研究目的
To develop a novel strategy for achieving solid materials with highly tunable reverse photochromism using commercially available spiropyran dyes without chemical derivatization, and to transfer this behavior to solid state for applications like rewritable devices.
研究成果
The research successfully developed a reaction-free, universal strategy for tunable reverse photochromism in solid materials using commercial spiropyrans. By varying solvents, different colors and switching rates were achieved without chemical modification. Encapsulation preserved these properties in solid state, enabling flexible films with multiple photochromic responses from a single dye, suitable for applications like rewritable papers.
研究不足
The study is limited to specific spiropyran dyes and solvents; other dyes or matrices may not exhibit similar tunability. Recolouration kinetics were slower in capsules compared to bulk for some dyes, possibly due to rigid subdomains in the polymer shell. The approach requires non-volatile solvents for encapsulation, which may restrict solvent choices.
1：Experimental Design and Method Selection:
The study involved dissolving spiropyran dyes in various non-volatile solvents to stabilize different merocyanine forms, encapsulating these solutions in polymer capsules, and integrating them into solid polymeric films. The approach leveraged acid-base properties and solvent interactions to tune photochromic responses.
2：Sample Selection and Data Sources:
Five commercially available spiropyrans (SP-1 to SP-5) were selected based on their differing basicities. Solvents included nonanoic acid (NA), n-dodecylphosphonic acid (DPA), dihydroxy-terminated poly(dimethylsiloxane-co-diphenylsiloxane) (PDMS-OH), and a tetradecanol-bisphenol A mixture (TD-BA).
3：List of Experimental Equipment and Materials:
Equipment included a scanning electron microscope (FEI Quanta 650 FEG), spectrophotometer (Cary 60), differential scanning calorimeter (TA Instruments Q20), and NMR spectrometers (Bruker DPX250 and DPX400). Materials included polymers (PMMA, PES, PC, PVA, PA), solvents (NA, DPA, PDMS-OH, TD, BA, HA, PA acids, HD), and spiropyran dyes (SP-1 to SP-5 from TCI chemicals).
4：0). Materials included polymers (PMMA, PES, PC, PVA, PA), solvents (NA, DPA, PDMS-OH, TD, BA, HA, PA acids, HD), and spiropyran dyes (SP-1 to SP-5 from TCI chemicals). Experimental Procedures and Operational Workflow:
4. Experimental Procedures and Operational Workflow: Solutions were prepared by dissolving dyes in solvents, characterized by absorption spectroscopy. Capsules were synthesized via solvent evaporation method: polymer dissolved in CH2Cl2, mixed with dye-solvent solution, emulsified in PVA water solution, heated to evaporate CH2Cl2, centrifuged, and freeze-dried. Films were made by dispersing capsules in polymer solutions and drop-casting.
5：Data Analysis Methods:
Absorption spectra analyzed using Kubelka-Munk equation for solids. Kinetics of thermal back-isomerization fitted to first-order kinetics. NMR and DSC used for payload and melting point determination.
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scanning electron microscope
FEI Quanta 650 FEG
FEI
Used for collecting SEM images of capsules and films to analyze morphology and structure.
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spectrophotometer
Cary 60
Agilent
Used for measuring absorption spectra of liquid and solid samples in transmittance and reflectance modes.
Cary 60 UV-Vis Spectrophotometer
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NMR spectrometer
Bruker DPX250
Bruker
Used for 1H-NMR spectroscopy to analyze capsule payload and confirm encapsulation.
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NMR spectrometer
Bruker DPX400
Bruker
Used for 1H-NMR spectroscopy to analyze capsule payload and confirm encapsulation.
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differential scanning calorimeter
TA Instruments Q20
TA Instruments
Used for DSC measurements to determine melting points of encapsulated materials.
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homogenizer
T18 Ultra-Turrax
IKA
Used for homogenizing emulsions during capsule synthesis.
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laser pointer
JD850
Used for visible light irradiation to induce color fading in photochromic materials.
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flashlight torch
UltraFire CREE XMLT6
UltraFire
Used for non-coherent visible light irradiation in experiments.
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