Thermal decomposition of peroxy acetyl nitrate CH3C(O)OONO2

The thermal decomposition of peroxy acetyl nitrate (PAN) is investigated by low pressure flash thermolysis of PAN highly diluted in noble gases and subsequent isolation of the products in noble gas matrices at low temperatures and by density functional computations. The IR spectroscopically observed formation of CH3C(O)OO and H2CCO (ketene) besides NO2, CO2, and HOO implies a unimolecular decay pathway for the thermal decomposition of PAN. The major decomposition reaction of PAN is bond fission of the O-N single bond yielding the peroxy radical. The O-O bond fission pathway is a minor route. In the latter case the primary reaction products undergo secondary reactions whose products are spectroscopically identified. No evidence for rearrangement processes as the formation of methyl nitrate is observed. A detailed mapping of the reaction pathways for primary and secondary reactions using quantum chemical calculations is in good agreement with the experiment and predicts homolytic O-N and O-O bond fissions within the PAN molecule as the lowest energetic primary processes. In addition, the first IR spectroscopic characterization of two rotameric forms for the radical CH3C(O)OO is given.     

Ligand dependence of the synthetic approach and chiroptical properties of a magic cluster protected with a bicyclic chiral thiolate

Chiral gold clusters stabilised by enantiopure thiolates were prepared, size-selected and characterised by circular dichroism and mass spectrometry. The product distribution is found to be ligand dependent. Au(25) clusters protected with camphorthiol show clear resemblance of their chiroptical properties with their glutathionate analogue.     

Utilization of maltodextrin based enantioselective, potentiometric membrane electrodes for the enantioselective assay of S-perindopril

Enantioselective, potentiometric membrane electrodes (EPMEs) based on carbon paste impregnated with different maltodextrins {dextrose equivalent (DE) 4.0-7.0 (I), 13.0-17.0 (II) and 16.5-19.5 (III)} as chiral selectors for the assay of S-perindopril is described. The proposed electrodes could be reliably employed in the assay of S-perindopril raw material and from its pharmaceutical formulation, Coversyl^® tablets. The electrode based on maltodextrin (I) showed the best enantioselectivity and time-stability. The surfaces of the electrodes are easily renewable by simply polishing on an alumina paper.     

Phase diagram of polypeptide chains

We use a coarse grained protein model that enables us to determine the equilibrium phase diagram of natively folded α-helical and unfolded β-sheet forming peptides. The phase diagram shows that there are only two thermodynamically stable peptide phases, the peptide solution and the bulk fibrillar phase. In addition, it reveals the existence of various metastable peptide phases. The liquidlike oligomeric phases are metastable with respect to the fibrillar phases, and there is a hierarchy of metastability. The presented phase diagram provides a solid basis for understanding the assembly of polypeptide chains into the phases formed in their natively folded and unfolded conformations.     

Zeolite synthesis: an energetic perspective

Taking |D(H(2)O)(x)|[AlSiO(4)] based materials (where D is Li, Na, K, Rb or Cs) as an archetypal aluminosilicate system, we use accurate density functional theory calculations to demonstrate how the substitution of silicon cations in silica, with pairs of aluminium and (alkali metal) cations, changes the energetic ordering of different competing structure-types. For large alkali metal cations we further show that the formation of porous aluminosilicate structures, the so-called zeolites, is energetically favored. These findings unequivocally demonstrate that zeolites can be energetic preferred reaction products, rather than being kinetically determined, and that the size of the (hydrated) cations in the pore, be it inorganic or organic, is critical for directing zeolite synthesis.     

Polyether Natural Product Inspired Cascade Cyclizations: Autocatalysis on π‐Acidic Aromatic Surfaces

Anion‐π catalysis functions by stabilizing anionic transition states on aromatic π surfaces, thus providing a new approach to molecular transformation. The delocalized nature of anion–π interactions suggests that they serve best in stabilizing long‐distance charge displacements. Aiming therefore for an anionic cascade reaction that is as charismatic as the steroid cyclization is for conventional cation‐π biocatalysis, reported here is the anion‐π‐catalyzed epoxide‐opening ether cyclizations of oligomers. Only on π‐acidic aromatic surfaces having a positive quadrupole moment, such as hexafluorobenzene to naphthalenediimides, do these polyether cascade cyclizations proceed with exceptionally high autocatalysis (rate enhancements k_auto/k_cat >10⁴ m ^?1). This distinctive characteristic adds complexity to reaction mechanisms (Goldilocks‐type substrate concentration dependence, entropy‐centered substrate destabilization) and opens intriguing perspectives for future developments.     

DABCOnium: An Efficient and High‐Voltage Stable Singlet Oxygen Quencher for Metal–O2 Cells

Singlet oxygen (¹O₂) causes a major fraction of the parasitic chemistry during the cycling of non‐aqueous alkali metal‐O₂ batteries and also contributes to interfacial reactivity of transition‐metal oxide intercalation compounds. We introduce DABCOnium, the mono alkylated form of 1,4‐diazabicyclo[2.2.2]octane (DABCO), as an efficient ¹O₂ quencher with an unusually high oxidative stability of ca. 4.2 V vs. Li/Li⁺. Previous quenchers are strongly Lewis basic amines with too low oxidative stability. DABCOnium is an ionic liquid, non‐volatile, highly soluble in the electrolyte, stable against superoxide and peroxide, and compatible with lithium metal. The electrochemical stability covers the required range for metal–O₂ batteries and greatly reduces ¹O₂ related parasitic chemistry as demonstrated for the Li–O₂ cell.     

What is the role of acid–acid interactions in asymmetric phosphoric acid organocatalysis? A detailed mechanistic study using interlocked and non-interlocked catalysts

Organocatalysis has revolutionized asymmetric synthesis. However, the supramolecular interactions of organocatalysts in solution are often neglected, although the formation of catalyst aggregates can have a strong impact on the catalytic reaction. For phosphoric acid based organocatalysts, we have now established that catalyst–catalyst interactions can be suppressed by using macrocyclic catalysts, which react predominantly in a monomeric fashion, while they can be favored by integration into a bifunctional catenane, which reacts mainly as phosphoric acid dimers. For acyclic phosphoric acids, we found a strongly concentration dependent behavior, involving both monomeric and dimeric catalytic pathways. Based on a detailed experimental analysis, DFT-calculations and direct NMR-based observation of the catalyst aggregates, we could demonstrate that intermolecular acid–acid interactions have a drastic influence on the reaction rate and stereoselectivity of asymmetric transfer-hydrogenation catalyzed by chiral phosphoric acids.

Supramolecular acid–acid interactions lead to competing monomeric and dimeric pathways in phosphoric acid catalysis – so that stereoselectivities depend on catalyst concentration.