Wavelength-dependent electron and energy transfer pathways in a side-to-face ruthenium porphyrin/perylene bisimide assembly

A new side-to-face supramolecular array of chromophores, where a pyridyl-substituted perylene bisimide dye axially binds to two ruthenium porphyrin fragments, has been prepared by self-assembly. The array is formulated as DPyPBI[Ru(TPP)(CO)](2), where DPyPBI = N,N'-di(4-pyridyl)-1,6,7,12-tetra(4-tert-butylphenoxy)perylene-3,4:9,10-tetracarboxylic acid bisimide and TPP = 5,10,15,20-tetraphenylporphyrin. The photophysical behavior of DPyPBI[Ru(TPP)(CO)](2) has been studied by fast (nanoseconds) and ultrafast (femtoseconds) time-resolved techniques. The observed behavior sharply changes with excitation wavelength, depending on whether the DPyPBI or Ru(TPP)(CO) units are excited. After DPyPBI excitation, the strong fluorescence typical of this unit is completely quenched, and time-resolved spectroscopy reveals the occurrence of photoinduced electron transfer from the ruthenium porphyrin to the perylene bisimide dye (tau = 5.6 ps) followed by charge recombination (tau = 270 ps). Upon excitation of the Ru(TPP)(CO) fragments, on the other hand, ultrafast (tau < 1 ps) intersystem crossing is followed by triplet energy transfer from the ruthenium porphyrin to the perylene bisimide dye (tau = 720 ps). The perylene-based triplet state decays to the ground state on a longer time scale (tau = 9.8 micros). The photophysics of this supramolecular array provides remarkable examples of (i) wavelength-dependent behavior (a small change in excitation wavelength causes a sharp switch from electron to energy transfer) and (ii) intramolecular sensitization (the triplet state of the perylene bisimide, inaccessible in the free dye, is efficiently populated in the array).     

Evolution of the Pt layer deposited on MgO(001) by pulsed laser deposition as a function of the deposition parameters: a scanning tunneling microscopy and energy dispersive X-ray diffractometry/reflectometry study

A combined ultrahigh vacuum scanning tunneling microscopy (STM-UHV) and energy dispersive X-ray diffractometry/reflectometry (EDXD/EDXR) study of the evolution of face-centered cubic (fcc) Pt layer growth on MgO(100) by pulsed laser deposition as a function of the process parameters such as deposition temperature and deposition duration has been carried out. The aim of this study is to define the best experimental conditions to obtain a controlled film deposition selective on the Pt growth direction (either [111] or [002]). The evolution of the Pt surface morphology as a function of the deposition temperature (T(dep)) from 300 to 700 degrees C has been studied with STM and ED techniques. Results show that the Pt surface, characterized at T(dep) = 300 degrees C by a 3D island morphology, evolves at higher temperatures to a morphology in which the original islands coexist with a distribution of orthogonal 2D stripes. The two features can be associated with the [111] and [002] Pt growth directions of the fcc phase, respectively. For T(dep) = 700 degrees C, the island morphology of the (111) face completely disappears, while the merging process of the (002) stripes reaches completion. The evolution of the morphology at T(dep) = 600 degrees C as a function of the deposition time and thickness has then been studied with STM-UHV, revealing an initial growth of mosaic-like 3D islands. These independent islands, already interconnected, expand along two orthogonal directions and, for longer deposition times, lead to the texture of orthogonal stripes. The EDXR characterization providing the morphological parameters of the films, i.e., thickness and roughness, confirms the above observation and quantifies the effect of such morphological changes on the surface roughness of the Pt film, an important parameter for applications of Pt films as underlayer in magnetic recording media.     

Turbulent Drag Reduction by a Near Wall Surface Tension Active Interface

In this work we study the turbulence modulation in a viscosity-stratified two-phase flow using Direct Numerical Simulation (DNS) of turbulence and the Phase Field Method (PFM) to simulate the interfacial phenomena. Specifically we consider the case of two immiscible fluid layers driven in a closed rectangular channel by an imposed mean pressure gradient. The present problem, which may mimic the behaviour of an oil flowing under a thin layer of different oil, thickness ratio h₂/h₁ =?9, is described by three main flow parameters: the shear Reynolds number Re _τ (which quantifies the importance of inertia compared to viscous effects), the Weber number We (which quantifies surface tension effects) and the viscosity ratio λ = ν₁/ν₂ between the two fluids. For this first study, the density ratio of the two fluid layers is the same (ρ₂ = ρ₁), we keep Re _τ and We constant, but we consider three different values for the viscosity ratio: λ =?1, λ =?0.875 and λ =?0.75. Compared to a single phase flow at the same shear Reynolds number (Re _τ =?100), in the two phase flow case we observe a decrease of the wall-shear stress and a strong turbulence modulation in particular in the proximity of the interface. Interestingly, we observe that the modulation of turbulence by the liquid-liquid interface extends up to the top wall (i.e. the closest to the interface) and produces local shear stress inversions and flow recirculation regions. The observed results depend primarily on the interface deformability and on the viscosity ratio between the two fluids (λ).     

Negatively buoyant plume dispersion: a comparison of simple mathematical models, hydraulic simulations and field data

Summary The ground-level concentration distribution for negatively buoyant gases of various densities, emitted from stacks with heights, diameters and exit velocities varying in the typical range of geothermal drilling activities, was studied by means of hydraulic simulations performed in neutral conditions at different flow speeds. These measurements, and a few others taken in the field in nearly neutral and unstable atmosphere during tests of CO₂ release from a geothermal well, were compared with the values expected from a Gaussian formula corrected for denser-than-air, tilted plumes. For calculating theoretical concentrations, three couples of horizontal and vertical plume standard deviations as functions of downwind distance from source were employed: those given by Singer-Smith and Briggs and a third one obtained by our group during a previous water channel experiment. Also the maximum ground-level concentration and its distance from the source were measured in each simulation and compared with the prediction of our Gaussian formula, as well as with a best-fit expression given by Meroney. The concentration pattern χ(x, y, 0) given by the corrected Gaussian formula proved to be in good agreement with experimental data, especially in association with Singer-Smith's or our sigmas. When only maximum g.l. concentrations are needed, also the simple formula suggested by Meroney can give a good approximation.

---

Riassunto Una serie di simulazioni in vasca senza stratificazione, condotte a varie velocità della vena idraulica, ha permesso di studiare la distribuzione di concentrazione al suolo dovuta a gas con varie densità maggiori di quella dell'aria, emessi da ciminiere con altezze, diametri e velocità di efflusso variabili entro intervalli tipici delle attività di perforazione geotermica. Queste misure, ed alcune altre ottenute in campo in condizioni di atmosfera circa neutra e instabile durante prove di rilascio di CO₂ da un pozzo geotermico, sono state confrontate con i valori attesi in base ad una formula gaussiana corretta per pennacchi inclinati. Nel calcolo delle concentrazioni teoriche si sono impiegate tre diverse coppie di espressioni per le deviazioni standard orizzontale e verticale del pennacchio: quelle date da Singer-Smith e Briggs ed una terza ottenuta dal nostro gruppo durante una precedente esperienza in canale idraulico. In ciascuna prova si è misurata anche la concentrazione massima al suolo e la sua distanza dalla sorgente; queste quantità sono state raffrontate con le previsioni della formula gaussiana e con una espressione empirica proposta da Meroney. Il campo di concentrazione χ(x, y, 0) dato dalla formula gaussiana corretta è risultato in buon accordo con le misure, specialmente se associato alle sigma di Singer-Smith o alle nostre. Quando sia sufficiente una valutazione della concentrazione massima, anche la semplice formula di Meroney può dare una buona approssimazione.

     

The inorganic perspective of nerve growth factor: interactions of Cu2+ and Zn2+ with the N-terminus fragment of nerve growth factor encompassing the recognition domain of the TrkA receptor

There is a significant overlap between brain areas with Zn(2+) and Cu(2+) pathological dys-homeostasis and those in which the nerve growth factor (NGF) performs its biological role. The protein NGF is necessary for the development and maintenance of the sympathetic and sensory nervous systems. Its flexible N-terminal region has been shown to be a critical domain for TrkA receptor binding and activation. Computational analyses show that Zn(2+) and Cu(2+) form pentacoordinate complexes involving both the His4 and His8 residues of the N-terminal domain of one monomeric unit and the His84 and Asp105 residues of the other monomeric unit of the NGF active dimer. To date, neither experimental data on the coordination features have been reported, nor has one of the hypotheses according to which Zn(2+) and Cu(2+) may have different binding environments or the Ser1 α-amino group could be involved in coordination been supported. The peptide fragment, encompassing the 1-14 sequence of the human NGF amino-terminal domain (NGF(1-14)), blocked at the C terminus, was synthesised and its Cu(2+) and Zn(2+) complexes characterized by means of potentiometric and spectroscopic (UV/Vis, CD, NMR, and EPR) techniques. The N-terminus-acetylated form of NGF(1-14) was also investigated to evaluate the involvement of the Ser1 α-amino group in metal-ion coordination. Our results demonstrate that the amino group is the first anchoring site for Cu(2+) and is involved in Zn(2+) coordination at physiological pH. Finally, a synergic proliferative activity of both NGF(1-14) and the whole protein on SHSY5Y neuroblastoma cell line was found after treatment in the presence of Cu(2+). This effect was not observed after treatment with the N-acetylated peptide fragment, demonstrating a functional involvement of the N-terminal amino group in metal binding and peptide activity.     

Base promoted synthesis of activated cyclopropanes bearing homologated carbonyl groups via tandem Michael addition-intramolecular enolate trapping

A simple base promoted intramolecular Michael initiated ring closure reaction of γ-hydroxyenone derived diphenyl phosphinates with 1,3-indandione, enabled the synthesis of novel activated cyclopropanes with homologated carbonyl moiety in good yield. Promising levels of enantioselectivity are achieved when using cinchona derivatives as promoters.     

Deligne��s representation theory in complex rank and objects of integral type

Working with Pierre Deligne??s category of representations of the ??symmetric group S _t with t a complex number?? we give negative answers to certain questions on ${\otimes}$ -categories raised by Bruno Kahn and Charles A. Weibel.     

Vibrational analysis of x-ray absorption fine structure thermal factors by ab initio molecular dynamics: the Zn(II) ion in aqueous solution as a case study

In this work, we consider a new combination of vibrational analysis and normal-like mode decomposition of Debye-Waller factors of solvated ions entirely based on molecular dynamics data. Such a novel time-dependent analysis procedure provides a direct link between x-ray absorption fine structure parameters and normal mode contributions for an ion-solvent system. The potentialities of such a methodology rely on two fundamental aspects which distinguish it from already available tools. First, a general vibrational analysis that does not require any Gaussian or harmonic model for describing atomic fluctuations in liquids. Second, a very accurate sampling of the short range motions around the structural probe via the recently developed atom centered density matrix propagation/general liquid optimized boundary method. This novel molecular dynamics methodology is based on an integrated ab initio/classical potential using localized basis functions and nonperiodic boundary conditions. As a case study we have chosen the Zn(II) ion in aqueous solution. The consistency of our results and the observed good agreement with experiments show how the key support to advanced structural techniques from molecular dynamics can be further expanded and investigated.     

Development and validation of a liquid chromatography/electrospray ionization tandem mass spectrometry method for the quantification of latanoprost free acid in rabbit aqueous humor and ciliary body

A rapid, selective and sensitive method for quantification of latanoprost free acid in rabbit aqueous humor (AH) and ciliary body (CB) using reverse phase-high performance liquid chromatography coupled with electrospray ionization (ESI)-mass spectrometry/mass spectrometry has been developed and validated. Quantification in AH and CB was achieved by stable isotope dilution employing tetra-deuterated analog of latanoprost free acid, used as internal standard. Sample preparation was based on protein precipitation with methanol in AH, and on liquid extraction with a mixture of ethyl acetate and isopropanol 60:40 (v/v) in CB. Elution was achieved on an octylsilica (C8) column, using an isocratic elution method. Detection was performed on a triple quadrupole mass spectrometer, using ESI in positive ion selected reaction monitoring mode. Calibration curves were linear in the validated concentration ranges of 10-160 ng/mL in AH and 80-1280 ng/g in CB. The accuracy and precision values, obtained from three different sets of quality control samples, each analyzed in triplicate on three different days, were within the generally accepted criteria for analytical methods (< 15%). The limit of detection was 30.66 pg/mL in AH and 237.75 pg/g in CB. The assay proved to be accurate and precise when applied to the in vivo study of latanoprost free acid in rabbit AH and CB after single administration of an eye drops containing latanoprost.