Sparkle/AM1 modeling of holmium (III) complexes

The sparkle/AM1 model, recently defined for Eu(III), Gd(III) and Tb(III), is now extended to Ho(III). A set of 15 complexes with various representative ligands was chosen by cluster analysis from the set formed by the 27 Ho(III) complexes structures of high crystallographic quality (R factor < 0.05 Å) available in the Cambridge Structural Database and which possess oxygen or nitrogen as coordinating atoms. In the validation procedure, we included the remaining 12 Ho(III) complexes. For these 27 complexes, the Sparkle/AM1 unsigned mean error for all interatomic distances between the Ho(III) ion and the ligand atoms of the first sphere of coordination is 0.05 Å. Sparkle/AM1 constitutes the only semiempirical model for the quantum chemical calculation of Ho(III) coordination compounds available, with geometry prediction accuracies comparable to present day rare earth complex ab initio/ECP calculations, while being hundreds of times faster.     

Intra- and intermolecular 1,3-dipolar cycloaddition of sugar ketonitrones with mono-, di-, and trisubstituted dipolarophiles

The 1,3-dipolar cycloaddition of sugar ketonitrones is a useful synthetic procedure to build up nitrogenated quaternary centers in terms of scope (substrate, dipolarophile, inter- and intramolecular versions), yield, and regio- and stereoselectivity. The hybrid ONIOM (B3LYP/6-31G(d):AM1) theoretical method followed by single-point energy calculations at the B3LYP/6-31G(d) level adequately perform to model this cycloaddition for the relatively large ketosugar precursors commonly used.     

Chemical Modifications on Human Hair Studied by Means of Contact Angle Determination

Wetting properties of a solid surface can change as a consequence of chemical treatment. There is a relationship between the molecular structure of a surface and the macroscopic properties of this surface such as wetting and adhesion. Information on the surface energy of a solid was obtained by calculating polar and dispersion force contributions by means of contact angle determination. The superficial modification undergone by human hair treatments with or without hydrogen peroxide at alkaline pH was studied by means of wetting force measurements. The wetting increase in treated human hair fibers was analyzed following the Hüttinger method using contact angle data, taking into account the acid-base and dispersion components of the total wetting adhesion work. The hydrogen peroxide treatment at alkaline pH leads to a partial removal of hydrocarbon chains and to the formation of ionic groups (cysteic acid residues) on the outer scale cell surface. The latter phenomenon was observed by means of an increase in the acid-base adhesion work versus water wetting liquid at alkaline pH. Copyright 2001 Academic Press.     

On the mass spectrum of the 2+1 gauge-Higgs lattice quantum field theory

We investigate the mass spectrum of a 2+1 lattice gauge-Higgs quantum field theory with Wilson action A _P+A _H, whereA _P(A _H) is the gauge (gauge-Higgs) interaction. We determine the complete spectrum exactly for all , >0 by an explicit diagonalization of the gauge invariant transfer matrix in the approximation that the interaction terms in the spatial directions are omitted; all gauge invariant eigenfunctions are generated directly. For fixed momentum the energy spectrum is pure point and disjoint simple planar loops and strings are energy eigenfunctions. However, depending on the gauge group and Higgs representations, there are bound state energy eigenfunctions not of this form. The approximate model has a rich particle spectrum with level crossings and we expect that it provides an intuitive picture of the number and location of bound states and resonances in the full model for small , >0. We determine the mass spectrum, obtaining convergent expansions for the first two groups of masses above the vacuum, for small , and confirm our expectations.Research partially supported by CNPq, Brasil     

Aspects concerning the acoustical performance of school buildings in Portugal

Acoustic measurements were performed in eight schools of different levels of education (from kindergarten to college) located in Viseu – Portugal. The acoustic evaluation was made in order to analyze the most common problems that may condition the acoustic environment inside school building.     

Mechanisms of Cysteine-Lysine Covalent Linkage—The Role of Reactive Oxygen Species and Competition with Disulfide Bonds**

Recently, a new naturally occurring covalent linkage was characterised, involving a cysteine and a lysine, bridged through an oxygen atom. The latter was dubbed as the NOS bond, reflecting the individual atoms involved in this uncommon bond which finds little parallel in lab chemistry. It is found to form under oxidising conditions and is reversible upon addition of reducing agents. Further studies have identified the bond in crystal structures across a variety of systems and organisms, potentially playing an important role in regulation, cellular defense and replication. Not only that, double NOS bonds have been identified and even found to be competitive in relation to the formation of disulfide bonds. This raises several questions about how this exotic bond comes to be, what are the intermediates involved in its formation and how it competes with other pathways of sulfide oxidation. With this objective in mind, we revisited our first proposed mechanism for the reaction with model electronic structure calculations, adding information about the reactivity with alternative reactive oxygen species and other potential competing products of oxidation. We present a network with more than 30 reactions which provides one of the most encompassing pictures for cysteine oxidation pathways to date.     

Integrating multi-unit electrophysiology and plastic culture dishes for network neuroscience

The electrophysiological characterisation of cultured neurons is of paramount importance for drug discovery, safety pharmacology and basic research in the neurosciences. Technologies offering low cost, low technical complexity and potential for scalability towards high-throughput electrophysiology on in vitro neurons would be advantageous, in particular for screening purposes. Here we describe a plastic culture substrate supporting low-complexity multi-unit loose-patch recording and stimulation of developing networks while retaining manufacturability compatible with low-cost and large-scale production. Our hybrid polydimethylsilane (PDMS)-on-polystyrene structures include chambers (6 mm in diameter) and microchannels (25 microm x 3.7 microm x 1 mm) serving as substrate-embedded recording pipettes. Somas are plated and retained in the chambers due to geometrical constraints and their processes grow along the microchannels, effectively establishing a loose-patch configuration without human intervention. We demonstrate that off-the-shelf voltage-clamp, current-clamp and extracellular amplifiers can be used to record and stimulate multi-unit activity with the aid of our dishes. Spikes up to 50 pA in voltage-clamp and 300 microV in current-clamp modes are recorded in sparse and bursting activity patterns characteristic of 1 week-old hippocampal cultures. Moreover, spike sorting employing principal component analysis (PCA) confirms that single microchannels support the recording of multiple neurons. Overall, this work suggests a strategy to endow conventional culture plasticware with added functionality to enable cost-efficient network electrophysiology.     

Theoretical and experimental studies of the photoluminescent properties of the coordination polymer [Eu(DPA)(HDPA)(H2O)2].4H2O

We report on the hydrothermal synthesis of the [Eu(DPA)(HDPA)(H(2)O)(2)].4H(2)O lanthanide-organic framework (where H2DPA stands for pyridine-2,6-dicarboxylic acid), its full structural characterization including single-crystal X-ray diffraction and vibrational spectroscopy studies, plus detailed investigations on the experimental and predicted (using the Sparkle/PM3 model) photophysical luminescent properties. We demonstrate that the Sparkle/PM3 model arises as a valid and efficient alternative to the simulation and prediction of the photoluminescent properties of lanthanide-organic frameworks when compared with methods traditionally used. Crystallographic investigations showed that the material is composed of neutral one-dimensional coordination polymers infinity(1)[Eu(DPA)(HDPA)(H(2)O)(2)] which are interconnected via a series of hydrogen bonding interactions involving the water molecules (both coordinated and located in the interstitial spaces of the structure). In particular, connections between bilayer arrangements of infinity(1)[Eu(DPA)(HDPA)(H(2)O)(2)] are assured by a centrosymmetric hexameric water cluster. The presence of this large number of O-H oscillators intensifies the vibronic coupling with water molecules and, as a consequence, increases the number of nonradiative decay pathways controlling the relaxation process, ultimately considerably reducing the quantum efficiency (eta = 12.7%). The intensity parameters (Omega(2), Omega(4), and Omega(6)) were first calculated by using both the X-ray and the Sparkle/PM3 structures and were then used to calculate the rates of energy transfer (W(ET)) and back-transfer (W(BT)). Intensity parameters were used to predict the radiative decay rate. The calculated quantum yield obtained from the X-ray and Sparkle/PM3 structures (both of about 12.5%) are in good agreement with the experimental value (12.0 +/- 5%). These results clearly attest for the efficacy of the theoretical models employed in all calculations and create open new interesting possibilities for the design in silico of novel and highly efficient lanthanide-organic frameworks.     

Gold nanoparticles for the development of clinical diagnosis methods

The impact of advances in nanotechnology is particularly relevant in biodiagnostics, where nanoparticle-based assays have been developed for specific detection of bioanalytes of clinical interest. Gold nanoparticles show easily tuned physical properties, including unique optical properties, robustness, and high surface areas, making them ideal candidates for developing biomarker platforms. Modulation of these physicochemical properties can be easily achieved by adequate synthetic strategies and give gold nanoparticles advantages over conventional detection methods currently used in clinical diagnostics. The surface of gold nanoparticles can be tailored by ligand functionalization to selectively bind biomarkers. Thiol-linking of DNA and chemical functionalization of gold nanoparticles for specific protein/antibody binding are the most common approaches. Simple and inexpensive methods based on these bio-nanoprobes were initially applied for detection of specific DNA sequences and are presently being expanded to clinical diagnosis. Figure Colorimetric DNA/RNA detection using salt induced aggregation of AuNP-DNA nanoprobes.     

Direct determination of the ionization energies of PtC, PtO, and PtO2 with VUV radiation

Photoionization efficiency curves were measured for gas-phase PtC, PtO, and PtO2 using tunable vacuum ultraviolet (VUV) radiation at the Advanced Light Source. The molecules were prepared by laser ablation of a platinum tube, followed by reaction with CH4 or N2O and supersonic expansion. These measurements provide the first directly measured ionization energy for PtC, IE(PtC) = 9.45 +/- 0.05 eV. The direct measurement also gives greatly improved ionization energies for the platinum oxides, IE(PtO) = 10.0 +/- 0.1 eV and IE(PtO2) = 11.35 +/- 0.05 eV. The ionization energy connects the dissociation energies of the neutral and cation, leading to greatly improved 0 K bond dissociation energies for the neutrals: D0(Pt-C) = 5.95 +/- 0.07 eV, D0(Pt-O) = 4.30 +/- 0.12 eV, and D0(OPt-O) = 4.41 +/- 0.13 eV, as well as enthalpies of formation for the gas-phase molecules DeltaH(0)(f,0)(PtC(g)) = 701 +/- 7 kJ/mol, DeltaH(0)(f,0)(PtO(g)) = 396 +/- 12 kJ/mol, and DeltaH(0)(f,0)(PtO2(g)) = 218 +/- 11 kJ/mol. Much of the error in previous Knudsen cell measurements of platinum oxide bond dissociation energies is due to the use of thermodynamic second law extrapolations. Third law values calculated using statistical mechanical thermodynamic functions are in much better agreement with values obtained from ionization energies and ion energetics. These experiments demonstrate that laser ablation production with direct VUV ionization measurements is a versatile tool to measure ionization energies and bond dissociation energies for catalytically interesting species such as metal oxides and carbides.