Highly metallized polymers: synthesis, characterization, and lithographic patterning of polyferrocenylsilanes with pendant cobalt, molybdenum, and nickel cluster substituents

High molecular weight, soluble, air- and moisture-stable, highly metallized (>25 wt% metal) polyferrocenylsilanes (PFS) [Fe(eta-C5H4)2Si(Me){Co2(CO)6C2Ph}]n (Co-PFS), [Fe(eta-C5H4)2Si(Me){Mo2-Cp2(CO)4C2Ph}]n (Mo-PFS), and [Fe(eta-C5H4)2Si(Me){Ni2Cp2C2Ph}]n (Ni-PFS) containing pendant cobalt, molybdenum, and nickel clusters, respectively, have been prepared via macromolecular clusterization of an acetylide-substituted PFS [Fe(eta-C5H4)2Si(Me)C(triple bond)CPh]n with [Co(2)(CO)8], [{MoCp(CO)(2)}2], or [{NiCp(CO)}2]. The extent of clusterization achieved was in the range of 70-75%. All three highly metallized polymers were demonstrated to function as negative-tone resists in electron-beam lithography, while Co-PFS and Mo-PFS were successfully patterned by UV-photolithography, allowing the fabrication of micron-sized bars, dots, and lines. These studies suggest that the highly metallized polymers may be useful in the fabrication of patterned arrays of alloy nanoparticles for both materials science and catalytic applications.     

Data completion via an energy error functional

We propose, in this Note, a new procedure for data completion based on the minimization of an energy like error functional. The efficiency of the proposed method is illustrated by a thermostatic application. To cite this article: S. Andrieux et al., C. R. Mecanique 333 (2005).     

Photoinduced charge-transfer dehydrogenation in a gas-phase metal-DNA base complex: Al-cytosine

An Al-cytosine association complex has been generated via laser ablation of a mixture of aluminum and cytosine powders that were pressed into a rod form. The ionization energy of the complex is found to be 5.16 +/- 0.01 eV. The photoionization efficiency spectrum of Al-cytosine has also been collected. DFT calculations indicate that binding of Al to cytosine manifests a significant weakening of the N-H bond, predicted to have a strength of 1.5 eV in the complex, and a significant stabilization of the oxo tautomeric form relative to the hydroxy forms. The predicted ionization energy of 5.2 eV agrees well with the experimental value. The threshold for dehydrogenation/ionization of Al-cytosine, forming (Al-cytosine-H)+, is found to occur at photoexcitation energies between 11.4 and 12.8 eV. This is a two-photon process that is proposed to occur via photoinduced electron transfer from Al to an antibonding (sigma) orbital localized on N-H. In the context of this mechanism, this work constitutes the first time charge transfer between a metal and DNA base has been photoinitiated in the gas phase.     

Scaling near the quantum-critical point in the SO(5) theory of the high-T(c) superconductivity

We study the quantum-critical point scenario within the unified theory of superconductivity and antiferromagnetism based on the SO(5) symmetry. Closed-form expression for the quantum-critical scaling function for the dynamic spin susceptibility is obtained from the lattice SO(5) quantum nonlinear sigma-model in three dimensions, revealing that in the quantum-critical region the frequency scale for spin excitations is simply set by the absolute temperature. Implications for the non-Fermi liquid behavior of the normal-state resistivity due to spin fluctuations in the quantum-critical region are also presented.     

Physicochemical and thermodynamic characterization of hydroxy pentacyclic triterpenoic acid/γ-cyclodextrin inclusion complexes

Hydroxy pentacyclic triterpenoic acids (HPTAs) have been described to exhibit numerous pharmacological properties. They also exhibit poor hydrosolubility, thus affecting their potential clinical interest. The association of these active substances with cyclodextrins could be employed to improve some properties such as bioavailability and activity. 1:1 Inclusion complexes of ursolic, oleanolic and betulinic acids with γ-cyclodextrin were evaluated by DSC and ¹H NMR spectroscopy. The apparent formation constants (K_f) of the formed complexes were determined using RP-HPLC. Thermodynamic parameters ΔGo, ΔHo and ΔSo were calculated with temperatures ranging from 25 to 45?°C to evaluate the complexation process. Finally the influence of γ-CD on the HPTA water solubility was investigated by phase-solubility studies.     

Rheological constitutive equation of solids: a link between models based on irreversible thermodynamics and on fractional order derivative equations

In this paper we focus on the rheological problem of defining a constitutive equation for viscoelastic materials. In this simple case, we show that writing the dissipative component of the observable response to a given excitation as the result of multiple internal processes working for equilibrium recovery (flux of internal hidden variables), can yield a recursive series in time. This can be obtained when use is made of the theorem of created entropy equipartition as a model for fluctuation regression. A distribution (spectrum) for relaxation times naturally follows. The model thus obtained reflects the concept of a hierarchically constrained dynamic behavior. The conclusion is that the operator of non-integer differentiation in time applied to field variables can also be recovered from pure thermodynamic considerations.