Redox-active silica nanoparticles. Part 4. Synthesis, size distribution, and electrochemical adsorption behavior of ferrocene- and (diamine)(diphosphine)-ruthenium(II)-modified Stöber silica colloidal particles

Stöber silica nanoparticles with a diameter of approximately 800 nm are covalently modified by redox-active ferrocene or (diamine)(diphosphine) ruthenium(II) units attached to a spacer. The particles are characterized by NMR spectroscopic and chemical techniques. Two variants of modification by condensation are compared. Besides an estimation of the size and the particle porosity, the agglomeration behavior in solvents of different polarity is investigated. The adsorption of the particles to an electrode surface is followed.     

Note on Vector Translation with Respect to Thompson’s Metric

It is known that vector translations are contractive with respect to Thompson’s part metric. Here, we give a simple proof, based on a representation of Thompson’s metric through positive functionals. Moreover, we use contractivity of translations to prove a fixed point result for mappings that are Lipschitz continuous with respect to Thompson’s metric with Lipschitz constant r>1. The case r = 1 for order preserving or order reversing mappings has been recently studied by Lawson and Lim. We apply our result to a nonlinear boundary value problem.     

Natural Abundance 15N NMR by Dynamic Nuclear Polarization: Fast Analysis of Binding Sites of a Novel Amine‐Carboxyl‐Linked Immobilized Dirhodium Catalyst

A novel heterogeneous dirhodium catalyst has been synthesized. This stable catalyst is constructed from dirhodium acetate dimer (Rh₂(OAc)₄) units, which are covalently linked to amine‐ and carboxyl‐bifunctionalized mesoporous silica (SBA‐15?NH₂?COOH). It shows good efficiency in catalyzing the cyclopropanation reaction of styrene and ethyl diazoacetate (EDA) forming cis‐ and trans‐1‐ethoxycarbonyl‐2‐phenylcyclopropane. To characterize the structure of this catalyst and to confirm the successful immobilization, heteronuclear solid‐state NMR experiments have been performed. The high application potential of dynamic nuclear polarization (DNP) NMR for the analysis of binding sites in this novel catalyst is demonstrated. Signal‐enhanced ¹³C CP MAS and ¹⁵N CP MAS techniques have been employed to detect different carboxyl and amine binding sites in natural abundance on a fast time scale. The interpretation of the experimental chemical shift values for different binding sites has been corroborated by quantum chemical calculations on dirhodium model complexes.     

Assessment of T1, T1ρ, and T2 values of the ulnocarpal disc in healthy subjects at 3 tesla

Objective

The purpose of this study was to implement clinically feasible imaging techniques for determination of T₁, T_1ρ, and T₂ values of the ulnocarpal disc and to assess those values in a cohort of asymptomatic subjects at 3 tesla. Resulting values were compared between different age groups, since former histological findings of the ulnocarpal disc indicated frequent early degenerative changes of this tissue starting in the third decade of life, even in asymptomatic subjects.

Materials and methods

Twenty-seven healthy subjects were included in this study. T₁ measurements were performed using 3D spoiled gradient-echo (GRE) sequence with variable flip angle. A series of T_1ρ and T₂-weighted images was acquired by a 3D GRE sequence after suitable magnetization preparation. T_1,T_1ρ, and T₂ maps of the ulnocarpal disc were calculated pixel-wise. Representative mean values from extended regions were analysed.

Results

Mean T₁ values of the ulnocarpal disc ranged from 722 ms in a 39 year-old subject to 1264 ms in a 65 year-old subject, T_1ρ ranged from 9.2 ms (26 year-old subject) to 25.9 ms (65 year-old subject). Calculated T₂ values showed a large range from 4.1 ms to 22.3 ms. T_1ρ and T₁ values tended to increase with age (p < 0.05), whereas T₂ did not.

Conclusions

MR relaxometry of the ulnocarpal disc is feasible, and T_1,T_1ρ, and T₂ values show modest variance in asymptomatic subjects. The potential of relaxation mapping to reveal relevant structural changes in patients has to be investigated in further studies.