Tetra-Sensitive Graft Copolymer Gels as Active Material of Chemomechanical Valves

Stimuli-responsive hydrogels combine sensor and actuator properties by converting an environmental stimulus into mechanical work. Those materials are highly interesting for applications as a chemomechanical valve in microsystem technologies. However, studies about key characteristics of hydrogels for this application are comparatively rare, and further research is needed to emphasize their real potential. The first part of this study depicts the synthesis of grafted hydrogels based on a poly­(<i>N</i>-isopropylacrylamide) backbone and pH-sensitive poly­(acrylic acid) graft chains. The chosen approach of grafted hydrogels provides the preparation of multiresponsive hydrogels, which retain temperature sensitivity besides being pH-responsive. A pronounced salt and solvent response is additionally achieved. Key characteristics for an application as a chemomechanical valve of the graft hydrogels are revealed: (1) independently addressable response to all stimuli, (2) significant volume change, (3) sharp transition, (4) reversible swelling–shrinking behavior, and (5) accelerated response time. To prove the concept of multiresponsive hydrogels for flow control, a <i>net</i>-poly­(<i>N</i>-acrylamide)-<i>g</i>-poly­(acrylic acid) hydrogel containing 0.6 mol % poly­(acrylic acid)-vinyl is employed as active material for chemomechanical valves. Remarkably, the chemomechanical valve can be opened and closed in a fluidic platform with four different stimuli

Fullerene-Functionalized Donor–Acceptor Block Copolymers through Etherification as Stabilizers for Bulk Heterojunction Solar Cells

A new synthetic method for the covalent linking of fullerenes to polymers is introduced. The Bingel-reaction was used to prepare bromine-functionalized fullerene building blocks that could be covalently linked to hydroxyl groups of model copolymers by the cesium carbonate promoted Williamson ether synthesis. Subsequently, block copolymers with a second block based on styrene and hydroxystyrene or hydroxyethyl methacrylate could be synthesized with a poly­(3-hexylthiophene)–TEMPO macroinitiator through NMRP. Fullerene derivatives were linked to these polymers in a controlled manner and donor–acceptor block copolymers with high fullerene contents of near 50 wt % were achieved

Synthesis of High-Crystallinity DPP Polymers with Balanced Electron and Hole Mobility

We review the Stille coupling synthesis of P­(DPP2OD-T) (Poly­[[2,5-di­(2-octyldodecyl)­pyrrolo­[3,4-<i>c</i>]­pyrrole-1,4­(2<i>H</i>,5<i>H</i>)-dione-3,6-diyl]-<i>alt</i>-[2,2′:5′,2″-terthiophene-5,5″-diyl]]) and show that high-quality, high molecular weight polymer chains are already obtained after as little as 15 min of reaction time. The results of UV–vis spectroscopy, grazing incidence wide-angle X-ray scattering (GIWAXS), and atomic force microscopy show that longer reaction times are unnecessary and do not produce any improvement in film quality. We achieve the best charge transport properties with polymer batches obtained from short reaction times and demonstrate that the catalyst washing step is responsible for the introduction of charge-trapping sites for both holes and electrons. These trap sites decrease the charge injection efficiency, strongly reducing the measured currents. The careful tuning of the synthesis allows us to reduce the reaction time by more than 100 times, achieving a more environmentally friendly, less costly process that leads to high and balanced hole and electron transport, the latter being the best reported for an isotropic, spin-coated DPP polymer

Molecular Doping of a High Mobility Diketopyrrolopyrrole–Dithienylthieno[3,2‑<i>b</i>]thiophene Donor–Acceptor Copolymer with F6TCNNQ

Herein we present a molecular doping of a high mobility diketopyrrolopyrrole–dithienylthieno­[3,2-<i>b</i>]­thiophene donor–acceptor copolymer poly­[3,6-(dithiophene-2-yl)-2,5-di­(6-dodecyl­octadecyl)­pyrrolo­[3,4-<i>c</i>]­pyrrole-1,4-dione-<i>alt</i>-thieno­[3,2-<i>b</i>]­thiophene], PDPP­(6-DO)₂TT, with the electron-deficient compound hexafluoro­tetracyano­naphthoquino­dimethane (F6TCNNQ). Despite a slightly negative HOMO_donor–LUMO_acceptor offset of −0.12 eV which may suggest a reduced driving force for the charge transfer (CT), a partial charge CT was experimentally observed in PDPP­(6-DO)₂TT:F6TCNNQ by absorption, vibrational, and electron paramagnetic resonance spectroscopies and predicted by density functional theory calculations. Despite the modest CT, PDPP­(6-DO)₂TT:F6TCNNQ films possess unexpectedly high conductivities up to 2 S/cm (comparable with the conductivities of the benchmark doped polymer system P3HT:F4TCNQ having a large positive offset). The observation of the high conductivity in doped PDPP­(6-DO)₂TT films can be explained by a high hole mobility in PDPP­(6-DO)₂TT blends which compensates a lowered (relatively to P3HT:F4TCNQ) concentration of free charge carriers. We also show that F6TCNNQ-doped P3HT, the system which has not been reported so far to the best of our knowledge, exhibits a conductivity up to 7 S/cm, which exceeds the conductivity of the benchmark P3HT:F4TCNQ system