Assessing and measuring financial sustainability model of the Spanish HIV HGM BioBank.

Background: The Spanish HIV HGM BioBank is of great relevance for basic and clinical investigation, and for those groups trying to establish large networks focused on investigation on specific clinical problems. The collection of different types of samples from HIV-infected individuals is the beginning of the chain of translational investigation, starting in 2004 a prospective national HIV BioBank that expanded in 2009 a local node (HGM: Hospital Gregorio Marañón) for diverse pathologies and clinical networks, not only in adults but also in paediatric patients, becoming the Spanish HIV HGM BioBank. Our main objective is to find a general criteria and analytical tools to widespread its economic management to assure their sustainability and the future exploitation of the extreme high valuable biomaterial they custody.

Nucleophilic Additions to Coordinated 1,10-Phenanthroline: Intramolecular, Intermolecular, Reversible, and Irreversible.

KN(SiMe ) reacts with [Re(CO) (phen)(PMe )]OTf via reversible addition to the phen ligand and irreversible deprotonation of the PMe ligand followed by intramolecular attack to phen by the deprotonated phosphane, whereas MeLi irreversibly adds to phen. The addition of MeLi has been shown to be intermolecular, unlike previously known nucleophilic additions to pyridines.

Synthesis of Silver(I) and Gold(I) Complexes Containing Enantiopure Pybox Ligands. First Assays on the Silver(I)-Catalyzed Asymmetric Addition of Alkynes to Imines.

Dinuclear complexes [Ag2(CF3SO3){(S,S)-(i)Pr-pybox}2][CF3SO3] (1), [Ag2(R-pybox)2][X]2 [R-pybox = 2,6-bis[4-(S)-isopropyloxazolin-2-yl]pyridine (S,S)-(i)Pr-pybox and X = PF6 (2) and BF4 (3); R-pybox = 2,6-bis[(3aS,8aR)-8,8a-dihydro-3aH-indeno[1,2-d]oxazol-2-yl]pyridine (3aS,3a'S,8aR,8a'R)-indane-pybox and X = CF3SO3 (4)], [Ag2{(S,S)-(i)Pr-pybox}{(3aS,3a'S,8aR,8a'R)-indane-pybox}][CF3SO3]2 (5), and [Ag2(R-pybox)3][X]2 [R-pybox = (3aS,3a'S,8aR,8a'R)-indane-pybox and X = CF3SO3 (10), SF6 (11), and PF6 (12)] as well as mononuclear complexes [Ag(R-pybox)2][X] [R-pybox = (S,S)-(i)Pr-pybox and X = SbF6 (6), PF6 (7), and BF4 (8); R-pybox = (3aS,3a'S,8aR,8a'R)-indane-pybox) and X = BF4 (9)] have been prepared by the reaction of the corresponding silver salts and pybox ligands using the appropriate molar ratio conditions. The first gold(I)/pybox complex [Au6Cl4{(S,S)-(i)Pr-pybox}4][AuCl2]2 (13) has been synthesized by the reaction of [AuCl{S(CH3)2}] and (S,S)-(i)Pr-pybox (1:1 molar ratio) in acetonitrile. The structures of the dinuclear (1, 4, 5, 10, and 11) and mononuclear (6 and 9) silver complexes and the hexanuclear gold complex 13 have been determined by single-crystal X-ray diffraction analysis.

Synthesis and structure of ruthenium(IV) complexes featuring N-heterocyclic ligands with an N-H group as the hydrogen-bond donor: hydrogen interactions in solution and in the solid state.

The synthesis and characterization of novel ruthenium(IV) complexes [Ru(η(3):η(3)-C(10)H(16))Cl(2)L] [L = 3-methylpyrazole (2b), 3,5-dimethylpyrazole (2c), 3-methyl-5-phenylpyrazole (2d), 2-(1H-pyrazol-5-yl)phenol (2e), 6-azauracile (3), and 1H-indazol-3-ol (4)] are reported. Complex 2e is converted to the chelated complex [Ru(η(3):η(3)-C(10)H(16))Cl(κ(2)-N,O-2-(1H-pyrazol-3-yl)phenoxy)] (5) by treatment with an excess of NaOH. All of the ligands feature N-H, O-H, or C═O as the potential hydrogen-bonding group.

Synthesis of copper(I) complexes containing enantiopure pybox ligands. First assays on enantioselective synthesis of propargylamines catalyzed by isolated copper(I) complexes.

Dinuclear [Cu(2)(R-pybox)(2)][X](2) [X = PF(6), R-pybox = 2,6-bis[4'-(S)-isopropyloxazolin-2'-yl]pyridine (S,S)-(i)Pr-pybox (1), 2,6-bis[4'-(R)-phenyloxazolin-2'-yl]pyridine) (R,R)-Ph-pybox (2), 2,6-bis[4'-(S)-isopropyl-5',5'-difeniloxazolin-2'-yl]pyridine (S,S)-(i)Pr-pybox-diPh (3); X = OTf, (R,R)-Ph-pybox (4)] and mononuclear complexes [Cu(R-pybox)(2)][PF(6)] [R-pybox = (S,S)-(i)Pr-pybox (5), (R,R)-Ph-pybox (6)] have been diastereoselectively prepared by reaction of [Cu(MeCN)(4)][PF(6)] or CuOTf.0.5C(6)H(6) and the corresponding pybox ligand.

Up to seven-component adducts by unprecedented multiple alkyne and carbonyl insertions in the metal-carbon bond of chromium alkoxy alkynyl carbene complexes.

Chromium alkoxy alkynyl Fischer carbene complexes react with symmetrical internal alkynes to form new and different organometallic species, which result from consecutive insertions of several alkyne units and carbonyl groups into the metal-carbon bond. The insertion sequence can be controlled and, by slight modification of the reaction conditions, it can be directed to the preparation of either seven- or five-component adducts. Three molecules of alkyne, two carbonyl groups, the carbene ligand and the chromium metal moiety partake in the creation of seven new carbon-carbon bonds and two five-membered carbocycles in the first case while four new carbon-carbon bonds, a sigma Cr--C(sp(2)) bond and a cyclopentadienyl moiety are built in the second case.

[Adherence to codes of conduct for biomedical information on the internet in useful websites for pharmacotherapy follow-up].

Objectives: To assess adherence to four codes of conduct in websites providing information useful for pharmacotherapy follow-up.

Methods: We performed a descriptive study of adherence to quality criteria in 19 websites. These sites had been identified in a previous study as being those most frequently used by pharmacists.

The reaction of o-alkynylarene and heteroarene carboxaldehyde derivatives with iodonium ions and nucleophiles: a versatile and regioselective synthesis of 1H-isochromene, naphthalene, indole, benzofuran, and benzothiophene compounds.

The reaction of o-alkynylbenzaldehydes 1 with different alcohols, silylated nucleophiles 5, electron-rich arenes 10, and heteroarenes 12 in the presence of the reagent IPy(2)BF(4), at room temperature, gave functionalized 4-iodo-1H-isochromenes 2, 6, 11, and 13 in a regioselective manner. When alkynes 16 and alkenes 19 and 20 were used as nucleophiles, a regioselective benzannulation reaction took place to form 1-iodonaphthalenes 17 and 1-naphthyl ketones 18, respectively. Moreover, the latter process has been adapted to accomplish the synthesis of indole, benzofuran, and benzothiophene derivatives (23, 27, and 28, respectively).

Synthesis of donor-acceptor alkynylcyclopropanes by diastereoselective cyclopropanation of electron-deficient alkenes with alkoxyalkynyl Fischer carbene complexes.

The reaction of electron-deficient alkenes with alkoxyalkynyl Fischer carbene complexes (FCCs) represents a straightforward route to a new type of captodative (donor-acceptor) alkynylcyclopropanes, which have been prepared in moderate to high yields and in a diastereoselective manner. Some studies regarding the employment of additives to facilitate the recovery of the metal moiety after the reaction are also described. Finally, the first example of a cyclopropanation reaction through employing Fischer carbene complexes under microwave irradiation is presented; this method proved to be an advantageous alternative to the thermal reaction.

NMR spectroscopic analysis of new spiro-piperidylrifamycins.

New spiro-piperidylrifamycin derivatives are presented. These compounds were synthesized from the reaction of 3-amino-4-iminorifamycin S and enantiomerically pure 4-piperidones, which generate diasteroisomeric rifabutin analogues with a new stereocentre at the spiranic carbon. The (1)H and (13)C NMR spectra of these new compounds, and also the configuration of the new stereogenic centres, were assigned using 2D NMR spectroscopic techniques.

Fluoride-promoted oxidation of Fischer alkoxy carbene complexes: stoichiometric and catalytic conditions.

The utility of fluoride anion as promoter of the oxidation of Fischer carbene complexes is presented. Two different and complementary methods that allow the fast and convenient preparation of carbene-derived esters in good yields have been developed using stoichiometric or catalytic quantities of fluoride ion.

Asymmetric dearomatization of the furan ring promoted by conjugate organolithium addition to (menthyloxy)(3-furyl)carbene complexes of chromium.

The sequential low-temperature addition reaction of an organolithium compound and methyl triflate to (menthyloxy)(3-furyl)carbene complexes of chromium and tungsten proceeded with excellent regioselectivity (1,4-addition) and diastereoselectivity (2,3-trans disposition of the nucleophile and electrophile groups) to afford new 2,3-disubstituted (2,3-dihydro-3-furyl)carbene complexes. In addition, a high degree of diastereofacial selectivity was achieved by employing alkenyllithium compounds. After detachment of both the metal fragment and the chiral auxiliary group, trisubstituted 2,3-dihydrofuran derivatives containing a quaternary stereogenic center at the C3 position were obtained.

Stereoselective formal [3 + 2] cycloaddition of N-alkylidene glycine ester anions to chiral Fischer alkenylcarbene complexes. Asymmetric synthesis of 3,4,5-trisubstituted prolines.

The reaction between N-alkylidene glycine ester enolates, generated from glycine esters aldimines with LDA in THF at low temperature, and chiral alkoxyalkenylcarbene complexes of chromium provided directly 2,4,5-trisubstituted-3-pyrrolidinylcarbene complexes with total exo selectivity and very high syn and facial diastereoselectivity when carbene complexes bearing the (-)-8-phenylmenthyloxy group were employed. Oxidation of the metal carbene moiety followed by basic hydrolysis of the esters afforded enantiomerically highly enriched syn,exo-3,4,5-trisubstituted prolines, whereas acidic hydrolysis of the same functional groups proceeded with epimerization at the alpha-amino acid center leading to anti,exo-3,4,5-trisubstituted prolines of very high enantiomeric purity as well.

Stereoselective Michael Addition of Glycine Anions to Chiral Fischer Alkenylcarbene Complexes. Asymmetric Synthesis of beta-Substituted Glutamic Acids.

The reaction of lithium enolates of achiral N-protected glycine esters with chiral alkoxyalkenylcarbene complexes of chromium provided the corresponding Michael adducts with either high anti or syn selectivity depending on the nature of the nitrogen protecting group, and high diastereofacial selectivity when carbene complexes containing the (-)-8-phenylmenthyloxy group were employed. Subsequent oxidation of the metal-carbene moiety followed by deprotection of the amine group and hydrolysis of both carboxylic esters afforded enantiomerically enriched 3-substituted glutamic acids of natural as well as unnatural stereochemistry. Alternatively, when the deprotection step was performed previously to the oxidation, cyclic aminocarbene complexes were formed, which finally led to optically active 3-substituted pyroglutamic acids.