Atmospheric fate of methacrolein. 2. Formation of lactone and implications for organic aerosol production

We investigate the oxidation of methacryloylperoxy nitrate (MPAN) and methacrylicperoxy acid (MPAA) by the hydroxyl radical (OH) theoretically, using both density functional theory [B3LYP] and explicitly correlated coupled cluster theory [CCSD(T)-F12]. These two compounds are produced following the abstraction of a hydrogen atom from methacrolein (MACR) by the OH radical. We use a RRKM master equation analysis to estimate that the oxidation of MPAN leads to formation of hydroxymethyl-methyl-α-lactone (HMML) in high yield. HMML production follows a low potential energy path from both MPAN and MPAA following addition of OH (via elimination of the NO(3) and OH from MPAN and MPAA, respectively). We suggest that the subsequent heterogeneous phase chemistry of HMML may be the route to formation of 2-methylglyceric acid, a common component of organic aerosol produced in the oxidation of methacrolein. Oxidation of acrolein, a photo-oxidation product from 1,3-butadiene, is found to follow a similar route generating hydroxymethyl-α-lactone (HML).     

Building blocks for oligospiroketal (OSK) Rods and evaluation of their influence on rod rigidity

We report on the synthesis of three new sleeves and their incorporation in OSK rods. The structures of these sleeves are based on neo-inositol, terephthalaldehyde diacetals, and indacene. To quantify the influence of the sleeves on rod rigidity, we applied the worm-like chain (WLC) model on the new rods and found that this approach is rather disappointing. As the chief cause of this result, we assume that the rigidity of typical molecular rods largely exceeds the rigidity of polymers, which were successfully described by the WLC model. Alternatively, we suggest quantifying the rigidity of molecular rods by fitting an empirical function on the end-to-end distance distribution curve obtained by MD simulations. After checking various function types, the Levy-Martin function proved to be most suitable for this purpose. On the basis of this function, we defined the Levy-Martin parameter and suggest using this parameter for the characterization of the rigidity of molecular rods.     

Taurine

The structure of taurine (2‐amino­ethane­sulfonic acid), C₂H₇NO₃S, has been redetermined at 150 K, and is compared with the structures of glycine and β‐alanine which, like taurine, are enzymatically conjugated with bile acids.     

Iterated hard-thresholding for linear inverse problems with sparsity constraints

We describe an iterative algorithm for the minimization of Tikhonov type functionals which involve sparsity constraints in form of ℓ^p -penalties which have been proposed recently for the regularization of ill-posed problems. In contrast to the well-known algorithm considered by Daubechies, Defrise and De Mol, it uses hard instead of soft thresholding. This hard thresholding algorithm is based on the generalized conditional gradient method. General results on the convergence of the generalized conditional gradient method enable us to prove strong convergence of the iterates. Furthermore we are able to establish convergence rates of O (n^–1/2) and O (λⁿ) for p = 1 and 1 < p ≤ 2 respectively. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the application of a single‐crystal κ‐diffractometer and a CCD area detector for studies of thin films

A multipurpose six‐axis κ‐diffractometer, together with the brilliance of the ESRF light source and a CCD area detector, has been explored for studying epitaxial relations and crystallinity in thin film systems. The geometrical flexibility of the six‐axis goniometer allows measurement of a large volume in reciprocal space, providing an in‐depth understanding of sample crystal relationships. By a set of examples of LaAlO₃ thin films deposited by the atomic layer deposition technique, the possibilities of the set‐up are presented. A fast panoramic scan provides determination of the crystal orientation matrices, prior to more thorough inspection of single Bragg nodes. Such information, in addition to a broadening analysis of families of single reflections, is shown to correlate well with the crystallinity, crystallite size, strain and epitaxial relationships in the thin films. The proposed set‐up offers fast and easy sample mounting and alignment, along with crucial information on key features of the thin film structures.     

A Catalytic Oxidative Quinone Heterofunctionalization Method: Synthesis of Strongylophorine‐26

The preparation of heteroatom‐substituted p‐quinones is ideally performed by direct addition of a nucleophile followed by in situ reoxidation. Albeit an appealing strategy, the reactivity of the p‐quinone moiety is not easily tamed and no broadly applicable method for heteroatom functionalization exists. Shown herein is that Co(OAc)₂ and Mn(OAc)₃?2 H₂O act as powerful catalysts for oxidative p‐quinone functionalization with a collection of O, N, and S nucleophiles, using oxygen as the terminal oxidant. Preliminary mechanistic observations and the first synthesis of the cytotoxic natural product strongylophorine‐26 is presented.     

Some stability results for explicit Runge-Kutta methods

The theory of positive real functions is used to provide bounds for the largest possible disk to be inscribed in the stability region of an explicit Runge-Kutta method. In particular, we show that the closed disk |+r| r can be contained in the stability region of an explicitm-stage Runge-Kutta method of order two if and only ifr m – 1.