Polymer Composites – Polyolefin Fractionation – Polymeric Peptidomimetics – Collagens

In recent years there has been an increasing amount of interest, both commercially and scientifically, in the emerging field of “self-reinforced polymer composites”. These materials, which are sometimes also referred to as “single polymer composites”, or “all-polymer composites”, were first conceived in the 1970s, and are now beginning to appear in a range of commercial products. While high mechanical performance polymer fibres or tapes are an obvious precursor for composite development, various different technologies have been developed to consolidate these into two- or three-dimensional structures. This paper presents a review of the various processing techniques that have been reported in the literature for the manufacture of self-reinforced polymer composites from fibres or tapes of different polymers, and so exploit the fibre or tape performance in a commercial material or product.

The synthesis and characterization of polyolefins continues to be one of the most important areas for academic and industrial research. One consequence of the development of new “tailor-made” polyolefins is the need for new and improved analytical techniques for the analysis of polyolefins with respect to molar mass, molecular topology and chemical composition distribution. This review presents different new and relevant techniques for polyolefin analysis. The analysis of copolymers by combining high-temperature SEC and FTIR spectroscopy yields information on chemical composition and molecular topology as a function of molar mass. Crystallization based fractionation techniques are powerful methods for the analysis of short-chain branching in LLDPE and the analysis of polyolefin blends. These methods include temperature-rising elution fractionation, crystallization analysis fractionation and the recently developed crystallization-elution fractionation.

The latest development in the field of polyolefin fractionation is high-temperature interaction chromatography. Based on the principles of gradient HPLC and liquid chromatography at critical conditions this method is used for fast analysis of the chemical composition distribution of complex olefin copolymers. The efficiency of HPLC based systems for the separation of various olefin copolymers will be discussed. The ultimate development in high-temperature fractionation of polyolefins is comprehensive high-temperature two-dimensional liquid chromatography. The review will discuss some of the pioneering work that has been done since 2008.

Finally, the correlation between molar mass and chemical composition can be accessed by on-line coupling of high-temperature SEC and ¹H-NMR spectroscopy. It is shown that the on-line NMR analysis of chromatographic fractions from high-temperature fractionations is possible and yields information on microstructure and tacticity in addition to molar mass and copolymer composition.

Polymer-based peptidomimetics, or proteinomimetics, are a relatively young and dynamic field of research. The ability to successfully mimic the biochemical activity of antimicrobial peptides (AMPs) has been demonstrated by several groups. This has been accomplished by careful tuning of the molecule’s hydrophobicity and charge density. At the same time, many important questions remain to be answered, including the role of backbone rigidity, details of membrane insertion, and the role of curvature in the self-assemblies between these novel peptidemimetics and phospholipids. As the biological properties of polymeric synthetic mimics of AMPs (SMAMPs) result from the interplay of many parameters, it is not yet possible to predict the exact properties of such molecules from their mere chemical structure. However, as demonstrated here, the effect of certain design features such as charge and hydrophobicity on the properties across a polymer series is understood. Compared to the mechanistic specifics that are known about the interactions of AMPs or small antibacterial molecules with membranes and cells, relatively little is known concerning the interaction of polymeric SMAMPs with membranes. Beyond SMAMPs, numerous opportunities exist and protein transduction domain mimics are an active area of research in the Tew laboratory. These two examples, one quite new and the other studied for almost a decade, demonstrate that it is possible to teach synthetic polymers to behave like peptides, despite their lack of sequence specificity and secondary structure.

The extracellular matrix is a complex biological structure encoded with various proteins, among which the collagen family is the most significant and abundant of all, contributing 30–35% of the whole-body protein. “Collagen” is a generic term for proteins that forms a triple-helical structure with three polypeptide chains, and around 29 types of collagen have been identified up to now. Although most of the members of the collagen family form such supramolecular structures, extensive diversity exists between each type of collagen. The diversity is not only based on the molecular assembly and supramolecular structures of collagen types but is also observed within its tissue distribution, function, and pathology. Collagens possess complex hierarchical structures and are present in various forms such as collagen fibrils (1.5–3.5 nm wide), collagen fibers (50–70 nm wide), and collagen bundles (150–250 nm wide), with distinct properties characteristic of each tissue providing elasticity to skin, softness of the cartilage, stiffness of the bone and tendon, transparency of the cornea, opaqueness of the sclera, etc. There exists an exclusive relation between the structural features of collagen in human tissues (such as the collagen composition, collagen fibril length and diameter, collagen distribution, and collagen fiber orientation) and its tissue-specific mechanical properties. In bone, a transverse collagen fiber orientation prevails in regions of higher compressive stress whereas longitudinally oriented collagen fibers correlate to higher tensile stress. The immense versatility of collagen compels a thorough understanding of the collagen types and this review discusses the major types of collagen found in different human tissues, highlighting their tissue-specific uniqueness based on their structure and mechanical function. The changes in collagen during a specific tissue damage or injury are discussed further, focusing on the many tissue engineering applications for which collagen scaffolds are currently being applied.