A standard addition method to assay the concentration of biologically interesting polyphenols in grape berries by reversed-phase HPLC

A reversed-phase HPLC method which allows the simultaneous assay of (+)- catechin, (-)-epicatechin, trans-resveratrol, quercetin and quercetin glycosides in grape berries is described. Kromasil 100 served as stationary phase and a gradient of acetic acid, water and methanol was used. The analytical run requires 42 min for complete sample elution. Satisfactory peak resolution was achieved following a novel extraction process and direct injection of a 20 microL sample. The method was used for the analyses of eighteen samples. Linearities were in the range of 0.98 to 0.999 regression coefficient, for all phenolics, while detection limits ranged from 30 microg mL(-1) for trans-resveratrol to 1.5 mg mL(-1) for (+)-catechin. Recoveries ranged from 95.1 to 98.7% while the method provided good precision, with standard deviations between 3.5 and 6.1%, n=5.     

Structure elucidation and vasodilator activity of methoxy flavonols from Calycotome villosa subsp. intermedia

Two flavonols identified as 3,5,7,4′-tetrahydroxy-3′-methoxyflavone (1) and 3,5,7,4′-tetrahydroxy-8-methoxyflavone (2) were isolated from the seeds of Calycotome villosa subsp. intermedia. The structure elucidation of the isolated compounds was performed by the spectroscopic methods (UV, IR, ¹H NMR, ¹³C NMR and MS) and also by a single crystal X-ray analysis in the case of compound (2). Vasodilator activity of compound (2) was demonstrated in isolated rat aorta contracted with high KCl or with noradrenaline.     

Construction of a l-lysine biosensor by immobilizing lysine oxidase on a gold-poly(o-phenylenediamine) electrode

The construction of a l-lysine biosensor on a Si-gold strip electrode (SGSE) is described in this study. The construction comprises (a) the formation of poly(o-phenylenediamine, o-PD) membrane on the electrode surface via electropolymerization and (b) the immobilization of lysine oxidase on the gold/poly(o-PD) electrode with glutaraldehyde. The behavior of the gold/poly(o-PD) electrode against H(2)O(2) and lysine, as well as the repeatability of the electropolymerization and the time stability of the polymer were studied. The study showed that the electropolymerization procedure is repeatable, and that the polymer is quite stable for at least 40 days. The biosensor showed a linear calibration curve in the range 0.01-1x10(-5) M (0.1-10 muM) lysine. The interfering effect of other amino acids on the biosensor performance was also studied and amperometric selectivity coefficients were calculated. The biosensor responded mainly against tyrosine and cysteine, while the response to phenylalanine, arginine, histidine and ornithine was very low. By changing the electropolymerization conditions, the effect of interferents was further reduced.     

Unsteady circular Couette flow of a Bingham plastic with the Augmented Lagrangian Method

Numerical simulations are undertaken for unsteady flows of an ideal Bingham fluid in a circular Couette viscometer. The main difficulties in such simulations are caused by the non-differentiability of the constitutive equation and the need to determine the position and shape of the yield surface separating the yielded zones from the unyielded ones. In this work, these difficulties are overcome by using a numerical method based on variational inequalities, i.e. the augmented Lagrangian/Uzawa method. The start-up and cessation of circular Couette flows of a Bingham fluid are solved numerically assuming that only one of the cylinders is rotating. An improved theoretical upper bound for the stopping time in the case of cessation is derived. The numerical estimates for the stopping time compare well with the theoretical bounds. Moreover, with the adopted method the evolution of the velocity profiles and the locations of yielded/unyielded surfaces are accurately calculated. In flow cessation, we observe an interesting effect, namely the appearance of a small unyielded region adjoined to the outer cylinder shortly before cessation.     

Anionic amphiphilic end‐linked conetworks by the combination of quasiliving carbocationic and group transfer polymerizations

A series of amphiphilic end‐linked conetworks was synthesized by the combination of two “quasiliving” polymerization techniques, quasiliving carbocationic (QLCCP) and group transfer polymerizations (GTP). The hydrophobic monomer was polyisobutylene methacrylate synthesized by the QLCCP of isobutylene and subsequent terminal modification reactions. The hydrophilic monomer was methacrylic acid (MAA) introduced via the polymerization of 2‐tetrahydropyranyl methacrylate followed by acid hydrolysis after (co)network formation. The conetwork syntheses were performed by sequential monomer/crosslinker additions under GTP conditions. All the precursors and the extractables from the conetworks were characterized by gel permeation chromatography and ¹H NMR. The resulting polymer conetworks were investigated in terms of their degree of swelling (DS) in aqueous media and in tetrahydrofuran (THF) over the whole range of ionization of the MAA units and in n‐hexane for uncharged conetworks. The DSs in water increased with the degree of ionization (DI) of the MAA units and the hydrophilic content in the conetwork, whereas the DSs in THF increased with the reduction of the DI of the MAA units. The effective pK of the MAA units in the conetworks increased from 8.4 to 10.5 with decreasing MAA content. These findings can facilitate the design of similar unique conetworks with adjustable swelling behavior and composition‐dependent pK values. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4289–4301, 2009     

Self-dual codes from circulant matrices

In this paper, two general methods for constructing self-dual codes are presented. These methods use circulant matrices in circulant or bordered circulant structures to construct the suitable generator matrices. The necessary and sufficient conditions, for the generated codes to be self-dual, are provided. Special cases of the proposed methods include the well known “Pure Double Circulant” construction and the “Bordered Double circulant” construction of self-dual codes. As an example, the methods were applied to search for self-dual codes in GF(5). Many new inequivalent self-dual codes with best known distance are found.     

MDS Self-Dual Codes over Large Prime Fields

Combinatorial designs have been used widely in the construction of self-dual codes. Recently a new method of constructing self-dual codes was established using orthogonal designs. This method has led to the construction of many new self-dual codes over small finite fields and rings. In this paper, we generalize this method by using generalized orthogonal designs, and we give another new method that creates and solves Diophantine equations over GF(p) in order to find suitable generator matrices for self-dual codes. We show that under the necessary conditions these methods can be applied as well to small and large fields. We apply these two methods to study self-dual codes over GF(31) and GF(37). Using these methods we obtain some new maximum distance separable self-dual codes of small orders.     

A characterization of Weingarten surfaces in hyperbolic 3-space

We study 2-dimensional submanifolds of the space \({\mathbb{L}}({\mathbb{H}}^{3})\) of oriented geodesics of hyperbolic 3-space, endowed with the canonical neutral Kähler structure. Such a surface is Lagrangian iff there exists a surface in ?³ orthogonal to the geodesics of Σ.We prove that the induced metric on a Lagrangian surface in \({\mathbb{L}}({\mathbb{H}}^{3})\) has zero Gauss curvature iff the orthogonal surfaces in ?³ are Weingarten: the eigenvalues of the second fundamental form are functionally related. We then classify the totally null surfaces in \({\mathbb{L}}({\mathbb{H}}^{3})\) and recover the well-known holomorphic constructions of flat and CMC 1 surfaces in ?³.     

Comparative Interaction Studies of Quercetin with 2-Hydroxyl-propyl-β-cyclodextrin and 2,6-Methylated-β-cyclodextrin

Quercetin (QUE) is a well-known natural product that can exert beneficial properties on human health. However, due to its low solubility its bioavailability is limited. In the present study, we examine whether its formulation with two cyclodextrins (CDs) may enhance its pharmacological profile. Comparative interaction studies of quercetin with 2-hydroxyl-propyl-β-cyclodextrin (2HP-β-CD) and 2,6-methylated cyclodextrin (2,6Me-β-CD) were performed using NMR spectroscopy, DFT calculations, and in silico molecular dynamics (MD) simulations. Using T1 relaxation experiments and 2D DOSY it was illustrated that both cyclodextrin vehicles can host quercetin. Quantum mechanical calculations showed the formation of hydrogen bonds between QUE with 2HP-β-CD and 2,6Μe-β-CD. Six hydrogen bonds are formed ranging between 2 to 2.8 Å with 2HP-β-CD and four hydrogen bonds within 2.8 Å with 2,6Μe-β-CD. Calculations of absolute binding free energies show that quercetin binds favorably to both 2,6Me-β-CD and 2HP-β-CD. MM/GBSA results show equally favorable binding of quercetin in the two CDs. Fluorescence spectroscopy shows moderate binding of quercetin in 2HP-β-CD (520 M⁻¹) and 2,6Me-β-CD (770 M⁻¹). Thus, we propose that both formulations (2HP-β-CD:quercetin, 2,6Me-β-CD:quercetin) could be further explored and exploited as small molecule carriers in biological studies.