Philipp Schattling

Multi-stimuli responsive polymers – the all-in-one talents

Stimuli-responsive polymers have gained increasing attention, which is attributed to the manifold applications they can be used for. Several years intensive research was invested in stimuli-responsive polymers. Their stimuli-responsiveness led not only to novel responsive groups, which enabled the translation of an external physical impact into a change of a material property, but also to polymers that are equipped with more than one responsive group. The integration of several responsive moieties within one polymer yields smart polymers exhibiting complex responsive behaviour of the polymers. This review summarises recent developments in the area of multi-stimuli responsive polymers, laying the focus on the improved, multifaceted response of polymer materials depending on the impact of several external stimuli.

Multi-responsive copolymers: using thermo-, light- and redox stimuli as three independent inputs towards polymeric information processing

We report on triple responsive polymers, exhibiting a distinct and reversible lower critical solution temperature in water that can be altered by light and redox stimuli, and we suggest their evaluation for molecular information processing.

Covalently bonded layer-by-layer assembly of multifunctional thin films based on activated esters.

We demonstrate that chemically stable, multifunctional polymer thin films can be obtained using the layer-by-layer (LbL) deposition based on covalent bonds between adsorbing chains. Poly(pentafluorophenyl-4-vinylbenzoate) (P1) or poly(pentafluorophenylacrylate) (P2) polymers were assembled with poly(allyl amine) (PAAm) to yield LbL multilayer films through amide bond formation by the reaction between activated esters of P1 or P2 and amine groups in PAAm, which was quantitatively monitored by Fourier transform infrared spectroscopy (FT-IR). It was found that the difference in the solubility of P1 and P2 against ethanol, which was used as the solvent for PAAm, during the LbL deposition yields different reaction conversion for the activated esters in either P1 or P2: the reaction conversion of P2 is higher than the conversion with P1. In addition, free (or unreacted) activated esters and amine groups remaining in the PAAm/P1 LbL film were further utilized for the incorporation of multiple functional materials (5-((2-aminoethyl)amino)naphthalene-1-sulfonic acid (EDANS) and Rhodamine B dyes in the present case) by post-treatments in order to further tailor the film properties. It was also demonstrated that the surface functional groups (activated esters) in the LbL films can also be utilized for surface patterning with one functional material, followed by functionalization with a second functional material during the post-treatment throughout the whole film. Finally, the PAAm/P1 and PAAm/P2 LbL films were shown to be quite stable in the extreme pH range, and free-standing films can easily be obtained by the treatment of the films with mild acidic conditions. The versatility of incorporating multiple functional materials into a single multilayer film as well as the excellent physicochemical stability of the covalently bonded multilayer free-standing films proves to be quite useful to design flexible and multifunctional thin film structures for many chemical and biological applications.

Nanotube Friendly Poly(N-isopropylacrylamide).

Poly(N-ispropylacrylamide) [PNIPAM] is a widely studied polymer for use in biological applications due to its lower critical solution temperature (LCST) being so close to the human body temperature. Unfortunately, attempts to combine carbon nanotubes (CNTs) with PNIPAM have been unsuccessful due to poor interactions between these two materials. In this work, a PNIPAM copolymer with 1u2009mol-% pyrene side group [p-PNIPAM] was used to produce a thermoresponsive polymer capable of stabilizing both single and multi-walled carbon nanotubes (MWNTs) in water. The presence of pyrene in the polymer chain lowers the LCST less than 4u2009°C and the interaction with nanotubes does not show any influence on LCST. Moreover, p-PNIPAM stabilized nanotubes show a temperature-dependent dispersion in water that allows the level of nanotube exfoliation/bundling to be controlled. Cryo-TEM images, turbidity, and viscosity of these suspensions were used to characterize these thermoresponsive changes. This ability to manipulate the dispersion state of CNTs in water with p-PNIPAM will likely benefit many biological applications, such as drug delivery, optical sensors, and hydrogels.

Redox active polymers with phenothiazine moieties for nanoscale patterning via conductive scanning force microscopy

Redox active polymers with phenothiazine moieties have been synthesized by Atomic Transfer Radical Polymerization (ATRP). These novel polymers reveal bistable behaviour upon application of a bias potential above the oxidation threshold value. Using conductive Scanning Force Microscopy, two distinguishable conductivity levels were induced on a nanoscale level. These levels were related to a high conducting “On” and a low conducting “Off” state. The “On” state is generated by the oxidation of the phenothiazine side chains to form stable phenothiazine radical cations. The formation and stability of the radical sites was examined by cyclic voltammetry, electron spin resonance and optical spectroscopy. Polymers with phenothiazine moieties show the ability to retain their redox state for several hours and can therefore be used for nonvolatile organic memory devices. Furthermore, thin films made from the phenothiazine containing polymers show high mechanical nanowear stability.

Reactive nanorods based on activated ester polymers: a versatile template-assisted approach for the fabrication of functional nanorods

A new route for the fabrication of polymeric nanorods with functional moieties via post-modification of reactive nanorods is described. To this end reactive nanorods with a homogenous and narrow size distribution were fabricated by utilizing an anodic aluminium oxide (AAO) template-assisted approach. The nanorods are based on activated pentafluorophenyl esters, to enable quantitative post-modification with amines under very mild reaction conditions yielding the corresponding functionalized amide. Post-modification with fluorescent dyes as well as the conversion into well-dispersed rod-shaped poly(N-isopropylacrylamide) (PNIPAM) hydrogels that exhibit a thermal-responsive phase transition was demonstrated. The platform of reactive nanorods provides the fabrication of various functional nanoobjects and may find application in research fields like drug delivery.