Polymorphism and Stretch-Induced Transformations of Sustainable Polyethylene-Like Materials.

Herein we demonstrate that polyethylene-like bioderived, biodegradable, and fully recyclable unbranched aliphatic polyesters, such as PE-2,18, develop hexagonal crystal structures upon quenching from the melt to temperatures <∼50 °C and orthorhombic-like packing at higher quenching temperatures or after isothermal crystallization. Both crystal types are layered. While CH packing characterizes the structure of the orthorhombic-like form, there is significant conformational disorder in the staggered long CH sequences of the hexagonal crystals.

Crystallization of Long-Spaced Precision Polyacetals III: Polymorphism and Crystallization Kinetics of Even Polyacetals Spaced by 6 to 26 Methylenes.

In this paper we extend the study of polymorphism and crystallization kinetics of aliphatic polyacetals to include shorter (PA-6) and longer (PA-26) methylene lengths in a series of even long-spaced systems. On a deep quenching to 0 °C, the longest even polyacetals, PA-18 and PA-26, develop mesomorphic-like disordered structures which, on heating, transform progressively to hexagonal, Form I, and Form II crystallites. Shorter polyacetals, such as PA-6 and PA-12 cannot bypass the formation of Form I.

Infrared Spectroscopy and X-ray Diffraction Characterization of Dimorphic Crystalline Structures of Polyethylenes with Halogens Placed at Equal Distance along the Backbone.

Polyethylenes with halogens placed on each and every 21st, 15th, or ninth backbone carbon display crystallization patterns enabled by the size of the halogen and by changing crystallization kinetics. The different structures have been identified from X-ray patterns combined with a detailed analysis of the infrared spectra of series containing F, Cl, or Br atoms that were either fast or isothermally crystallized from the melt. Under both crystallization modes, all specimens develop layered crystallites that accommodate 5-9 repeating units along the chain's axis.

Carbon nanotubes on a spider silk scaffold.

Understanding the compatibility between spider silk and conducting materials is essential to advance the use of spider silk in electronic applications. Spider silk is tough, but becomes soft when exposed to water. Here we report a strong affinity of amine-functionalised multi-walled carbon nanotubes for spider silk, with coating assisted by a water and mechanical shear method.

Distinct solid and solution state self-assembly pathways of RADA16-I designer peptide.

Solid state NMR measurements on selectively (13) C-labeled RADA16-I peptide (COCH3 -RADARADARADARADA-NH2 ) were used to obtain new molecular level information on the conversion of α-helices to β-sheets through self-assembly in the solid state with increasing temperature. Isotopic labeling at the A4 Cβ site enabled rapid detection of (13) C NMR signals. Heating to 344-363 K with simultaneous NMR detection allowed production of samples with systematic variation of α-helix and β-strand content.

Solid state self-assembly mechanism of RADA16-I designer peptide.

We report that synthetic RADA16-I peptide transforms to β-strand secondary structure and develops intermolecular organization into β-sheets when stored in the solid state at room temperature. Secondary structural changes were probed using solid state nuclear magnetic resonance spectroscopy (ssNMR) and Fourier transform infrared spectroscopy (FTIR). Intermolecular organization was analyzed via wide-angle X-ray diffraction (WAXD).

Physical characterization of functionalized spider silk: electronic and sensing properties.

This work explores functional, fundamental and applied aspects of naturally harvested spider silk fibers. Natural silk is a protein polymer where different amino acids control the physical properties of fibroin bundles, producing, for example, combinations of β-sheet (crystalline) and amorphous (helical) structural regions. This complexity presents opportunities for functional modification to obtain new types of material properties.

Separation of short-chain branched polyolefins by high-temperature gradient adsorption liquid chromatography.

A new separation principle was recently introduced into the analytical characterization of polyolefins by researchers from the German Institute for Polymers in Darmstadt. It was demonstrated that polyolefins can be selectively separated via high-performance liquid chromatography on the basis of their adsorption/desorption behaviours at temperatures as high as 160 °C. A Hypercarb® column packed with porous graphite gave the best results.