Stimuli‐Driven Assembly of Chromogenic Dye Molecules: a Versatile Approach for the Design of Responsive Polymers

Makowski, Brian T.; Kunzelman, Jill; Weder, Christoph

doi:10.1002/9783527633739.ch5

Cited by 10 publications

(8 citation statements)

References 83 publications

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“…In the solid state, the formation of BBS aggregates is likely favored by the planar molecule conformation, where aggregated structures present sandwich-type conformations with interplanar distances of a few Angstroms (Pucci et al, 2007). Fluorescence emission of dye aggregates occurs at a lower energy with respect to the emission of the single molecule (Makowski et al, 2011). This lower energy level corresponds to a larger wavelength in the emitted light and a shift of the coloration in the visible spectrum from blue (monomer) to green (excimer), see Figure 1(b).…”

Section: Fabrication Of Mechanochromic Materialsmentioning

confidence: 99%

“…Fluorescence emission of TPU-BBS blends is controlled by the spatial configuration of the dye molecules in the polymer. During the deformation process, the state of aggregation, spatial distribution, and orientation of BBS molecules evolve due to the interaction of the dye molecular structures with the background polymer (Ciardelli et al, 2013;Makowski et al, 2011). In the TPU-BBS composite, the BBS molecules interact with the host polymer network through π − π interactions with the aromatic rings and hydrogenbonding interactions with the polar carbamate groups in the polymer network (Bao et al, 2013).…”

Section: Constitutive Modelmentioning

confidence: 99%

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Large deformations and fluorescence response of mechanochromic polyurethane sensors

Cellini

Zhou

Peterson

et al. 2016

Mechanics of Materials

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A mechanochromic composite comprises an excimer-forming fluorescent dye dispersed in a compatible polymeric host. Upon large deformation of the polymeric structure, a shift of the fluorescence emission from the excimer band to the monomer band is observed, due to reorganization of dye aggregates. Mechanochromic elastomers can be tailored to produce a reversible optical response during cyclic deformation. Here, we study the optomechanical properties of mechanochromic elastomers undergoing large uniaxial and biaxial deformations. Through detailed experiments and constitutive modeling, we relate the optical response of the mechanochromic elastomer to the deformation of the polymer network. We confirm that optical response is largely reversible and is modulated by the initial dye concentration in the polymer. We adapt the classical Arruda-Boyce model to elucidate microstructural modifications of the polymer-dye blend. We propose a constitutive hypothesis for the optical behavior of the material, which relates variations of the emission spectrum to surface stretching. This knowledge can aid in the design of strain and stress sensors for applications in mechanics, biomechanics, and life sciences.

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Section: Fabrication Of Mechanochromic Materialsmentioning

confidence: 99%

Section: Constitutive Modelmentioning

confidence: 99%

Large deformations and fluorescence response of mechanochromic polyurethane sensors

Cellini

Zhou

Peterson

et al. 2016

Mechanics of Materials

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“…light, heat, mechanical stress and chemical stimuli) through a macroscopic optical output. [4,7,8] The energy of the stimulus is properly transduced into optical variations (i.e., absorption, emission, refractive index) as a function of external interference.…”

Section: Introductionmentioning

confidence: 99%

Julolidine fluorescent molecular rotors as vapour sensing probes in polystyrene films

et al. 2015

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We introduce a new sensing polymer system for detection of volatile organic compounds (VOCs) based\ud on the optical response of polystyrene (PS) films doped with julolidine fluorescent molecular rotors\ud (FMRs). The julolidine FMRs exhibited viscosity-dependent changes in the fluorescence intensity, that\ud was enhanced when glycerol was added to ethanol solutions and when they were dispersed in PS films.\ud Thus, reduction in medium mobility slowed down internal motions and allowed for a major radiative\ud decay pathway. The FMR/PS films were exposed to several VOCs, and showed a significant decrease in\ud fluorescence emission when exposed to chloroform, whereas a negligible variation in their emission\ud occurred when methanol was utilized. This vapour sensing behaviour was much more evident when a\ud perfluorodecyl chain was linked to the julolidine core being the molecule segregated at the film surface.\ud This responsive behaviour was affected by solvent composition and its reproducible response was easily\ud determined by luminescence experiments

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“…light, heat, mechanical stress and chemical stimuli) through a macroscopic optical output. [5,7,8] The energy of the stimulus is properly transduced into optical variations (i.e., absorption, emission, refractive index) as a function of external interference. This mechanism allows the preparation of "smart" devices for many different applications, such as anti-counterfeiting systems, attoreactor sensors and informational displays.…”

Section: Introductionmentioning

confidence: 99%

Zn(II)-bisthienylethynylbipyridine complex: Preparation, characterization and vapochromic behaviour in polymer films

et al. 2014

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In the present work, we report the vapochromic behaviour of PMMA films doped with small amounts of 1a:Zn fluorophore, a Zn 2+ adduct of the bisthienylethynylbipyridine ligand. 1a:Zn exhibited polarity-dependent changes in the fluorescence spectral properties when dissolved in solvents with different polarity index, indicating that its fluorescence states are of intramolecular charge transfer character. When 1a:Zn was dispersed in the PMMA matrix, its emission resulted barely influenced by the polymer environment. By contrast, 1a:Zn/PMMA films showed a significant variation of its emission with a 40 nm red-shift when exposed to a saturated atmosphere of dichloromethane. This vapochromic behaviour was much less evident when progressive amounts of methanol were added to dichloromethane due to both lower vapour pressure and limited interaction of the former with PMMA. The experiments revealed also that the rate constants associated with the vapochromic behaviour were affected by solvent composition and easily determined by luminescent experiments.

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Stimuli‐Driven Assembly of Chromogenic Dye Molecules: a Versatile Approach for the Design of Responsive Polymers

Cited by 10 publications

References 83 publications

Large deformations and fluorescence response of mechanochromic polyurethane sensors

Large deformations and fluorescence response of mechanochromic polyurethane sensors

Julolidine fluorescent molecular rotors as vapour sensing probes in polystyrene films

Zn(II)-bisthienylethynylbipyridine complex: Preparation, characterization and vapochromic behaviour in polymer films

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