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The structures and synthesis of polyzwitterions ("polybetaines") are reviewed, emphasizing the literature of the past decade. Particular attention is given to the general challenges faced, and to successful strategies to obtain polymers with a true balance of permanent cationic and anionic groups, thus resulting in an overall zero charge. Also, the progress due to applying new methodologies from general polymer synthesis, such as controlled polymerization methods or the use of "click" chemical reactions is presented. Furthermore, the emerging topic of responsive ("smart") polyzwitterions is addressed. The considerations and critical discussions are illustrated by typical examples.
Shape-memory polymers
(2004)
Aldehyde oxidases are molybdenum and flavin dependent enzymes characterized by a very wide substrate specificity and performing diverse reactions that include oxidations (e.g., aldehydes and azaheterocycles), hydrolysis of amide bonds, and reductions (e.g., nitro, S-oxides and N-oxides). Oxidation reactions and amide hydrolysis occur at the molybdenum site while the reductions are proposed to occur at the flavin site. AOX activity affects the metabolism of different drugs and xenobiotics, some of which designed to resist other liver metabolizing enzymes (e.g., cytochrome P450 monooxygenase isoenzymes), raising its importance in drug development. This work consists of a comprehensive overview on aldehyde oxidases, concerning the genetic evolution of AOX, its diversity among the human population, the crystal structures available, the known catalytic reactions and the consequences in pre-clinical pharmacokinetic and pharmacodynamic studies. Analysis of the different animal models generally used for pre-clinical trials and comparison between the human (hAOX1), mouse homologs as well as the related xanthine oxidase (XOR) are extensively considered. The data reviewed also include a systematic analysis of representative classes of molecules that are hAOX1 substrates as well as of typical and well characterized hAOX1 inhibitors. The considerations made on the basis of a structural and functional analysis are correlated with reported kinetic and metabolic data for typical classes of drugs, searching for potential structural determinants that may dictate substrate and/or inhibitor specificities.
Acyclic diene metathesis a versatile tool for the construction of defined polymer architectures
(2011)
Two decades have passed since the metathesis polymerisation of alpha,omega-dienes was successfully demonstrated by the group of Wagener and the term acyclic diene metathesis (ADMET) polymerisation was coined. Since then, the advances of metathesis chemistry have allowed to expand the scope of this versatile polymerisation reaction that nowadays finds applications in different fields, such as polymer, material, or medicinal chemistry. This critical review provides an insight into the historical aspects of ADMET and a detailed overview of the work done to date applying this versatile polymerisation reaction (221 references).
Polymeric biomaterials are of specific relevance in medical and pharmaceutical applications due to their wide range of tailorable properties and functionalities. The knowledge about interactions of biomaterials with their biological environment is of crucial importance for developing highly sophisticated medical devices. To achieve optimal in vivo performance, a description at the molecular level is required to gain better understanding about the surface of synthetic materials for tailoring their properties. This is still challenging and requires the comprehensive characterization of morphological structures, polymer chain arrangements and degradation behaviour. The review discusses selected aspects for evaluating polymeric biomaterial-environment interfaces by Langmuir monolayer methods as powerful techniques for studying interfacial properties, such as morphological and degradation processes. The combination of spectroscopic, microscopic and scattering methods with the Langmuir techniques adapted to polymers can substantially improve the understanding of their in vivo behaviour.
Ionogels (IGs), also termed ion gels, are functional hybrid materials based on an ionic liquid (IL) and a polymeric, hybrid, or inorganic matrix. IGs combine the properties of the matrix such as mechanical strength with IL properties like high ionic conductivity, high thermal stability, or catalytic activity. IGs are thus attractive for many applications, but the vast majority of IGs made and published so far are bulk materials or dense films. Applications like sensing or catalysis, however, would benefit from IGs with high surface areas or defined surface morphologies or architectures. In spite of this, only relatively few examples of high-surface-area IGs have been made so far; this has mostly been achieved by electrospinning, which has proven to be a promising strategy towards advanced IGs. The current review discusses first developments and outlines the future potential of electrospun ionogels, predominantly from a materials and inorganic chemistry perspective.
A class of adsorbents currently receiving growing attention is the clay-polymer nanocomposite (CPN) adsorbents. CPNs effectively treat water by adsorption and flocculation of both inorganic and organic micropollutants from aqueous solutions. Some of these CPNs - when modified with biocides - also have the ability to efficiently remove microorganisms such as Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Candida albicans from water. CPNs are far more easily recovered from aqueous media than neat clay. They also exhibit far better treatment times than either polymer or clay adsorbents. They have higher adsorption capacity and better life cycles compared with clay alone. CPNs therefore show an excellent potential as highly efficient water and waste treatment agents.
This article reviews the various CPNs that have been prepared recently and used as adsorbents in the removal of micropollutants (inorganic, organic and biological) from aqueous solutions. A special focus is placed on CPNs that are not only interesting from an academic point of view but also effectively reduce the concentration of micropollutants in water to safe limits and also on new developments bordering on CPN use as water treatment agent that have not yet realized their full potential. (C) 2014 Elsevier B.V. All rights reserved.
The importance of carbohydrate chemistry in biological and medicinal chemistry has led to enormous developments in the synthesis of carbohydrate mimics. In this context, the synthesis of branched sugars in general and of 2-C-branched carbohydrates in particular, as well as the synthesis of 1,2-annulated sugars, have received immense attention. They serve not only as carbohydrate mimics in the form of stand-alone molecules, but also as useful intermediates in the synthesis of many natural products, their analogues, and glycosidase inhibitors. This microreview covers the recent synthetic efforts in this area and puts the subject matter into proper perspective for future developments.
Stimuli-responsive macromolecules (i.e., pH-, thermo-, photo-, chemo-, and bioresponsive polymers) have gained exponential importance in materials science, nanotechnology, and biotechnology during the last two decades. This chapter describes the usefulness of this class of polymer for preparing smart surfaces (e.g., modified planar surfaces, particles surfaces, and surfaces of three-dimensional scaffolds). Some efficient pathways for connecting these macromolecules to inorganic, polymer, or biological substrates are described. In addition, some emerging bioapplications of smart polymer surfaces (e.g., antifouling surfaces, cell engineering, protein chromatography, tissue engineering, biochips, and bioassays) are critically discussed.