Isolation and characterization of a novel tetrahydro‐[2,2′]bipyrrolyl dimer as an impurity from a knorr reaction

A novel dimer, tetraethyl 2,2′,3,3′‐tetramethyl‐1,1′,2,2′‐tetrahydro‐4H,4′H‐2,2′‐bipyrrolyl‐5,5,5′,5′‐tetracarboxylate, has been isolated as an impurity (0.4% yield) from a Knorr reaction for the synthesis of ethyl 3,5‐dimethylpyrrole‐2‐carboxylate from 2,4‐pentanedione and diethyl oximinomalonate in a dissolving zinc reduction. The solid‐state structure of this novel dimer was determined by X‐ray crystallography. Knorr reactions typically rely upon the requisite pyrrole being the only water‐insoluble crystalline material present in the reaction mixture, and so work‐up and purification procedures for Knorr reactions should be monitored carefully given the water‐insolubility of this dimer. Investigations regarding mechanistic implications and reductive dimerization are underway.     

Monte Carlo Simulation of Degradation of Porous Poly(lactide) Scaffolds, 1

Summary: Monte Carlo method was used to simulate the degradation of porous PLA scaffolds. The simulated volume was assumed to be divided homogeneously between the pore and solid PLA with the ratio equal to the bulk porosity of the scaffold. The volume was divided into surface and bulk elements where the surface elements were in direct contact with the aqueous degradation medium, while the bulk elements were surrounded by the pore and solid PLA. The effect of degradation time on PLA ester groups and carboxylic acid end‐groups for surface and bulk elements, pH, PLA degradation rate and mass loss, and PLA molecular weight distribution was simulated. For surface elements, pH remained constant at 7.4 over the entire time of degradation, while for bulk elements its value decreased significantly to as low as 5.8. The highest drop in pH within the scaffold was observed for the highest porosity of 90%. There was a lag time of at least 7 weeks in the mass loss for surface as well as bulk elements for porosities ranging from 70 to 90%. The mass loss for bulk elements was considerably faster than the surface elements. This difference in the rate of mass loss between the surface and bulk elements could affect the 3D morphology and dimensional stability of the scaffold in vivo as degradation proceeds. The simulation predicts that, due to differences in the rate of bulk and surface degradation, hollow structures could form inside the scaffold after 19, 17, and 15 weeks for initial porosities of 70, 80, and 90%, respectively.

A schematic diagram illustrating the degradation of an element on the outer surface of the scaffold (surface element) versus an element within the volume of the scaffold (bulk element).     

New routes to the synthesis of pyridazinone,ethoxypyridine, pyrazole and pyrazolo[1,5‐a]pyrimidine derivatives incorporating a benzotriazole moiety

A new approach to the synthesis of pyridazinone, ethoxypyridine, pyrazole and 7‐aminopyrazolo‐[1,5‐a]pyrimidine derivatives. The structure of the newly synthesized compounds was elucidated by elemental analyses, ir, ¹H nmr spectra and in some cases by ¹³C nmr investigations.     

A biocompatible composite based on poly(ε‐caprolactone fumarate) and hydroxyapatite

Fabrication of biodegradable composites applicable as hard tissue substitutes consisting of poly(ε‐caprolactone fumarate) (PCLF), methacrylic acid (MAA), and hydroxyapatite (HA) was investigated. PCLF macromers were synthesized by reaction of PCL diol with fumaryl chloride in the presence of propylene oxide and characterized by gel permeation chromatography, FTIR, and ¹H NMR spectroscopy. Composites were fabricated by incorporating HA as inorganic filler in PCLF matrix which followed by thermal curing of the composition using benzoyl peroxide and MAA as a free radical initiator and reactive diluent, respectively. Uniform distribution of the fine ceramic phase in the polymer matrix was elucidated by scanning electron microscopy. The effects of the initial macromer molecular weight and the filler volume fraction on mechanical properties and cytotoxicity of the composites were also examined. Significant enhancement in the mechanical properties was observed upon increasing HA content and/or initial PCLF molecular weight. The biocompatibility of the specimens was also improved with increasing ceramic phase. Copyright © 2010 John Wiley & Sons, Ltd.     

Photoinduced Anisotropy in Poly(Methyl Methacrylate)/Sudan Red III Thin Films

The dynamic behavior of photoinduced optical anisotropy of amorphous PMMA/Sudan Red III thin films has been investigated using the pump-probe method. The results showed that the anisotropy increased rapidly in an exponential fashion in the first seconds of pumping, so that a photostationary state was reached as a result of the photoisomerization process cycles. The anisotropy relaxation phase decreased exponentially in a slow manner, which means the anisotropy did not disappear instantaneously when the irradiation was switched off. Evidence of the existence of the Angular Hole Burning (AHB) and the Angular Redistribution (AR) effects in the Sudan Red III molecules in the PMMA polymeric host is presented. The relative photoinduced optical anisotropy was calculated. The results showed that, at room temperature, the thermal isotropic relaxation of the photoisomer was negligible compared to the anisotropic reverse photoisomerization that occurred as soon as the pump beam was cut-off.     

A novel model to describe the intervertebral disc mechanical response

The main objective of the present work is the development of a simplified, efficient and easy-to-implement single-phase material model, which is able to describe the essential effects characterising the behaviour of multi-phase saturated materials, such as of intervertebral discs (IVDs). The presented new model mainly focuses on extending a viscoelastic material model in order to not only take the mechanical behaviour of the solid part into account, but also the fluid-flow-dependent behaviour of the material. By applying this model, the complexity and constitutive parameters are reduced, the implementation is more convenient and the experimental investigations can be better supported in comparison to multi-phase material models of IVDs. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)