Fullerene-derivatized amino acids: synthesis, characterization, antioxidant properties, and solid-phase peptide synthesis

A series of [60]fullerene-substituted phenylalanine (Baa) and lysine derivatives have been prepared by the condensation of 1,2-(4'-oxocyclohexano)fullerene with the appropriately protected (4-amino)phenylalanine and lysine, respectively. Conversion of the imine to the corresponding amine is achieved by di-acid catalyzed hydroboration. The reduction of the imine is not accompanied by hydroboration of the fullerene cage. The [70]fullerene phenylalanine derivative has also been prepared as have the di-amino acid derivatives. The compounds were characterized by MALDI-TOF mass spectrometry, UV/Vis spectroscopy, and cyclic voltammetry. 1H and 13C NMR spectroscopy allowed the observation of diastereomers. Fullerene-substituted peptides may be synthesized on relatively large scale by solid-phase peptide synthesis. The presence of the C60-substituted amino acid in a peptide has a significant effect on the secondary structures and self-assembly properties of peptides as compared to the native peptide. The antioxidant assay of Baa and a Baa-derived anionic peptide was determined to be significantly more potent than Trolox.     

A quantitative ionicity scale for liquid chloride salts

Knowledge of ionicity is requisite for successful identification of those salt qualities required to design and couple the most appropriate fluid for performance of an intended chemical function. We report on utilisation of (35)Cl(-) quadrupolar coupling constants (C(Q)) to quantitatively assess the ionicities of given chloride salts, by exploiting the electronic response of the quadrupolar chlorine atom as a function of its immediate chemical environment. We find that protic salts in particular, like their aprotic analogues, are highly ionised, while at the same time being highly associated, in stark contrast to literature reports claiming in general that they are of sub-ionic origin.     

Rh2(II)-catalyzed intramolecular aliphatic C-H bond amination reactions using aryl azides as the N-atom source

Rhodium(II) dicarboxylate complexes were discovered to catalyze the intramolecular amination of unactivated primary, secondary, or tertiary aliphatic C-H bonds using aryl azides as the N-atom precursor. While a strong electron-withdrawing group on the nitrogen atom is typically required to achieve this reaction, we found that both electron-rich and electron-poor aryl azides are efficient sources for the metal nitrene reactive intermediate.     

Gradient estimates for positive harmonic functions by stochastic analysis

We prove Cheng–Yau type inequalities for positive harmonic functions on Riemannian manifolds by using methods of Stochastic Analysis. Rather than evaluating an exact Bismut formula for the differential of a harmonic function, our method relies on a Bismut type inequality which is derived by an elementary integration by parts argument from an underlying submartingale. It is the monotonicity inherited in this submartingale which allows us to establish the pointwise estimates.     

Convergence of simultaneous Hermite-Padé approximants to then-tuple ofq-hypergeometric series\{ {}_1\Phi _1 (_{(c,\gamma _j )}^{(1,1)} ;z)\} _{j = 1}^n

We investigate the convergence of simultaneous Hermite-Padé approximants to then-tuple of power series $$f_i (z) = \sum\limits_{k = 0}^\infty {C_k^{(i)} z^k ,} i = 1,2,...,n,$$ where $$C_0^{(i)} = 1;C_k^{(i)} = \prod\limits_{p = 0}^{k - 1} {\frac{1}{{(C - q^{\gamma i + p} )}},} k \ge 1.$$ HereC, q∈?, γ _i ∈?,i=1, 2,...,n. For |C|≠1, ifq=e^iθ, θ∈(0, 2π) and θ/2π is irrational, eachf _i (z),i=1,...,n, has a natural boundary on its circle of convergence. We show that “close-to-diagonal” and other sequences of Hermite-Padé approximants converge in capacity to (f ₁(z),..., f_n (z)) inside the common circle of convergence of eachf _i (z),i=1,...,n.