Although the technological and scientific importance of functional polymers has been well established over the last few decades, the most recent focus that has attracted much attention has been on stimuli-responsive polymers. This group of materials is of particular interest due to its ability to respond to internal and/or external chemico-physical stimuli, which is often manifested as large macroscopic responses. Aside from scientific challenges of designing stimuli-responsive polymers, the main technological interest lies in their numerous applications ranging from catalysis through microsystem technology and chemomechanical actuators to sensors that have been extensively explored. Since the phase transition phenomenon of hydrogels is theoretically well understood advanced materials based on the predictions can be prepared. Since the volume phase transition of hydrogels is a diffusion-limited process the size of the synthesized hydrogels is an important factor. Consistent downscaling of the gel size will result in fast smart gels with sufficient response times. In order to apply smart gels in microsystems and sensors, new preparation techniques for hydrogels have to be developed. For the up-coming nanotechnology, nano-sized gels as actuating materials would be of great interest.
Cross-linked polymers have attracted an immense attention over the years, however, there are many flaws of these systems, e.g. softness and brittleness; such materials possess non-adjustable properties and cannot recover from damage and thus are limited in their practical applications. Supramolecular chemistry offers a variety of dynamic interactions that when integrated into polymeric gels endow the systems with reversibility and responsiveness to external stimuli. A combination of different cross-links in a single gel could be the key to tackle these drawbacks, since covalent or chemical cross-linking serve to maintain the permanent shape of the material and to improve overall mechanical performance, whereas non-covalent cross-links impart dynamicity, reversibility, stimuli-responsiveness and often toughness to the material. In the present review we sought to give a comprehensive overview of the progress in design strategies of different types of dually cross-linked single gels made by researchers over the past decade as well as the successful implementations of these advances in many demanding fields where versatile multifunctional materials are required, such as tissue engineering, drug delivery, self-healing and adhesive systems, sensors as well as shape memory materials and actuators.
There is an increasing interest in sensing applications for a variety of analytes in aqueous environments, as conventional methods do not work reliably under humid conditions or they require complex equipment with experienced operators. Hydrogel sensors are easy to fabricate, are incredibly sensitive, and have broad dynamic ranges. Experiments on their robustness, reliability, and reusability have indicated the possible long-term applications of these systems in a variety of fields, including disease diagnosis, detection of pharmaceuticals, and in environmental testing. It is possible to produce hydrogels, which, upon sensing a specific analyte, can adsorb it onto their 3D-structure and can therefore be used to remove them from a given environment. High specificity can be obtained by using molecularly imprinted polymers. Typical detection principles involve optical methods including fluorescence and chemiluminescence, and volume changes in colloidal photonic crystals, as well as electrochemical methods. Here, we explore the current research utilizing hydrogel-based sensors in three main areas: (1) biomedical applications, (2) for detecting and quantifying pharmaceuticals of interest, and (3) detecting and quantifying environmental contaminants in aqueous environments.
Aliphatic polycarbonates have attracted significant attention for biomedical application over the last few years due to their biodegradability, low toxicity and good biocompatibility. However, in most cases, the use of metal-based catalysts is required for the preparation of aliphatic polycarbonates by the polycondensation method, which is difficult to remove completely from the final polymer. For this reason, our work is focused on the synthesis of high-molecular-weight aliphatic polycarbonates using organo-catalysts via a two-step polycondensation of dimethyl carbonate and a linear alkane diol as monomers. A variety of organo-catalysts have been surveyed for the synthesis of aliphatic polycarbonates. The influence of thiourea with mono- or bi-electron acceptor groups as cocatalysts, which were found to activate the carbonyl groups of lactide and trimethylene carbonate in the ring opening polymerization successfully, was investigated in the polycondensation. In summary, high-molecular-weight aliphatic polycarbonates, such as poly(1,4-butylene carbonate) (PBC), poly(1,5-pentamethylene carbonate) (PPC) and poly(1,6-hexamethylene carbonate) (PHC), were successfully prepared with number averaged molar masses (Mn) up to 23 000 g mol−1, dispersities below 1.8 and high yield of >80% under relatively mild operating conditions (T < 130 °C) using 4-dimethylaminopyridine (DMAP) as the catalyst. At 170 °C the poly(1,4-butylene carbonate) with Mn of 52 000 g mol−1 was synthesized. Additionally, hydroxyl group terminated poly(1,4-butylene carbonate) with Mn up to 17 000 g mol−1 was obtained and characterized by 1H NMR spectroscopy and ESI-TOF-mass spectrometry. The ratio of end groups (–OH/–OC(O)O–CH3) could be adjusted by using different feed ratios or catalysts.
22 April 2013 in Journal of Polymer Science Part A: Polymer Chemistry