Monohydroxy alcohols show a structural relaxation and at longer time scales a Debye-type dielectric peak. From spin-lattice relaxation experiments using different nuclear probes an intermediate, slower-than-structural dynamics is identified for n-butanol. Based on these findings and on diffusion measurements, a model of self-restructuring, transient chains is proposed. The model is demonstrated to explain consistently the so far puzzling observations made for this class of hydrogen-bonded glass forming liquids.
We use differential scanning calorimetry, broadband dielectric spectroscopy, and deuteron nuclear magnetic resonance to investigate water dynamics in MCM-41 pores with a diameter of d = 2.5 nm. At high pore fillings, partial crystallization at T m = 221 K leads to a dynamic crossover. The reorientation of all water molecules shows non-Arrhenius temperature dependence above 221 K, while two Arrhenius processes associated with liquid and crystalline water species can be distinguished below this temperature. Thus, the confined liquid water fraction exhibits an apparent fragile-to-strong transition as a consequence of a reduction of the accessible pore volume to a narrow interfacial layer during fractional freezing. The confined crystalline water fraction shows considerable dynamics with water reorientation in the milliseconds regime near 200 K. At low pore fillings, we observe neither partial crystallization nor a dynamic crossover.
In this work, the preparation of highly thermoresponsive and fully reversible stretch-tunable elastomeric opal films featuring switchable structural colors is reported. Novel particle architectures based on poly(diethylene glycol methylether methacrylate-co-ethyl acrylate) (PDEGMEMA-co-PEA) as shell polymer are synthesized via seeded and stepwise emulsion polymerization protocols. The use of DEGMEMA as comonomer and herein established synthetic strategies leads to monodisperse soft shell particles, which can be directly processed to opal films by using the feasible melt-shear organization technique. Subsequent UV crosslinking strategies open access to mechanically stable and homogeneous elastomeric opal films. The structural colors of the opal films feature mechano- and thermoresponsiveness, which is found to be fully reversible. Optical characterization shows that the combination of both stimuli provokes a photonic bandgap shift of more than 50 nm from 560 nm in the stretched state to 611 nm in the fully swollen state. In addition, versatile colorful patterns onto the colloidal crystal structure are produced by spatial UV-induced crosslinking by using a photomask. This facile approach enables the generation of spatially cross-linked switchable opal films with fascinating optical properties. Herein described strategies for the preparation of PDEGMEMA-containing colloidal architectures, application of the melt-shear ordering technique, and patterned crosslinking of the final opal films open access to novel stimuli-responsive colloidal crystal films, which are expected to be promising materials in the field of security and sensing applications.
Redox-responsive polyvinylferrocene-grafted
silica nanoparticles have been used for modulating the catalytic activity
of surface-attached Grubbs second generation type catalysts for the
ring-opening metathesis polymerization (ROMP) of norbornene monomer.
A facile and very efficient protocol for the modification of living
polyvinylferrocene chains was developed to introduce a suitable functional
group for the intended “grafting onto” approach. Grafted
particles were characterized by using TEM, SEM/energy dispersive X-ray
spectroscopy (EDS), XPS, small-angle X-ray scattering (SAXS), dynamic
light scattering (DLS), and cyclic voltammetry, revealing both the
presence of redox-responsive polymers and the presence of Grubbs catalyst
in the particle exterior. Chemical oxidation protocols for immobilized
polymers were applied to deactivate surface-attached catalysts in
ROMP protocols, while chemical in situ reduction
immediately led to catalyst’s reactivation.
A novel and convenient route for the preparation of monodisperse ferrocene-containing core-interlayershell particles using emulsion polymerisation protocols is described. These metallopolymer-based particles can be used to produce highly ordered elastomeric opal films with fascinating distinct reflection colours.The present work additionally describes the combined addressability of both stimuli, redox-chemistry and mechanical stress. The obtained materials are interesting since application of the melt-shear process followed by crosslinking of the matrix provides access to large-area, mechano-responsive elastomeric opal films featuring an additional redox response. Both, basic synthesis aspects and first steps towards application in the field of stimuli-responsive sensing of respective materials are discussed.
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