Chiral Supramolecular Nanotubes of Single-Chain Magnets

We report a single-chain magnet (SCM) made of a terbium(III) building block and a nitronyl-nitroxide radical (NIT) functionalized with an aliphatic chain. This substitution is targeted to induce a long-range distortion of the polymeric chain and accordingly it gives rise to chains that are curled with almost 20 nm helical pitch. They self-organize as a chiral tubular superstructure made of 11 chains wound around each other. The supramolecular tubes have a 4.5 nm internal diameter. Overall, this forms a porous chiral network with almost 44 % porosity. Ab initio calculations highlight that each Tb^III ion possesses high magnetic anisotropy. Indeed, notwithstanding the supramolecular arrangement each chain behaves as a SCM. Magnetic relaxation with both finite and infinite-size regimes is observed and confirms the validity of the Ising approximation. This is associated with quite strong coercive field and magnetic remanence (H_c=2400 Oe M_R=2.09 μ_B at 0.5 K) for this class of compounds.     

Reagent-injection flow analysis: application to the determination of nanomolar levels of hydrogen peroxide in seawater

A reagent-injection flow technique, which allows automatic control of the volume of reagent to be injected, is described. The sensitivity of the measurements can be adjusted over a wide range by changing the injection volume. This technique also eliminates problems in photometric determinations arising from refractive index effects and from light scattering by suspended particles in the sample. Consequently, absorbances as small as 0.00004 can be measured. The capabilities of this reagent-injection flow technique were tested by using it to determine hydrogen peroxide in seawater at nanomolar levels with photometric detection. The concentration of hydrogen peroxide was determined as the colored condensation product of N-ethyl-N-(sulfopropyl)aniline and 4-aminoantipyrene; the detection limit was 12 nM.     

SECM for Studying the Immobilization and Repartition of a Redox Anti-tetracycline Aptamer on Screen-printed Carbon Electrodes

Scanning electrochemical microscopy (SECM) is discussed as a versatile tool to provide a unique approach of localized electrochemical information in the context of biosensing research. The step-by-step immobilization of DNA aptamer with intrinsic redox activity on screen-printed carbon electrode (SPCE) was successfully monitored using SECM imaging tool. Control experiments were performed with a non-electroactive aptamer. After immobilization of these aptamers, SECM images showed the repartition of the electroactive anti-tetracycline aptamer when comparing with images produced for control and for all modification steps of SPCE. The possibility of tetracycline detection was also proved by causing a decrease in recorded current.     

Molecule-bridged mixed-valent intermediates involving the Ru I oxidation state

The diruthenium(II) complexes {(mu-L)[RuCl(Cym)]2}(PF6)n, Cym = p-cymene = 4-isopropyltoluene, L = 2,2'-azobispyridine = abpy and n = 1, or L = 2,5-bis(1-phenyliminoethyl)pyrazine = bpip and n = 2, were synthesized and characterized by NMR (n = 2) or EPR spectroscopy (n = 1). Whereas the (n = 1) species are ligand radical-bridged RuIIRuII complexes, the three-electron reduction under loss of both chloride ions produces the ions {(mu-L)[Ru(Cym)]2}+, which could be identified as RuI(4d7)-containing mixed-valent species (Ru0RuI or RuIRuII) through UV-vis-NIR spectroelectrochemistry (intervalence charge-transfer bands around 1500 nm) and EPR (rhombic g tensor anisotropy). The weak metal-metal interaction of the dsigma electrons from the eg set is responsible for the small electrochemical coupling with comproportionation constants Kc approximately 102.     

Chemically assisted vapour transport for bulk ZnO crystal growth

A chemically assisted vapour phase transport (CVT) method is proposed for the growth of bulk ZnO crystals. Thermodynamic computations have confirmed the possibility of using CO as a sublimation activator for enhancing the sublimation rate of the feed material in a large range of pressures (10⁻³ to 1 atm) and temperatures (800–1200 °C). Growth runs in a specific and patented design yielded single ZnO crystals up to 46 mm in diameter and 8 mm in thickness, with growth rates up to 400 μm/h. These values are compatible with an industrial production rate. N type ZnO crystals (μ=182 cm²/(V s) and n=7 10¹⁵ cm⁻³) obtained by this CVT method (Chemical Vapour Transport) present a high level of purity (10–30 times better than hydrothermal ZnO crystals), which may be an advantage for obtaining p-type doped layers ([Li] and [Al] <10⁺¹⁵ cm⁻³). Structural (HR-XRD), defect density (EPD), electrical (Hall measurements) and optical (photoluminescence) properties are presented.     

Urea cyclisation reaction studies

Synthetic approaches of N-α-hydroxyalkyl amides or urea derivatives are described. In particularly, a new 1,4,6-oxadiazocine-2,5,8-trione was obtained by condensation of glyoxylic acid on urea derivatives in acidic catalysis condition.     

An Artificial Intelligence Approach for Tackling Conformational Energy Uncertainties in Chiroptical Spectroscopies

Determination of the absolute configuration of chiral molecules is a prerequisite for obtaining a fundamental understanding in any chirality-related field. The interaction with polarised light has proven to be a powerful means to determine this absolute configuration, but its application rests on the comparison between experimental and computed spectra for which the inherent uncertainty in conformational Boltzmann factors has proven to be extremely hard to tackle. Here we present a novel approach that overcomes this issue by combining a genetic algorithm that identifies the relevant conformers by accounting for the uncertainties in DFT relative energies, and a hierarchical clustering algorithm that analyses the trends in the spectra of the considered conformers and identifies on-the-fly when a given chiroptical technique is not able to make reliable predictions. The effectiveness of this approach is demonstrated by considering the challenging cases of papuamine and haliclonadiamine, two bis-indane natural products with eight chiral centres and considerable conformational heterogeneity that could not be assigned unambiguously with current approaches.