Coupling Interrupted Fischer and Multicomponent Joullié-Ugi to Chase Chemical Diversity: from Batch to Sustainable Flow Synthesis of Peptidomimetics

The generation of peptidomimetic substructures for medicinal chemistry purposes requires effective and divergent synthetic methods. We present in this work an efficient flow process that allows quick modulation of reagents for Joullié-Ugi multicomponent reaction, using spiroindolenines as core motifs. This sterically hindered imine equivalent could successfully be diversified using various isocyanides and amino acids in generally good space-time yields. A telescoped flow process combining interrupted Fischer reaction for spiroindolenine synthesis and subsequent Joullié-Ugi-type modification resulted in product formation in very good overall yield in less than 2 hours compared to 48 hours required in batch mode. The developed protocol can be seen as a general tool for rapid and facile generation of peptidomimetic compounds. We also showcase preliminary biological assessments for the prepared compounds.     

A case study in the mechanical verification of fault tolerance

To date, there is little evidence that modular reasoning about fault-tolerant systems can simplify the verification process in practice. This question is studied using a prominent example from the fault tolerance literature: the problem of reliable broadcast in point-to-point networks subject to crash failures of processes. The experiences from this case study show how modular specification techniques and rigorous proof re-use can indeed help in such undertakings.     

Phase-sensitive non-classicality criteria for phase-independent quantum states

A recently introduced hierarchy of necessary and sufficient conditions for non-classicality of a quantum state [Th. Richter and W. Vogel, Phys. Rev. Lett. 89 283601 (2002)] is applied to the characterization of phase-insensitive quantum states. Even under such conditions it may be important to analyse the relation between different phase values in the quadrature distributions in order to demonstrate the non-classical nature of the state under study.     

Mechanical material characterization of photosensitive polymers

In addition to the development of materials and technologies for smart HARMST applications the analysis of the thermo-mechanical material properties seems to be necessary to describe the photosensitive polymers applied. To do this, a microtensile analysis system has been developed to determine stress–strain curves, Young’s modulus and Poisson’s ratio. The results are compared with those of dynamical mechanical thermal analysis and discussed.     

Controlling micro‐ and nanofibrillar morphology of polymer blends in low‐speed melt spinning process. Part II: Influences of extrusion rate on morphological changes of a PLA/PVA blend through a capillary die

The effects of the extrusion rate on the morphological changes of poly(lactic acid) (PLA)/poly(vinyl alcohol) (PVA) blend through a capillary die were investigated. In this study, the extrusion rate or mass flow rate is altered from 0.5 g min^?1 to 2 g min^?1 with an increment of 0.5 g min^?1. The PLA/PVA blend with a composition of 30/70 (wt %) exhibits a particle matrix morphology with dispersed PLA droplets within the PVA matrix. It is found that, the spherical or ellipsoidal dispersed PLA droplets are elongated and coalesced into rod‐like or longer ellipsoidal droplets when they pass through the capillary die. When the extrusion rate increases, the coalescence between the large PLA droplets occurs more intense. However, the changes of the extrusion rate have no strong effect on the coalescence of small droplets having diameter less than about 150 nm. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44257.     

High‐Temperature Neutron Diffraction,Raman Spectroscopy,and First‐Principles Calculations of Ti3SnC2 and Ti2SnC

Herein, we report—for the first time—on the additive‐free bulk synthesis of Ti₃SnC₂. A detailed experimental study of the structure of the latter together with a secondary phase, Ti₂SnC, is presented through the use of X‐ray diffraction (XRD), and high‐resolution transmission microscopy (HRTEM). A previous sample of Ti₃SnC₂, made using Fe as an additive and Ti₂SnC as a secondary phase, was studied by high‐temperature neutron diffraction (HTND) and XRD. The room‐temperature crystallographic parameters of the two MAX phases in the two samples are quite similar. Based on Rietveld analysis of the HTND data, the average linear thermal expansion coefficients of Ti₃SnC₂ in the a and c directions were found to be 8.5 (2)·10^?6 K^?1 and 8.9 (1)·10^?6 K^?1, respectively. The respective values for the Ti₂SnC phase are 10.1 (3)·10^?6 K^?1 and 10.8 (6)·10^?6 K^?1. Unlike other MAX phases, the atomic displacement parameters of the Sn atoms in Ti₃SnC₂ are comparable to those of the Ti and C atoms. When the predictions of the atomic displacement parameters obtained from density functional theory are compared to the experimental results, good quantitative agreement is found for the Sn atoms. In the case of the Ti and C atoms, the agreement is more qualitative. We also used first principles to calculate the elastic properties of both Ti₂SnC and Ti₃SnC₂ and their Raman active modes. The latter are compared to experiment and the agreement was found to be good.     

Shear‐induced shish‐kebab structures in isotactic polypropylene using acicular precipitated calcium carbonate as whisker

It has been reported in the technical literature that whiskers of rodlike single crystals can be used in order to generate shish‐kebab structures or other different lamellae morphologies during isothermal or dynamic crystallization of sheared or presheared polymer melts. The expected advantage of the changed crystalline structure is a reinforcing effect of the composite. A lot of papers reported about the application of inorganic and organic whiskers such as cellulose and chitin whiskers. This study reports on an attempt to use acicular PCC as appropriate whisker for improving mechanical properties of polypropylene. In this article special attention is given to demonstrate the effect of flow induced crystallization under varying shear conditions in order to improve the mechanical properties. The effects were demonstrated using rheology, thermal analysis, tensile testing, and transmission electron microscopy. POLYM. ENG. SCI., 54:2057–2063, 2014. © 2013 Society of Plastics Engineers