Regiospecific synthesis of quercetin O-β-d-glucosylated and O-β-d-glucuronidated isomers

Quercetin, the polyphenolic compound, which has the highest daily intake, is well known for its protective effects against aging diseases and has received a lot of attention for this reason. Both quercetin 3-O-β-d-glucuronide and quercetin 3′-O-β-d-glucuronide are human metabolites, which, together with their regioisomers, are required for biological as well as physical chemistry studies. We present here a novel synthetic route based on the sequential and selective protections of the hydroxyl functions of quercetin allowing selective glycosylation, followed by TEMPO-mediated oxidation to the glucuronide. This methodology enabled us to synthesize the five O-β-d-glucosides and four O-β-d-glucuronides of quercetin, including the major human metabolite, quercetin 3-O-β-d-glucuronide.     

Determination of strain and stress distribution on shearwalls by using the speckle photography technique

Speckle photography (SP) is a powerful tool that is adequate to determine small displacements in micrometer range. This information shows other characteristics of structure deformation under loads and can be determined as stress and strain distribution. In this paper we present the results of the application of the SP technique used to study the behaviour of discontinuities in a shearwall model. These structural elements are very important to the stability of buildings. The displacement whole field around the discontinuities and loading points was determined using the pointwise method. This allows us to determine stress distribution at the point of interest by means of the suitable equations. We also present the stress distribution obtained through the finite element method in order to compare the results obtained by means of these two techniques. Good correspondence was found between the displacements determined by both techniques (r=0.982) and also between the stress values we obtained.     

Transience and recurrence of quantum Markov semigroups

 This article introduces a concept of transience and recurrence for a Quantum Markov Semigroup and explores its main properties via the associated potential. We show that an irreducible semigroup is either recurrent or transient and characterize transient semigroups by means of the existence of non trivial superharmonic operators. Received: 27 January 2003 / Revised version: 19 February 2003 / Published online: 12 May 2003 This research has been partially supported by the ``Cátedra Presidencial en Análisis Cualitativo de Sistemas Dinámicos Cuánticos', DIPUC, FONDECYT project 1030552, MIUR program ``Probabilità Quantistica e Applicazioni', 2003-2004 and MECESUP PUC 0103. Mathematics Subject Classification (2000): 60J45, 81S25, 60J99, 37A50, 47A40 Key words or phrases: Quantum Markov semigroups – Potential theory – Markov processes     

The uniqueness of Hering's translation plane of order 27

It is shown that the following conjecture of Kallaher and Ostrom [2] is correct: Hering's translation plane of order 27 is the only translation plane of odd dimension over its kernel which has a collineation group isomorphic to SL(2, w) with w prime to 5 and to the characteristic, and having no affine perspectivity.     

Fundamental groupoids of digraphs and graphs

We introduce the notion of fundamental groupoid of a digraph and prove its basic properties. In particular, we obtain a product theorem and an analogue of the Van Kampen theorem. Considering the category of (undirected) graphs as the full subcategory of digraphs, we transfer the results to the category of graphs. As a corollary we obtain the corresponding results for the fundamental groups of digraphs and graphs. We give an application to graph coloring.     

Critical points of solutions of degenerate elliptic equations in the plane

We study the minimizer u of a convex functional in the plane which is not Gâteaux-differentiable. Namely, we show that the set of critical points of any C ¹-smooth minimizer can not have isolated points. Also, by means of some appropriate approximating scheme and viscosity solutions, we determine an Euler–Lagrange equation that u must satisfy. By applying the same approximating scheme, we can pair u with a function v which may be regarded as the stream function of u in a suitable generalized sense.     

Role of sequence and conformation on the photochemistry and the photophysics of A-T DNA dimers: an experimental and computational approach

The role of base sequence and conformation on the photochemistry and photophysics of thymidylyl (3'-5')-2'-deoxyadenosine sodium salt (TpdA) and 2-deoxyadenylyl (3'-5')-thymidine ammonium salt (dApT) was studied. To this end, nanosecond transient absorption at 266 nm, steady-state irradiation at 254 nm, and quantum chemical calculations were used. The transient absorption spectra show the solvated electron broad band in the visible region for each dinucleotide. In addition, low-intensity absorption bands are observed in the UV region, which are attributed to the deprotonated and protonated neutral radicals of adenine and thymine bases. Photoionization (PI) occurs by one- and two-photon pathways; the latter accounting for approximately 70% of the net PI yield. A diffusion-limited rate constant of 2.0 x 10(10) M(-1) s(-1) was obtained for the reaction of the neutral molecule with the photoejected electron in both sequences. The photodestruction yield, measured from the chromophore loss at 260 nm, decreases in the presence of well-known electron scavengers. This suggests the participation of base radical anions as one of the photodegradation pathways, which is higher in TpdA than in dApT. The intermediacy of a radical ion pair (charge separated state) between the adjacent adenine and thymine bases is proposed in the formation of the [2 + 2] cycloadduct intermediate. The [2 + 2] cycloadduct intermediate is known to be the precursor of the thymine-adenine eight-member ring photoproduct (TA*). Conformational constrains in the radical ion pair are suggested to explain the absence of the TA* photoproduct in dApT. This hypothesis is supported by semiempirical calculations performed on all relevant reactive intermediates proposed to participate in the mechanism of formation of TA*. Altogether, the results show that sequence and conformation profoundly influence the photochemistry and the photophysics of these DNA model systems.     

Microwave-assisted regioselective cycloaddition reactions between 9-substituted anthracenes and levoglucosenone

The cycloaddition reactions of 9-substituted anthracenes and levoglucosenone were investigated under microwave irradiation and conventional heating conditions. Considering time, yields, and regioselectivity, microwave technology has proven to be an ideal tool to achieve this chemical transformation. [reaction: see text].