Hierarchical Micelles via Polyphilic Interactions: Hydrogen-Bonded Supramolecular Dendrons and Double Immiscible Polymers.

Chen, S., et al. Nano Letters 2016, 16 (2), 1491-1496, DOI: http://dx.doi.org/10.1021/acs.nanolett.5b05203.

We report a simple strategy to form three-phase segregated hierarchical micelles via a counterbalanced phase segregation/self-assembly process. We do have designed and prepared mid- and α,β -barbiturate (Ba) functionalized poly(n-butyl acrylates), Ba-(PnBuA-Ba)2, together with a series of heterocomplementary α,β -Hamilton wedge (HW) functionalized polymers via reversible addition-fragmentation chain transfer (co)polymerization. Transmission electron microscopy demonstrates a unique, uncommon phase behavior showing remarkable three-phase segregated hierarchical micelles, indicative of the desired micellar multicompartments. Reproduced with permission. Copyright 2016©, American Chemical Society.

Orthogonal Modification of Polymers via Thio–Bromo “Click” Reaction and Supramolecular Chemistry: An Easy Method Toward Head-to-Tail Self-Assembled Supramolecular Polymers.

Chen, S., et al. ACS Macro Letters 2015, 4, 48-52, DOI: http://dx.doi.org/10.1021/mz500747t.

The successful synthesis of the heterotelechelic H-bonding polymer Ba-PnBuA-HW (Mn,NMR = 7700 g/mol, Mn,SEC = 7500 g/mol, PDI = 1.25) was accomplished. Self-assembly in a head-to-tail fashion driven by multiple H-bondings in solution and in the bulk was proven by temperature-dependent 1H NMR, concentration-dependent DOSY NMR studies, and rheological measurements. Reproduced with permission. Copyright 2015©, American Chemical Society.

Healing Materials from V- and H-Shaped Supramolecular Architectures.

Chen, S., et al. Angewandte Chemie International Edition 2015, 54 (35), 10188-10192, DOI: http://dx.doi.org/10.1002/anie.201504136.

We report the rational design of novel V-shaped barbiturate (Ba) functionalized soft–hard–soft triblock copolymers with a reversible supramolecular healing motif (Ba) in the central part of the hard block, which undergoes autonomic repair at 30 °C. Self-assembling with heterocomplementary α,ω-Hamilton wedge (HW) functionalized polyisoprene (PI; HW-PI-HW), results in an H-shaped supramolecular architecture with efficient self-healing capabilities that can recover up to around 95 % of the original mechanical performance at 30 °C within 24 h. Reproduced with permission. Copyright 2015©, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of an Amphiphilic β-Turn Mimetic Polymer Conjugate.

Malke, M., et al. ACS Macro Letters 2014, 4 (3), 393-397, DOI: http://pubs.acs.org/doi/abs/10.1021/mz500108n.

A new biomimetic polymer containing a beta-turn mimetic element (1) was synthesized, using a combination of living carbocationic polymerization (LCCP), amidation, and “click” chemistry. By means of size exclusion chromatography (SEC), matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), NMR spectroscopy, and LC/MALDI-TOF MS, a detailed structural proof of the β-turn mimetic PIB conjugate (1) was possible. Reproduced with permission. Copyright 2014©, American Chemical Society.

Facile preparation of supramolecular (ABAC)n multiblock copolymers from Hamilton wedge and barbiturate-functionalized RAFT agents.

Chen, S., et al. Polymer Chemistry 2014, 5 (8), 2891-2900, DOI: http://dx.doi.org/10.1039/C3PY01482G.

Two original Hamilton wedge (HW)/barbiturate (Ba) functionalized symmetrical trithiocarbonates have been successfully synthesized and their capability to efficiently mediate the polymerization of styrene, nBuA and isoprene was investigated. Reproduced by permission of The Royal Society of Chemistry.

Monitoring ROMP Crossover Chemistry via ESI-TOF MS.

Kurzhals, S., et al. Macromolecules 2013, 46 (3), 597-607, DOI: http://dx.doi.org/10.1021/ma302555q.

We report on the ESI-TOF MS investigation of oligomerization and co-oligomerization reactions via ring-opening metathesis polymerization of noncharged monomers. Reproduced with permission. Copyright 2013©, American Chemical Society.

Comparing solution and melt-state association of hydrogen bonds in supramolecular polymers

Herbst, F., et al. Polymer Chemistry 2013, 4, 3602-3609, DOI: http://xlink.rsc.org/?doi=C3PY00362K.

Mono- and bifunctional poly(n-butyl acrylate)s (PnBAs) bearing different hydrogen bonding motifs (thymine (THY) or 2,6-diaminotriazine (DAT)) were prepared by a combination of atom transfer radical polymerization (ATRP) and azide/alkyne “click”-reaction to investigate the association of hydrogen bonding motifs in solution (toluene-d8) and in the melt state. Reproduced by permission of The Royal Society of Chemistry.

Autocatalysis in the Room Temperature Copper(I)-Catalyzed Alkyne–Azide “Click” Cycloaddition of Multivalent Poly(acrylate)s and Poly(isobutylene)s.

Döhler, D., et al. Macromolecules 2012, 45 (8), 3335-3345, DOI: http://dx.doi.org/10.1021/ma300405v.

We investigate autocatalytic effects in cross-linking processes based on the copper(I)-catalyzed alkyne-azide “click” cycloaddition reaction (CuAAC), taking advantage of the 1,3-triazole rings formed during the CuAAC-based cross-linking, which act as ligands for subsequent “click”-reactions in turn accelerating the reaction rate of subsequent CuAAC-reactions. Multivalent polymeric alkynes and azides (random poly(propargyl acrylate-co-n-butyl acrylate)s, Mn = 7000-23400 g/mol) were prepared via nitroxide mediated polymerization (NMP). The now designable significant autocatalytic effects together with the optimized reaction rate via the lowest molecular weight compounds enabled the design of a new, highly efficient and fast cross-linking system acting at room temperature. Reproduced with permission. Copyright 2012©, American Chemical Society.