Gas phase hydrogen deuterium exchange reactions of a model peptide: FT-ICR and computational analyses of metal induced conformational mutations

We utilized gas phase hydrogen/deuterium (H/D) exchange reactions and ab initio calculations to investigate the complexation between a model peptide (Arg-Gly-AspRGD) with various alkali metal ions. The peptide conformation is drastically altered upon alkali metal ion complexation. The associated conformational changes depend on both the number and type of complexing alkali metal ions. Sodium has a smaller ionic diameter and prefers a multidentate interaction that involves all three amino acids of the peptide. Conversely, potassium and cesium form different types of complexes with the RGD. The [RGD + 2Cs − H]⁺ species exhibit the slowest H/D exchange reactivity (reaction rate constant of 6 × 10⁻¹³ cm³molecule⁻¹s⁻¹ for the fastest exchanging labile hydrogen with ND₃). The reaction rate constant of the protonated RGD is two orders of magnitude faster than that of the [RGD + 2Cs − H]⁺. Addition of the first cesium to the RGD reduces the H/D exchange reaction rate constant (i.e., D₀) by a factor of seven whereas sodium reduces this value by a factor of thirty. Conversely, addition of the second alkali metal ions has the opposite effect; the rate of D₀ disappearance for all [RGD + 2Met − H]⁺ species (MetNa, K, and Cs) decreases with the alkali metal ion size.     

On the Supra-LUMO Interaction: Case Study of a Sudden Change of Electronic Structure as a Functional Emergence

The synergistic functioning of redox-active components that emerges from prototypical 2,2′-di(N-methylpyrid-4-ylium)-1,1′-biphenyl is described. Interestingly, even if a trans conformation of the native assembly is expected, due to electrostatic repulsion between cationic pyridinium units, we demonstrate that cis conformation is equally energy-stabilized on account of a peculiar LUMO (SupLUMO) that develops through space, encompassing the two pyridiniums in a single, made-in-one-piece, electronic entity (superelectrophoric behavior). This SupLUMO emergence, with the cis species as superelectrophore embodiment, originates in a sudden change of electronic structure. This finding is substantiated by insights from solid state (single-crystal X-ray diffraction) and solution (NOE NMR and UV-vis-NIR spectroelectrochemistry) studies, combined with electronic structure computations. Electrochemistry shows that electron transfers are so strongly correlated that two-electron reduction manifests itself as a single-step process with a large potential inversion consistent with inner creation of a carbon-carbon bond (digital simulation). Besides, absence of reductive formation of dimers is a further indication of a preferential intramolecular reactivity determined by the SupLUMO interaction (cis isomer pre-organization). The redox-gated covalent bond, serving as electron reservoir, was studied via atropisomerism of the reduction product (VT NMR study). The overall picture derived from this in-depth study of 2,2′-di(N-methylpyrid-4-ylium)-1,1′-biphenyl proves that trans and cis species are worth considered as intrinsically sharply different, that is, as doubly-electrophoric and singly-superelectrophoric switchable assemblies, beyond conformational isomerism. Most importantly, the through-space-mediated SupLUMO may come in complement of other weak interactions encountered in Supramolecular Chemistry as a tool for the design of electroactive architectures.     

Cyclisation photochimique d'alkyl-2 aryl-3 cyclohexène-2 ones

In methanol, 2-alkyl-3-aryl-2-cyclohexenones undergo an oxidative photocyclization at 254 nm to provide polycyclic compounds with a phenanthrenic skeleton.     

Splines and Linear Control Theory

In this work, the relationship between splines and the linear control theory has been analyzed. We show that spline functions can be constructed naturally from the control theory. By establishing a framework based on control theory, we provide a simple and systematic way to construct splines. We have constructed the traditional spline functions including polynomial splines and the classical exponential spline. We have also discovered some new spline functions such as the combination of polynomial, exponential and trigonometric splines. The method proposed in this paper is easy to implement. Some numerical experiments are performed to investigate properties of different spline approximations.     

Tunable frequency-controlled laser source in the near ultraviolet based on doubling of a semiconductor diode laser

Continuously tunable ultraviolet laser radiation at 397 nm was generated by doubling the output of a semiconductor diode laser. The fundamental radiation was provided by a 150 mW AlGaAs laser diode injected by a low-power AlGaAs laser diode which was frequency stabilized by optical feedback using a new scheme of a miniature external cavity. Second-harmonic generation was produced in a lithium-triborate crystal placed in a compact enhancement cavity. The fundamental radiation was used for sub-Doppler spectroscopy of the Ar I 4s ³ P ⁰ ₀–4p ¹ P ₁ transition at 795 nm; the second-harmonic radiation was used for spectroscopy of the Ca II 4² S _1/2–4² P _1/2 transition at 397 nm.     

Zinc and copper complexes of prodigiosin: implications for copper-mediated double-strand DNA cleavage

[reaction: see text] Zinc(II) and copper(II) complexes of prodigiosin (1) have been characterized. All N-atoms of 1 bind Cu(II) to generate 5: the complex exhibits regiospecific oxidation of the C-pyrrole. In contrast, coordination by Zn(II) to 1 produces Zn(1)(2) (8), a 4-coordinate tetrahedral complex. The influence of these binding geometries on Cu-mediated double-strand (ds) DNA cleavage by 1 is discussed.     

Convenient access to new chiral ferroceno-(iso)quinolines

[Chemical reaction: see text] New chiral pyridine derivatives possessing the planar chirality of the ferrocene have been prepared by means of an aldolization-crotonization reaction. This very simple reaction has been applied to the synthesis of isomers 1-4 that differ in the position of the nitrogen atom on the pyridine ring. Following the same procedure, asymmetric synthesis of 1 has been achieved using an enantiopure ferrocenylzinc intermediate. This method has also allowed the preparation of a chiral analogue of 2,2'-bipyridine.     

First regioselective ortho-lithiation induced by a 2-chloropyridyl group complexation

It is shown that t-BuLi in Et(2)O promotes an exclusive regioselective metalation of 2-aryl-6-chloropyridine compounds at the aromatic ortho position demonstrating that the 2-chloropyridyl moiety may be considered as a directing group. This functionally directed metalation group was successfully used for the selective lithiation of substituted aromatics and for the straightforward preparation of new N,P ligands.