Listening to Contemporary Art Music: A Morphodynamic Model of Cognition.

This paper proposes that the perceptual and cognitive mechanisms involved when listening to certain genres within "sound-based" music, such as post-spectralism, glitch-electronica, and electroacoustic music and in various areas of sound art, are best understood within a connectionist cognitive framework described by morphodynamic theory. By analysing the specific characteristics of sound-based music, it is explored how this kind of music works at perceptual and cognitive levels. The sound patterns found in these pieces engage listeners more readily at a phenomenological level rather than through establishing long-term conceptual associations.

Novel Methinic Functionalized and Dendritic C-Scorpionates.

The study of chelating ligands is undoubtedly one of the most significant fields of research in chemistry. The present work is directed to the synthesis of new functionalized derivatives of tripodal C-scorpionate compounds. Tris-2,2,2-(1-pyrazolyl)ethanol, HOCH₂C(pz)₃ (), one of the most important derivatives of hydrotris(pyrazolyl)methane, was used as a building block for the synthesis of new functionalized C-scorpionates, aiming to expand the scope of this unexplored class of compounds.

Integration of cellular and molecular endpoints to assess the toxicity of polycyclic aromatic hydrocarbons in HepG2 cell line.

Polycyclic aromatic hydrocarbons (PAHs) are persistent pollutants present in the environment with known mutagenic and carcinogenic properties. In the present study the effects of exposure to single or multiple doses of benzo[a]anthracene (BaA), pyrene (Pyr), and 3 halogenated derivatives of these compounds (1-chloropyrene, 1-bromopyrene [1-BrPyr], and 7-chlorobenzo[a]anthracene [7-ClBaA]) were evaluated in a liver-derived human cell line (HepG2). Cytotoxicity as assessed by the classic 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and neutral red assays showed a mild toxic effect in response to single or multiple dose exposure for up to 72 h, except for multiple dose exposure to BaA and 7-ClBaA (1 μM/d for 4 d) and single exposure to 10 μM BaA.

The phenolic metabolites of the anti-HIV drug efavirenz: evidence for distinct reactivities upon oxidation with Frémy's salt.

Efavirenz (EFV) is a non-nucleoside reverse transcriptase inhibitor administered as first line treatment against HIV-1. The major drawbacks of EFV therapy are neurotoxicity and hepatotoxicity, which may result from bioactivation to reactive metabolites capable of reacting with bionucleophiles. We investigated the in vitro oxidation of the phenolic EFV metabolites, 7-hydroxy-efavirenz (7-OH-EFV) and 8-hydroxy-efavirenz (8-OH-EFV), with Frémy's salt.

The role of competitive binding to human serum albumin on efavirenz-warfarin interaction: a nuclear magnetic resonance study.

The potential for co-prescription of the anti-human immunodeficiency virus (anti-HIV) drug efavirenz (EFV) and the oral anticoagulant warfarin (WAR) is currently high as EFV is a drug of choice for HIV type 1 infection and because cardiovascular disease is increasing among HIV-infected individuals. However, clinical reports of EFV-WAR interaction, leading to WAR overdosing, call for elucidation of the mechanisms involved in this drug-drug interaction. Here we present the first report demonstrating competition of the two drugs for the same binding site of human serum albumin.

A novel di-compartmental bis-(2-hydroxyisophtalamide) macrocyclic ligand and its mononuclear Cu(II) and Ni(II) complexes.

The synthesis and characterisation of the new di-compartmental bis-(2-hydroxyisophtalamide) macrocyclic pro-ligand, LH(6), which comprises two phenol-diamide units linked by ethylene bridges, is herein reported, together with its corresponding di-phenolate salt, [NBu(4)](2)[LH(4)]. The three macrocyclic compounds, [LH(4)(OMe)(2)] (protected ligand), LH(6) and [LH(4)][NBu(4)](2) were fully characterised including X-ray crystallography for [LH(4)(OMe)(2)] and [NBu(4)](2)[LH(4)]. The results of solid-state and solution studies have indicated that the macrocycle can adopt specific conformations, which are influenced by H-bonding interactions as well as the deviation of the amide carbonyl relative to the phenol plane.

Biomimetic oxidation of aromatic xenobiotics: synthesis of the phenolic metabolites from the anti-HIV drug efavirenz.

We report the oxidation of the first line anti-HIV drug efavirenz (EFV), mediated by a bio-inspired nonheme Fe-complex. Depending upon the experimental conditions this system can be tuned either to yield the major EFV metabolite, 8-hydroxy-EFV, in enantiomerically pure form or to mimic cytochrome P450 (CYP) activity, yielding 8-hydroxy-EFV and 7-hydroxy-EFV, the two phenolic EFV metabolites reported to be formed in vivo. The successful oxidation of the anti-estrogen tamoxifen and the equine estrogen equilin into their CYP-mediated metabolites supports the general application of bio-inspired nonheme Fe-complexes in mirroring CYP activity.

Persistent hydrogen-bonded and non-hydrogen-bonded phenoxyl radicals.

The production of stable phenoxyl radicals is undoubtedly a synthetic chemical challenge. Yet it is a useful way to gain information on the properties of the biological tyrosyl radicals. Recently, several persistent phenoxyl radicals have been reported, but only limited synthetic variations could be achieved.

Synthesis and coordination chemistry of a new N4-polydentate class of pyridyl-functionalized scorpionate ligands: complexes of Fe(II), Zn(II), Ni(II), V(IV), Pd(II) and use for heterobimetallic systems.

The new potentially N(4)-multidentate pyridyl-functionalized scorpionates 4-((tris-2,2,2-(pyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy, (1)) and 4-((tris-2,2,2-(3-phenylpyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy(Ph), (2)) have been synthesized and their coordination behavior toward Fe(II), Ni(II), Zn(II), Cu(II), Pd(II), and V(III) centers has been studied. Reaction of (1) with Fe(BF(4))(2) x 6 H(2)O yields [Fe(TpmPy)(2)](BF(4))(2) (3), that, in the solid state, shows the sandwich structure with trihapto ligand coordination via the pyrazolyl arms, and is completely low spin (LS) until 400 K. Reactions of 2 equiv of (1) or (2) with Zn(II) or Ni(II) chlorides give the corresponding metal complexes with general formula [MCl(2)(TpmPy*)(2)] (M = Zn, Ni; TpmPy* = TpmPy, TpmPy(Ph)) (4-7) where the ligand is able to coordinate through either the pyrazolyl rings (in case of [Ni(TpmPy)(2)]Cl(2) (5)) or the pyridyl-side (for [ZnCl(2)(TpmPy)(2)] (4), [ZnCl(2)(TpmPy(Ph))(2)] (6) and [NiCl(2)(TpmPy(Ph))(2)] (7)).

Cu(II) complexes bearing the 2,2,2-tris(1-pyrazolyl)ethanol or 2,2,2-tris(1-pyrazolyl)ethyl methanesulfonate scorpionates. X-Ray structural characterization and application in the mild catalytic peroxidative oxidation of cyclohexane.

Reactions between CuCl2 and the functionalized scorpionate 2,2,2-tris(1-pyrazolyl)ethanol HOCH2C(pz)3 1 (pz = pyrazolyl) or 2,2,2-tris(1-pyrazolyl)ethyl methanesulfonate CH3SO2OCH2C(pz)3 2 yield the corresponding water soluble CuII complexes [CuCl2{HOCH2C(pz)3}] 3 or [CuCl2{CH3SO2OCH2C(pz)3}]2 4. In 3 the scorpionate ligand shows the typical N,N,N-coordination mode, whereas in the dinuclear complex 4 it binds the metal as a bidentate species. Compounds 1-4 have been characterized by IR, far-IR, elemental analysis and (for 2-4) single crystal X-ray diffraction.

Electrocatalytic reduction of organohalides mediated by the dihalo-molybdenum phosphinic complexes trans-[MoX(2)(Ph(2)PCH(2)CH(2)PPh(2))(2)] (X = I, Br)-A mechanistic study by cyclic voltammetry digital simulation.

trans-[MoX(2)(dppe)(2)] (X = I, Br) act as inner-sphere electron-transfer mediators for the electrocatalytic reduction of organohalides RX to R + X(-), at both Mo(II)--> Mo(I) and Mo(I)--> Mo(0) reduction processes, each of them involving a cathodically induced heterolytic metal-halide bond cleavage with liberation of X(-) that is followed by addition of RX to the metal. Digital simulation of cyclic voltammetry at a wide range of scan rates allowed to estimate the rate constants of the various chemical steps for both electrocatalytic cycles, which were compared in terms of Mo-X bond dissociation energies, electronic and stereochemical effects.

Switching between kappa(2) and kappa(3) bis(pyrazol-1-yl)acetate ligands by tuning reaction conditions: synthesis, spectral, electrochemical, structural, and theoretical studies on arene-Ru(II) derivatives of bis(azol-1-yl)acetate ligands.

New (arene)ruthenium(II) derivatives containing neutral HL or anionic L(-) ligands (arene = p-cymene or benzene, HL in general, in particular HL(1) = bis(pyrazol-1-yl)acetic acid and HL(2) = bis(3,5-dimethylpyrazol-1-yl)acetic acid) have been synthesized and analytically and spectrally characterized. The ligands in neutral form coordinate ruthenium in a chelating kappa(2)-N,N'-bidentate fashion affording 1:1 derivatives of formula [Ru(arene)(HL)Cl]Cl, where the inner Cl can be replaced by a phosphine. These derivatives show very high conductance values in water, due to the contribution of H(3)O(+) produced by deprotonation of the -COOH fragment in HL ligands and consequent formation of 1:2 electrolytes such as [Ru(arene)(kappa(3)-N,N',O-L)]Cl(2) species.

Cu(I) complexes bearing the new sterically demanding and coordination flexible tris(3-phenyl-1-pyrazolyl)methanesulfonate ligand and the water-soluble phosphine 1,3,5-triaza-7-phosphaadamantane or related ligands.

The new sterically hindered scorpionate tris(3-phenylpyrazolyl)methanesulfonate (Tpms(Ph))(-) has been synthesized and its coordination behavior toward a Cu(I) center, in the presence of 1,3,5-triaza-7-phosphaadamantane (PTA), N-methyl-1,3,5-triaza-7-phosphaadamantane tetraphenylborate ((mPTA)[BPh4]) or hexamethylenetetramine (HMT) has been studied. The reaction between Li(Tpms(Ph)) (1) and [Cu(MeCN)4][PF6] yields [Cu(Tpms(Ph))(MeCN)] (2) which, upon further acetonitrile displacement on reaction with PTA, HMT, or (mPTA)[BPh4], gives the corresponding complexes [Cu(Tpms(Ph))(PTA)] (3), [Cu(Tpms(Ph))(HMT)] (4), and [Cu(Tpms(Ph))(mPTA)][PF6] (5). All the compounds have been characterized by (1)H, (31)P, (13)C, COSY or HMQC-NMR, IR, elemental analysis, and single crystal X-ray diffraction.

Areneruthenium(II) 4-acyl-5-pyrazolonate derivatives: coordination chemistry, redox properties, and reactivity.

Areneruthenium(II) molecular complexes of the formula [Ru(arene)(Q)Cl], containing diverse 4-acyl-5-pyrazolonate ligands Q with arene = cymene or benzene, have been synthesized by the interaction of HQ and [Ru(arene)Cl(micro-Cl)]2 dimers in methanol in the presence of sodium methoxide. The dinuclear compound [{Ru(cymene)Cl}2Q4Q] (H2Q4Q = bis(4-(1-phenyl-3-methyl-5-pyrazolone)dioxohexane), existing in the RRuSRu (meso form), has been prepared similarly. [Ru(cymene)(Q)Cl] reacts with sodium azide in acetone, affording [Ru(cymene)(Q)N3] derivatives, where Cl- has been replaced by N3-.