Experimental and theoretical investigations of the sulfite-based polyoxometalate cluster redox series: alpha- and beta-[Mo(18)O(54)(SO(3))(2)](4-/5-/6-)

The synthesis, isolation and structural characterization of the sulfite polyoxomolybdate clusters alpha-(D(3h))(C(20)H(44)N)(4){alpha-[Mo(18)O(54)(SO(3))(2)]}CH(3)CN and beta-(D(3d))(C(20)H(44)N)(4){beta-[Mo(18)O(54)(SO(3))(2)]}CH(3)CN is presented. Voltammetric studies in acetonitrile (0.1 M Hx(4)NClO(4), Hx(4)N=tetra-n-hexylammonium) reveal the presence of an extensive series of six one-electron reduction processes for both isomers. Under conditions of bulk electrolysis, the initial [Mo(18)O(54)(SO(3))(2)](4-/5-) and [Mo(18)O(54)(SO(3))(2)](5-/6-) processes produce stable [Mo(18)O(54)(SO(3))(2)](5-) and [Mo(18)O(54)(SO(3))(2)](6-) species, respectively, and the same reduced species may be produced by photochemical reduction. Spectroelectrochemical data imply that retention of structural form results upon reduction, so that both alpha and beta isomers are available at each of the 4-, 5-, and 6-redox levels. However, the alpha isomer is the thermodynamically favored species in both the one- and two-electron-reduced states, with beta-->alpha isomerization being detected in both cases on long time scales (days). EPR spectra also imply that increasing localization of the unpaired electron occurs over the alpha- and beta-[Mo(18)O(54)(SO(3))(2)](5-) frameworks as the temperature approaches 2 K where the EPR spectra show orthorhombic symmetry with different g and hyperfine values for the alpha and beta isomers. Theoretical studies support the observation that it is easier to reduce the alpha cluster than the beta form and also provide insight into the driving force for beta-->alpha isomerization in the reduced state. Data are compared with that obtained for the well studied alpha-[Mo(18)O(54)(SO(4))(2))](4-) sulfate cluster.     

Multifrequency EPR and redox reactivity investigations of a bis(mu-thiolato)-dicopper(II,II) complex

From a new tripodal ligand [N2SS'H] with mixed N, S(thioether), and S(thiolate) donor set, the corresponding bis(mu-thiolato)dicopper(II) complex has been prepared and characterized. X-ray crystallographic analysis of the complex [Cu2(N2SS')2](ClO4)2.C4H10O (1) demonstrates that the two five-coordinated Cu atoms are bridged by two thiolates leading to a nearly planar Cu2S2 core with a Cu1...Cu1* distance of 3.418(8) A and a large bridging angle Cu1S1Cu1* of 94.92 degrees. X-band (10 GHz), Q-band (34 GHz), and F-Band (115 GHz) EPR spectra of 1 are consistent with a weakly coupled dicopper(II,II) center attributed to an S = 1 state. Simulations for the three frequencies are obtained with a unique set of electronic parameters. The mean values of the spin Hamiltonian parameters for 1 are D = 0.210(3) cm(-1), E = 0.0295(5) cm(-1), |E/D| = 0.140, gx = 2.030(2), gy = 2.032(2), gz = 2.128(2). The electrochemical one-electron reduction of 1 generates the mixed-valent CuIICuI species. EPR and UV-vis spectra are consistent with a type I localized mixed-valent species, while dinuclear CuA centers of native cytochrome c oxidase (CcO)1-3 or nitrous oxide reductase (N2OR)4 have a delocalized CuIICuI mixed-valent state. After reoxidation of the CuIICuI species, the initial complex 1 is regenerated through a reversible interconversion process.     

Elaboration of silica colloid/polymer hybrid support for oligonucleotide synthesis

One way to increase the sensitivity of DNA diagnostic assays developed on microarrays is to improve the solid phase that allows the extraction of the target from a biological sample, before detection. Two parameters are influencing the performances of this capture step: (i) the specific surface area being offered for the capture and (ii) the number and the accessibility of oligonucleotide probes immobilized on the surface. In this context, we have developed an attractive approach which fulfills these two points. Our strategy was to elaborate a new material of high specific surface area, suitable to serve as support for both solid-phase oligonucleotide synthesis and in vitro diagnostic assay. This material has consisted of aggregates of colloidal amino-silica nanoparticles covalently linked by poly(ethylene oxide) (PEO) arms. The aggregation of amino-silica particles in the presence of reactive bis-isocyanate PEO was achieved in a controlled manner. The aggregate size and structure were examined by microscopy. The specific surface area of this material was measured by nitrogen adsorption technique. The composition of aggregate was studied by thermogravimetry and X-ray photoelectron spectroscopy. Then, this material has been successfully used as support for oligonucleotide synthesis of high yield and purity. The resulting system will be further evaluated in a diagnostic assay on a microarray.     

Structural and magnetic properties of Mn(III) and Cu(II) tetranuclear azido polyoxometalate complexes: multifrequency high-field EPR spectroscopy of Cu4 clusters with S = 1 and S = 2 ground states

Two new azido-bridged polyoxometalate compounds were synthesized in acetonitrile/methanol media and their molecular structures have been determined by X-ray crystallography. The [[(gamma-SiW10O36)Mn2(OH)2(N3)(0.5)(H2O)(0.5)]2(mu-1,3-N3)](10-) (1 a) tetranuclear Mn(III) complex, in which an end-to-end N3- ligand acts as a linker between two [(gamma-SiW10O36)Mn2(OH)2]4- units, represents the first manganese-azido polyoxometalate. The magnetic properties have been studied considering the spin Hamiltonian H = -J1(S1S2+S1*S2*)-J2(S1S1*), showing that antiferromagnetic interactions between the paramagnetic centers (g = 1.98) occur both through the di-(mu-OH) bridge (J1 = -25.5 cm(-1)) and the mu-1,3-azido bridge (J2 = -19.6 cm(-1)). The [(gamma-SiW10O36)2Cu4(mu-1,1,1-N3)2(mu-1,1-N3)2]12- (2 a) tetranuclear Cu(II) complex consists of two [gamma-SiW10O36Cu2(N3)2]6- subunits connected through the two mu-1,1,1-azido ligands, the four paramagnetic centers forming a lozenge. The magnetic susceptibility data have been fitted. This reveals ferromagnetic interactions between the four Cu(II) centers, leading to an S=2 ground state (H = -J1(S1S2+S1*S2*)-J2(S2S2*), J1 = +294.5 cm(-1), J2 = +1.6 cm(-1), g = 2.085). The ferromagnetic coupling between the Cu(II) centers in each subunit is the strongest ever observed either in a polyoxometalate compound or in a diazido-bridged Cu(II) complex. Considering complex 2 a and the previously reported basal-basal di-(mu-1,1-N3)-bridged Cu(II) complexes in which the metallic centers are not connected by other magnetically coupling ligands, the linear correlation J1 = 2639.5-24.95*theta(av) between the theta(av) bridging angle and the J1 coupling parameter has been proposed. The electronic structure of complex 2 a has also been investigated by using multifrequency high-field electron paramagnetic resonance (HF-EPR) spectroscopy between 95 and 285 GHz. The spin Hamiltonian parameters of the S = 2 ground state (D = -0.135(2) cm(-1), E = -0.003(2) cm(-1), g(x) = 2.290(5), g(y) = 2.135(10), g(z) = 2.158(5)) as well as of the first excited spin state S = 1 (D = -0.960(4) cm(-1), E = -0.080(5) cm(-1), g(x) = 2.042(5), g(y) = 2.335(5), g(z) = 2.095(5)) have been determined, since the energy gap between these two spin states is very small (1.6 cm(-1)).     

New 3-D La(III)-Cu(II)-containing coordination polymer with a high potential porosity

A new 3-D coordination polymer containing both 3d and 4f ions has been designed. Its chemical formula is La2[Cu(pba)]3(H2O)8 . 8H2O. It crystallizes in the quadratic system, space group I41/a with a = 42.4947(9) Angstrom, c = 16.3378(3) Angstrom, and Z = 16. Its crystal structure can be described as a 3-D molecular framework exhibiting a complex network of interconnected zigzaglike channels. Once crystallization water molecules are removed, this compound presents a high potential porosity and a low density. The porosity has been evaluated using Connolly's algorithm.     

Estimating optical properties in layered tissues by use of the Born approximation of the radiative transport equation

We use the Born approximation of the radiative transport equation to recover simultaneously the absorption and scattering coefficients in a single layer of a two-layer tissue sample from reflectance data. This method reduces the estimation of both optical properties to a single linear, least-squares problem. It is valid over length scales smaller than a transport mean free path and hence is useful for epithelial tissue layers. We demonstrate the accuracy of this method by using spatially resolved reflectance data computed with Monte Carlo simulations.     

Siliceous spicules in marine demosponges (example Suberites domuncula)

All metazoan animals comprise a body plan of different complexity. Since--especially based on molecular and cell biological data--it is well established that all metazoan phyla, including the Porifera (sponges), evolved from a common ancestor the search for common, basic principles of pattern formation (body plan) in all phyla began. Common to all metazoan body plans is the formation of at least one axis that runs from the apical to the basal region; examples for this type of organization are the Porifera and the Cnidaria (diploblastic animals). It seems conceivable that the basis for the formation of the Bauplan in sponges is the construction of their skeleton by spicules. In Demospongiae (we use the model species Suberites domuncula) and Hexactinellida, the spicules consist of silica. The formation of the spicules as the building blocks of the skeleton, starts with the expression of an enzyme which was termed silicatein. Spicule growth begins intracellularly around an axial filament composed of silicatein. When the first layer of silica is made, the spicules are extruded from the cells and completed extracellularly to reach their the final form and size. While the first steps of spicule formation within the cells are becoming increasingly clear, it remains to be studied how the extracellularly present silicatein strings are formed. The understanding of especially this morphogenetic process will allow an insight into the construction of the amazingly diverse skeleton of the siliceous sponges; animals which evolved between two periods of glaciations, the Sturtian glaciation (710-680 MYA) and the Varanger-Marinoan ice ages (605-585 MYA). Sponges are--as living fossils--witnesses of evolutionary trends which remained unique in the metazoan kingdom.     

Harmonics-to-Noise Ratio: An Index of Vocal Aging

Distinguishing between vocal changes that occur with normal aging and those that are associated with disease is an important goal of research in voice. Several acoustic measures have been used in an attempt to illuminate the integrity of the vocal mechanism, including harmonics-to-noise ratio (HNR), jitter, and fundamental frequency (F₀). HNR is a measure that quantifies the amount of additive noise in the voice signal; jitter reflects the periodicity of vocal fold vibration. In this study, measures of HNR, jitter and F₀ were used to compare vocal function in three groups of normally speaking women: young adults, middle-aged adults, and elderly adults. Significant differences in HNR emerged between the elderly women and the other two groups. F₀ differences were also apparent between the elderly group and the two younger groups; there were no significant differences in jitter between the three groups. HNR was found to be a more sensitive index of vocal function than jitter. The significant lowering of HNR evident in the elderly speakers may be attributable in part to medications taken by the majority of these elderly subjects.     

A Luminescent and Sublimable Dy(III) -Based Single-Molecule Magnet

The reaction of [Ln(hfac)(3) ]?2?H(2) O and pyridine-N-oxide (PyNO) leads to isostructural dimers of the formula [Ln(hfac)(3) (PyNO)](2) (Ln=Eu, Gd, Tb, Dy). The Dy derivative shows a remarkable single-molecule magnet behavior with complex hysteresis at 1.4?K. The dynamics of the magnetization features are two relaxation regimes: a thermally activated one at high temperature (τ(0) =(5.62±0.4)×10(-11) s and Δ=(167±1)?K) and a quantum tunneling regime at low temperature with a tunneling frequency of 0.42?Hz. The analysis of the Gd derivative evidences intradimer antiferromagnetic interactions (J=(-0.034±0.001)?cm(-1) ). Moreover, the Eu, Tb, and Dy derivatives are luminescent with quantum yield of 51, 53, and 0.1?%, respectively. The thermal investigation of [Dy(hfac)(3) (PyNO)](2) shows that the dimers can be sublimated intact, suggesting their possible exploit as active materials for surface-confined nanostructures to be investigated by fluorimetry methods.