Maximum Spin Polarization in Chromium Dimer Cations as Demonstrated by X‐ray Magnetic Circular Dichroism Spectroscopy

X‐ray magnetic circular dichroism spectroscopy has been used to characterize the electronic structure and magnetic moment of Cr₂⁺. Our results indicate that the removal of a single electron from the 4sσ_g bonding orbital of Cr₂ drastically changes the preferred coupling of the 3d electronic spins. While the neutral molecule has a zero‐spin ground state with a very short bond length, the molecular cation exhibits a ferromagnetically coupled ground state with the highest possible spin of S=11/2, and almost twice the bond length of the neutral molecule. This spin configuration can be interpreted as a result of indirect exchange coupling between the 3d electrons of the two atoms that is mediated by the single 4s electron through a strong intraatomic 3d‐4s exchange interaction. Our finding allows an estimate of the relative energies of two states that are often discussed as ground‐state candidates, the ferromagnetically coupled ¹²Σ and the low‐spin ²Σ state.     

Measurement of the decay constant f(Ds+) using D(s+)-->l+ nu

We measure the decay constant f(Ds+) using the D(s+)-->l+ nu channel, where the l+ designates either a mu+ or a tau+, when the tau+ -->pi+ nu. Using both measurements we find f(Ds+)=274+/-13+/-7 MeV. Combining with our previous determination of f(D+), we compute the ratio f(Ds+)/f(D+)=1.23+/-0.11+/-0.04. We compare with theoretical estimates.     

Fluorescent organosilica micro- and nanoparticles with controllable size

This paper reports on the synthesis of uniformly dye-doped organosilica particles with narrow size distribution. The particle size can be controlled from tenths of nanometers up to several micrometers, whilst still maintaining monodispersity. Microparticles were observed to swell in various solvents up to approximately 2.5 times their original volume, suggesting the presence of a gel-like internal structure. As shown by confocal microscopy, this morphological control of particle swelling has important implications for the encoding of the nano/micro particles with organic dyes, such as rhodamine B isothiocyanate. Swelling allows the dye to penetrate the organosilica matrix and produce uniformly dye-doped nano- and microparticles. Finally, we suggest a coagulation model for the particle formation which significantly differs from conventional St?ber synthesis.     

Nanoscale patterning in mixed fluorocarbon-hydrocarbon phospholipid bilayers

A growing body of literature suggests that fluorocarbons can direct self-assembly within hydrocarbon environments. We report here the fabrication and characterization of supported lipid bilayers (SLBs) composed of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and a synthetic, fluorocarbon-functionalized analogue, 1. AFM investigation of these model membranes reveals an intricate, composition-dependent domain structure consisting of approximately 50 nm stripes interspersed between approximately 1 microm sized domains. Although DSC of 1 showed a phase transition near room temperature, DSC of DPPC:1 mixtures exhibited complex phase behavior suggesting domain segregation. Finally, temperature-dependent AFM of DPPC:1 bilayers shows that, while the stripe structures can be melted above the Tm of 1, the stripes and domains result from immiscibility of the hydrocarbon and fluorocarbon lipid gel phases. Fluorination appears to be a promising strategy for chemical self-assembly in two dimensions. In particular, because no modification is made to the lipid headgroups, it may be useful for nanopatterning biologically relevant ligands on bilayers in vitro or in living cells.     

Pressure-driven phase transitions in NaBH4: theory and experiments

We have investigated pressure-induced structural transitions in NaBH4 through density-functional theory calculations combined with X-ray and neutron diffraction experiments. Our calculations confirm that the cubic phase is stable up to 5.4 GPa and an orthorhombic phase occurs above 8.9 GPa, as observed in X-ray diffraction experiments. Both the calculations and X-ray diffraction measurements identify an intermediate tetragonal phase that appears between 6 and 8 GPa; that is, between the cubic and orthorhombic phases. This result is also confirmed by high-pressure neutron diffraction experiments performed on NaBD4. Our calculations and X-ray diffraction measurements show that the space group of the orthorhombic phase above 8.9 GPa is Pnma and the orthorhombic phase remains stable up to 30 GPa. The calculated equations of state are in excellent agreement with experiments.     

Activity of platinum-gold alloys for glucose electrooxidation in biofuel cells

Carbon supported Pt-Au catalysts with different bimetallic compositions were prepared by water in oil (w/o) microemulsion. Carbon Vulcan XC-72 was added during the synthesis of particles in order to obtain their good dispersion and a mean particle size distribution of 5.02 +/- 0.56 nm. Structural characterization was performed using XRD at wide angles (WAXS), which showed that Pt-Au particles exhibited alloy properties. Electrochemical characterization allowed to estimate the surface composition of Pt-Au alloys, which was close to that of the bulk material Pt(20)Au(80). This catalyst composition displayed the best catalytic activity in steady-state conditions in comparison with Pt(50)Au(50) or Pt and Au alone. Moreover, a Pt-Au/C catalyst with a metal loading of 40 wt % was immobilized onto a carbon porous tube as anode. A membrane-less biofuel cell was tested using laccase/ABTS biocathode in phosphate buffer (pH 5).     

Measuring molecular order in poly(3-alkylthiophene) thin films with polarizing spectroscopies

We measured the molecular order of poly(3-alkylthiophene) chains in thin films before and after melting through the combination of several polarized photon spectroscopies: infrared (IR) absorption, variable angle spectroscopic ellipsometry (SE), and near-edge X-ray absorption fine structure (NEXAFS). The data from the various techniques can be uniformly treated in the context of the dielectric constant tensor epsilon for the film. The combined spectroscopies allow determination of the orientation distribution of the main-chain axis (SE and IR), the conjugated pi system normal (NEXAFS), and the side-chain axis (IR). We find significant improvement in the backbone order of the films after recrystallization of the material at temperatures just below the melting temperature. Less aggressive thermal treatments are less effective. IR studies show that the changes in backbone structure occur without significant alteration of the structure of the alkyl side chains. The data indicate that the side chains exhibit significant disorder for all films regardless of the thermal history of the sample.     

An unexpected new optimum in the structure space of DNA solubilizing single-walled carbon nanotubes

Here we report quantitative data on the amount of single-walled carbon nanotubes that can be suspended with oligodeoxynucleotides in aqueous buffer, together with rate constants for the thermal denaturation of the resulting DNA-nanotube complexes at elevated temperatures. Sequence motifs d(GT)n and d(AC)n with n=2, 3, 5, 10, 20, or 40 were employed, both individually and as equimolar mixtures of the complementary strands. Unexpectedly, the greatest suspending efficiency was found for the mixture of short, complementary oligonucleotides d(GT)3 and d(AC)3. Unlike the suspending efficiency, the kinetic stability of the nanotube suspensions increases with increasing chain length of the DNA, with half life times of >25 h at 90 degrees C for the complexes of the longest strands. Our results identify a new, unexpected optimum in DNA sequence space for suspending carbon nanotubes. They also demonstrate that suspending power depends on the presence of complementary strands. Exploratory assays suggest that nanotubes can be deposited site-selectively from suspensions formed with short DNA sequences.     

Untersuchungen zur Sb–Sb‐Bindungsknüpfung in der Koordinationssphäre von Übergangsmetallen

Investigations of Sb–Sb Bond Formation Reactions in the Coordination Sphere of Transition Metals The reaction of SbCl₃ with various transition metal metalates of the type K[ML_n] [ML_n = Ni(CO)Cp*, Fe(CO)Cp′, Co(CO)₄; Cp* = η⁵‐C₅Me₅, Cp′ = η⁵‐C₅H₄Me] in the presence of [Cr(CO)₅thf] have been studied. With K[Ni(CO)Cp*] and K[Fe(CO)₂Cp′] the trigonal‐pyramidal complexes [(μ₃‐Sb){Ni(CO)Cp*}₃] ( 1 ) and [(μ₃‐Sb){Fe · (CO)₂Cp′}₃] ( 2 ), respectively, are obtained. The reaction with K[Co(CO)₄] leads to the tetrahedral cluster [Co₃(CO)₉(μ₃‐Sb{Cr(CO)₅})] ( 3 ) and the butterfly cluster [Co₂(CO)₆(μ‐SbCl)(μ‐SbCl{Cr(CO)₅})] ( 4 ). All products are characterised by X‐ray crystal structure determination. In contrast to the corresponding [(CO)₅CrPCl₃] system forming P–P bonds, starting from SbCl₃/[Cr(CO)₅thf] does not cause a Sb–Sb bond formation.