Charge and substituent effects on the stability of porphyrin/G‐quadruplex adducts

The adduct ions of two tetramolecular G‐quadruplexes formed from the d(TGGGGT) and d(TTGGGGGT) single strands with a group of cationic porphyrins, with different charges and substituents, and one neutral porphyrin, were investigated by ESI‐MS and ESI‐MS/MS in the negative ion mode. Formation of [Q + nNH₄⁺+P^p+‐(z + n + p)H⁺]^z‐ adduct ions (where Q = quadruplex, n = number of quartets minus 1, P = porphyrin and p⁺ =0,1,2,3,4) indicates that the porphyrins are bound outside the quadruplexes providing an additional stabilization to those structures. The fragmentation pathways of the [Q + nNH₄⁺+P^p+‐(z + n + p)H⁺]^z‐ adduct ions depend on the number of positive charges (p⁺) of the porphyrins and on the overall complex charge (z^‐), but do not show a significant dependence on the type of the substituent groups in the porphyrins. Formation of the ‘unfilled’ ions [Q + P^p+‐(z + p)H⁺]^z‐ predominates for porphyrins with a higher number of positive charges. Strand separation with the formation of [T + P^p+‐(z‐2 + p)H⁺]^(z‐2)‐ and (SS‐2H⁺)^2‐ ions, where T = [d(TG₄T)]₃ and [d(T₂G₅T)]₃ and SS = d(TG₄T) and d(T₂G₅T) is only observed for the complexes with a higher overall negative charge. Porphyrin loss with the formation of [Q + nNH₄⁺‐(z + n)H⁺]^z‐ ions occurs predominantly for the neutral and monocharged porphyrins. The predominant formation of the ‘unfilled’ ions, [Q + P^p+‐(z + n)H⁺]^z‐, for porphyrins with a higher number of charges shows that these porphyrins can prevent strand separation and preserve, at least partially, the quadruplex structure. Copyright © 2012 John Wiley & Sons, Ltd.     

Electronic structures of AlMoO(y)(-) (y = 1-4) determined by photoelectron spectroscopy and density functional theory calculations

Vibrationally-resolved photoelectron spectra of AlMoO(y)(-) (y = 1-4) are presented and analyzed in conjunction with density functional theory computational results. The structures determined for the AlMoO(y) anion and neutral clusters suggest ionic bonding between Al(+) and a MoO(y)(-) or MoO(y)(-2) moiety, and point to the relative stability of Mo=O versus Al=O bonds. The highest occupied and partially occupied orbitals in the anions and neutrals can be described as Mo atomic-like orbitals, so while the Mo is in a higher oxidation state than Al, the most energetically accessible electrons are localized on the molybdenum center.     

Nuclear resonance vibrational spectra of five-coordinate imidazole-ligated iron(II) porphyrinates

Nuclear resonance vibrational spectra have been obtained for six five-coordinate imidazole-ligated iron(II) porphyrinates, [Fe(Por)(L)] (Por = tetraphenylporphyrinate, octaethylporphyrinate, tetratolylporphyrinate, or protoporphyrinate IX and L = 2-methylimidazole or 1,2-dimethylimidazole). Measurements have been made on both powder and oriented crystal samples. The spectra are dominated by strong signals around 200-300 cm(-1). Although the in-plane and out-of-plane vibrations are seriously overlapped, oriented crystal spectra allow their deconvolution. Thus, oriented crystal experimental data, along with density functional theory (DFT) calculations, enable the assignment of key vibrations in the spectra. Molecular dynamics are also discussed. The nature of the Fe-N(Im) vibrations has been elaborated further than was possible from resonance Raman studies. Our study suggests that the Fe motions are coupled with the porphyrin core and peripheral groups motions. Both peripheral groups and their conformations have significant influence on the vibrational spectra (position and shape).     

Benzene–kaolinite interaction properties

In this work, we present a theoretical study of interaction of benzene with kaolinite and an analysis of the vibrational spectra, electrostatic potential maps, and self consistent field (SCF) orbitals. B3LYP and MP2 benzene–kaolinite results indicate a preferential interaction of benzene on kaolinite octahedral surface. Population analysis indicates that the atoms modified their charges when the monoaromatic molecule and clay mineral are close to tetrahedral and octahedral surface of kaolinite, which suggests that the adsorbed molecule becomes slightly positive. Infrared vibrational data show the reduction in the band frequencies related to the kaolinite external hydroxyls, indicating a weak interaction of benzene with clay mineral. It also was verified, from the potential electrostatic maps, a change in electron density in both benzene and kaolinite. Electron localization function analysis was also carried out for this interaction. © 2011 Wiley Periodicals, Inc.     

Synthesis, magnetostructural correlation, and catalytic promiscuity of unsymmetric dinuclear copper(II) complexes: models for catechol oxidases and hydrolases

Herein, we report the synthesis and characterization, through elemental analysis, electronic spectroscopy, electrochemistry, potentiometric titration, electron paramagnetic resonance, and magnetochemistry, of two dinuclear copper(II) complexes, using the unsymmetrical ligands N',N',N-tris(2-pyridylmethyl)-N-(2-hydroxy-3,5-di-tert-butylbenzyl)-1,3-propanediamin-2-ol (L1) and N',N'-bis(2-pyridylmethyl)-N,N-(2-hydroxybenzyl)(2-hydroxy-3,5-di-tert-butylbenzyl)-1,3-propanediamin-2-ol (L2). The structures of the complexes [Cu(2)(L1)(μ-OAc)](ClO(4))(2)·(CH(3))(2)CHOH (1) and [Cu(2)(L2)(μ-OAc)](ClO(4))·H(2)O·(CH(3))(2)CHOH (2) were determined by X-ray crystallography. The complex [Cu(2)(L3)(μ-OAc)](2+) [3; L3 = N-(2-hydroxybenzyl)-N',N',N-tris(2-pyridylmethyl)-1,3-propanediamin-2-ol] was included in this study for comparison purposes only (Neves et al. Inorg. Chim. Acta2005, 358, 1807-1822). Magnetic data show that the Cu(II) centers in 1 and 2 are antiferromagnetically coupled and that the difference in the exchange coupling J found for these complexes (J = -4.3 cm(-1) for 1 and J = -40.0 cm(-1) for 2) is a function of the Cu-O-Cu bridging angle. In addition, 1 and 2 were tested as catalysts in the oxidation of the model substrate 3,5-di-tert-butylcatechol and can be considered as functional models for catechol oxidase. Because these complexes possess labile sites in their structures and in solution they have a potential nucleophile constituted by a terminal Cu(II)-bound hydroxo group, their activity toward hydrolysis of the model substrate 2,4-bis(dinitrophenyl)phosphate and DNA was also investigated. Double electrophilic activation of the phosphodiester by monodentate coordination to the Cu(II) center that contains the phenol group with tert-butyl substituents and hydrogen bonding of the protonated phenol with the phosphate O atom are proposed to increase the hydrolase activity (K(ass.) and k(cat.)) of 1 and 2 in comparison with that found for complex 3. In fact, complexes 1 and 2 show both oxidoreductase and hydrolase/nuclease activities and can thus be regarded as man-made models for studying catalytic promiscuity.     

Ligand Recruitment and Spin Transitions in the Solid-State Photochemistry of Fe((III))TPPCl

We report evidence for the formation of long-lived photoproducts following excitation of iron(III) tetraphenylporphyrin chloride (Fe((III))TPPCl) in a 1:1 glass of toluene and CH(2)Cl(2) at 77 K. The formation of these photoproducts is dependent on solvent environment and temperature, appearing only in the presence of toluene. No long-lived product is observed in neat CH(2)Cl(2) solvent. A 2-photon absorption model is proposed to account for the power-dependent photoproduct populations. The products are formed in a mixture of spin states of the central iron(III) metal atom. Metastable six-coordinate high-spin and low-spin complexes and a five-coordinate high-spin complex of iron(III) tetraphenylporphyrin are assigned using structure-sensitive vibrations in the resonance Raman spectrum. These species appear in conjunction with resonantly enhanced toluene solvent vibrations, indicating that the Fe((III)) compound formed following photoexcitation recruits a toluene ligand from the surrounding environment. Low-temperature transient absorption (TA) measurements are used to explain the dependence of product formation on excitation frequency in this photochemical model. The six-coordinate photoproduct is initially formed in the high-spin Fe((III)) state, but population relaxes into both high-spin and low-spin state at 77 K. This is the first demonstration of coupling between the optical and magnetic properties of an iron-centered porphyrin molecule.     

Binaural loudness summation for speech presented via earphones and loudspeaker with and without visual cues

Preliminary data [M. Epstein and M. Florentine, Ear. Hear. 30, 234-237 (2009)] obtained using speech stimuli from a visually present talker heard via loudspeakers in a sound-attenuating chamber indicate little difference in loudness when listening with one or two ears (i.e., significantly reduced binaural loudness summation, BLS), which is known as "binaural loudness constancy." These data challenge current understanding drawn from laboratory measurements that indicate a tone presented binaurally is louder than the same tone presented monaurally. Twelve normal listeners were presented recorded spondees, monaurally and binaurally across a wide range of levels via earphones and a loudspeaker with and without visual cues. Statistical analyses of binaural-to-monaural ratios of magnitude estimates indicate that the amount of BLS is significantly less for speech presented via a loudspeaker with visual cues than for stimuli with any other combination of test parameters (i.e., speech presented via earphones or a loudspeaker without visual cues, and speech presented via earphones with visual cues). These results indicate that the loudness of a visually present talker in daily environments is little affected by switching between binaural and monaural listening. This supports the phenomenon of binaural loudness constancy and underscores the importance of ecological validity in loudness research.     

Pitch-interval discrimination and musical expertise: Is the semitone a perceptual boundary?

The ability to discriminate pitch changes (or intervals) is foundational for speech and music. In an auditory psychophysical experiment, musicians and non-musicians were tested with fixed- and roving-pitch discrimination tasks to investigate the effects of musical expertise on interval discrimination. The tasks were administered parametrically to assess performance across varying pitch distances between intervals. Both groups showed improvements in fixed-pitch interval discrimination as a function of increasing interval difference. Only musicians showed better roving-pitch interval discrimination as interval differences increased, suggesting that this task was too demanding for non-musicians. Musicians had better interval discrimination than non-musicians across most interval differences in both tasks. Interestingly, musicians exhibited improved interval discrimination starting at interval differences of 100 cents (a semitone in Western music), whereas non-musicians showed enhanced discrimination at interval differences exceeding 125 cents. Although exposure to Western music and speech may help establish a basic interval-discrimination threshold between 100 and 200 cents (intervals that occur often in Western languages and music), musical training presumably enhances auditory processing and reduces this threshold to a semitone. As musical expertise does not decrease this threshold beyond 100 cents, the semitone may represent a musical training-induced intervallic limit to acoustic processing.     

Prestress effects on the eigenfrequencies of the soundboards: experimental results on a simplified string instrument

This paper presents an experimental study of the effects of prestresses on the vibration behavior of string instruments. These prestresses are created by gluing ribs (crowning) and tensioning string (downbearing). The effects of these prestresses were previously studied numerically for a piano soundboard by Mamou-Mani et al. [J. Acoust. Soc. Am. 123, 2401-2406 (2008)] and analytically for simplified models by Mamou-Mani et al. [Acta Acust. Unit. Acust. 95, 915-926 (2009)]. In the present study, a specified test bench is designed, including a simplified soundboard (a rectangular plate), a bridge, and a single string. The plate is subjected to in-plane and transverse loads. Vibrational eigenmodes are identified using nearfield acoustical holography (NAH) measurement. The evolution of eigenfrequencies with these specific prestresses is studied. The results show the effectiveness of NAH for this purpose and a very good qualitative concordance with previous numerical and analytical calculus.