Synthese von (+)-Aspicilin mit Bausteinen aus nachwachsenden Rohstoffen

Synthesis of (+)-Aspicilin Using Building Blocks from Renewable Resources The 18-membered lichen macrolide (+)-aspicilin ( 1 ) is easily built up from compounds 14 , 16 , 3 , and 24 following the C₃ + C₇ + C₆ + C₂ = C₁₈ pattern (see Schemes). The synthesis requires 15 steps and gives 1 in 13% overall yield from D -mannose ( 2 ). The latter compound provides the stereogenic centers C(4), C(5), and C(6). The stereogenic center C(17) is supplied by building block 14 (from (?)-(S)-ethyl lactate).     

Tuning the mechanical properties of silica microcapsules

Heat treatment is a standard method to increase the hardness of silica in various applications. Here, we tested the effect of high temperature annealing on the mechanical properties of silica microcapsules by force spectroscopy under point loads applied to the particle shell. The Young's modulus of the shells moderately increases after annealing at temperatures above 500 °C. Temperatures over 850 °C result in a much stronger increase and the Young's modulus is close to that of fused silica after annealing at 1100 °C. NMR analysis revealed that in untreated microcapsules synthesized by seeded growth using the St?ber method only 55% of the silicon atoms form siloxane bonds with four neighbors, whereas the remaining ones only form three or less siloxane bonds each and, thus, a large number of ethoxy and silanol groups still exist. During annealing at 500 °C, these are successively transformed into siloxane bonds through condensation reactions. This process correlates with only a moderate increase in Young's modulus. The strong increase at temperatures above 850 °C was associated with a densification which was associated by a decrease in capsule size and shell thickness while the shells remained homogenous and of spherical shape. The main strengthening of the shells is thus mainly due to compaction by sintering at length scales significantly larger than that of local siloxane bonds.     

Suprema of Chaos Processes and the Restricted Isometry Property

We present a new bound for suprema of a special type of chaos process indexed by a set of matrices, which is based on a chaining method. As applications we show significantly improved estimates for the restricted isometry constants of partial random circulant matrices and time‐frequency structured random matrices. In both cases the required condition on the number m of rows in terms of the sparsity s and the vector length n is m ? s log² s log² n. © 2014 Wiley Periodicals, Inc.     

Thiol‐ene photopolymerization for efficient curing of vinyl esters

Monomers for radical photopolymerization based on vinyl esters (VEs) have recently been identified as suitable alternatives to (meth)acrylates on account of their low irritancy and cytotoxicity. The drawback of most VEs with abstractable hydrogens is their relatively low reactivity compared with (meth)acrylates. Within this article, we proved by photo‐differential scanning calorimetry measurements and real‐time Fourier transform infrared spectroscopy that the thiol‐ene concept is able to improve the photoreactivity of these VEs to a large extent to a level between those of acrylates and methacrylates. Other VEs have now a reactivity of at least the level of similar acrylates. Mechanical properties as determined by Dynamic Mechanical Analysis and Charpy impact tests showed significant toughening of these materials. Furthermore, we were able to confirm low toxicity of all components by osteoblast cell culture experiments. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Ab initio study on the thermolysis of β-hydroxyolefins in gas phase

Thermolysis studies of β-hydroxyolefins in gas phase were realized using ab initio MP2 and DFT methods at the 6-31G^* levels to explore the possibility of determining a possible concerted process with a six-membered cyclic transition state (TS). Vibrational frequency calculations were carried out in order to confirm the stationary states, including TS structures. IRC calculations have been performed in all cases in order to verify that localized TS structures connect with the corresponding minimum stationary points associated with the reactant and products. With the aim of corroborating the postulated mechanism in the experimental study, we present a theoretical study in order to calculate the rate constants and the activation parameters. The results obtained are in accordance with the experimental conclusions.     

Designing Molecular Printboards: A Photolithographic Platform for Recodable Surfaces

A light induced strategy for the design of β‐cyclodextrin (CD) based supramolecular devices is introduced, presenting a novel tool to fabricate multifunctional biointerfaces. Precision photolithography of a modified β‐CD was established on a light sensitive tetrazole surface immobilized on a bioinspired polydopamine (PDA) anchor layer via various shadow masks, as well as via direct laser writing (DLW), in order to craft any desired printboard design. Interfacial molecular recognition provided by light generated cavitate domains was demonstrated via spatially resolved encoding, erasing, and recoding of distinct supramolecular guest patterns. Thus, the light directed shaping of receptor monolayers introduces a powerful path to control supramolecular assemblies on various surfaces.     

Low rank matrix recovery from rank one measurements

We study the recovery of Hermitian low rank matrices $X\in {\mathbb{C}}^{n\times n}$ from undersampled measurements via nuclear norm minimization. We consider the particular scenario where the measurements are Frobenius inner products with random rank-one matrices of the form $a_j{a}_j^{?}$ for some measurement vectors $a_1,\dots ,a_m$, i.e., the measurements are given by $b_j=\mathrm{tr}(X{a}_j{a}_j^{?})$. The case where the matrix $X=x{x}^{?}$ to be recovered is of rank one reduces to the problem of phaseless estimation (from measurements $b_j=|〈x,a_j〉{|}^2$) via the PhaseLift approach, which has been introduced recently. We derive bounds for the number m of measurements that guarantee successful uniform recovery of Hermitian rank r matrices, either for the vectors $a_j$, $j=1,\dots ,m$, being chosen independently at random according to a standard Gaussian distribution, or $a_j$ being sampled independently from an (approximate) complex projective t-design with $t=4$. In the Gaussian case, we require $m\ge Crn$ measurements, while in the case of 4-designs we need $m\ge \mathit{Cr}n\log ?(n)$. Our results are uniform in the sense that one random choice of the measurement vectors $a_j$ guarantees recovery of all rank r-matrices simultaneously with high probability. Moreover, we prove robustness of recovery under perturbation of the measurements by noise. The result for approximate 4-designs generalizes and improves a recent bound on phase retrieval due to Gross, Krahmer and Kueng. In addition, it has applications in quantum state tomography. Our proofs employ the so-called bowling scheme which is based on recent ideas by Mendelson and Koltchinskii.