat capacity of polypyrrole

Heat capacity measurements in the temperature range of 0.6 to 12 K have been conducted on doped polypyrrole films. At low temperature, a finite electronic contribution gamma prevails in all samples. The value of gamma for hexafluorophosphate doped polypyrrole PPy(PF6) is 6.31 mJ x K(-2) x mol(-1), but is 2.2 mJ x K(-2) x mol(-1) for p-toluene sulfonate doped polypyrrole PPy(TsO). With use of the free electron model, the corresponding densities of states at the Fermi level N(E(F)) are calculated and compared with those obtained from spin susceptibility data.