Rewritable Optical Patterns in Light-Responsive Ultrahigh Molecular Weight Polyethylene.
ABSTRACT: Spiropyran is used as a photochromic dye to create colored patterns in highly drawn ultrahigh molecular weight polyethylene (UHMW PE) films. The dye is incorporated in highly crystalline, drawn UHMW PE tapes and fibers and isomerizes to its merocyanine state upon UV light irradiation, resulting in a color change from transparent to purple. The isomerization from merocyanine to spiropyran to erase the color can be simply induced by using heat or a green LED light. The combination of the use of a mask and the reversibility of the isomerization results in colored patterns that can be written, erased, and rewritten using UV light and heat or green LED light.
Project description:Spiropyran dyes were attached to fluorescent core-shell CdSe/ZnS nanocrystals via thiol-containing linkers. Photoisomerization of the dye to its merocyanine form by UV irradiation caused a dramatic loss in the intrinsic nanoparticle fluorescence, which was regained upon reversing the isomerization with visible light. The fluorescence quenching efficiency increased with increasing spectral overlap of fluorescence emission and merocyanine adsorption bands, consistent with FRET as the quenching mechanism. Typically, complete quenching required at least 80 bound dye molecules per particle.
Project description:We show that FRET between Pacific Blue (PB) and Alexa488 (A488) covalently attached to a DNA scaffold can be reversibly controlled by photochromic switching of a spiropyran derivative. With the spiropyran in the closed spiro isomeric form, FRET occurs freely between PB and A488. UV-induced isomerization to the open merocyanine form shuts down the FRET process by efficient quenching of the PB excited state. The process is reversed by exposure to visible light, triggering the isomerization to the spiro isomer.
Project description:Spiropyrans undergo Cspiro-O bond breaking to their ring-open protonated E-merocyanine form upon protonation and irradiation via an intermediate protonated Z-merocyanine isomer. We show that the extent of acid-induced ring opening is controlled by matching both the concentration and strength of the acid used and with strong acids full ring opening to the Z-merocyanine isomer occurs spontaneously allowing its characterization by 1H NMR spectroscopy as well as UV/vis spectroscopy, and reversible switching between Z/ E-isomerization by irradiation with UV and visible light. Under sufficiently acidic conditions, both E- and Z-isomers are thermally stable. Judicious choice of acid such that its p Ka lies between that of the E- and Z-merocyanine forms enables thermally stable switching between spiropyran and E-merocyanine forms and hence pH gating between thermally irreversible and reversible photochromic switching.
Project description:The spiropyran family of photochromes are key components in molecular-based responsive materials and devices, e.g., as multiphotochromes, covalently coupled dyads, triads, etc. This attention is in no small part due to the change in properties that accompany the switch between spiropyran and merocyanine forms. Although the spiropyran is a single structural isomer, the merocyanine form represents a family of isomers (TTT, TTC, CCT, etc.) and protonation states. Combining two spiropyrans into one compound increases the number of possible structures dramatically and the interaction between the units determines, which are impeded due to intramolecular quenching of excited states. Here, we show that the coupling of two spiropyran photochromes through their phenol units yields favorable interactions (crosstalk) between the components that provides access to species inaccessible with the component monospiropyran alone. Specifically, the ring opening of one spiropyran unit, which is thermally stable at -30 °C, prevents ring opening of the second spiropyran unit. Furthermore, whereas protonated E- and Z-monomerocyanines were previously shown to undergo thermal- and photo-equilibration, the corresponding protonated E- and Z- bimerocyanines are thermally stable and show one-way photoisomerization from the Z,Z- to an emissive E,E-bimerocyanine form. Subsequent deprotonation at room temperature resets the system to the bispiro ring-closed form, but deprotonation at -30 °C yields the otherwise inaccessible bimerocyanine form. This form is photochemically inert but undergoes a two-step thermal relaxation via the merocyanine-spiropyran form, showing that the connection at the phenol units provides sufficient intramolecular interaction to fine-tune the complex isomerization pathways of spiropyrans and demonstrating noncommutability in photo- and pH-regulated multistep isomerization pathways.
Project description:Tunable and durable photochromic materials are a rapidly expanding area of interest, with applications ranging from biomedical devices to industrial-fields. Here we examine electrospun poly (methacrylic acid) PMAA nanofibers covalently modified with the highly photochromic molecule, spiropyran (SP) or a derivate SP which is firstly coupled to a cyclodextrin molecule (?CDSP). The photochromic properties of the starting materials and of the nanofibers were investigated. ?CDSP, PMAASP and PMAA-?CDSP polymers exhibited a reverse photochromism. The kinetic results revealed a faster isomerization process for the ?CDSP molecule, than that for the PMAA-?CDSP and for the PMAASP, the slowest one. The fastest isomerization is attributed to the presence of a large number of hydroxyl groups of the ?CD which stabilizes the merocyanine form via hydrogen bonding, and the slowest isomerization is related to the PMAA chain structure that stabilizes the spiropyran form. Thus, combining the PMAA and ?CD properties the photo-isomerization can be modulated. The photoreversibility of this material was verified by UV-visible measurements cycling visible and UV light. Infrared spectroscopy and water contact angle were used for the nanofiber surface characterization, demonstrating the presence of the spiropyran on the mats surface and also showing a minimal effect on nanofiber size and shape when compared to PMAA fiber.
Project description:Micro-capillaries, capable of light-regulated binding and qualitative detection of divalent metal ions in continuous flow, have been realised through functionalisation with spiropyran photochromic brush-type coatings. Upon irradiation with UV light, the coating switches from the passive non-binding spiropyran form to the active merocyanine form, which binds different divalent metal ions (Zn<sup>2+</sup>, Co<sup>2+</sup>, Cu<sup>2+</sup>, Ni<sup>2+</sup>, Cd<sup>2+</sup>), as they pass through the micro-capillary. Furthermore, the merocyanine visible absorbance spectrum changes upon metal ion binding, enabling the ion uptake to be detected optically. Irradiation with white light causes reversion of the merocyanine to the passive spiropyran form, with simultaneous release of the bound metal ion from the micro-capillary coating.
Project description:Enhanced force transmission to mechanophores is demonstrated in polymer nanocomposite materials. Spiropyran (SP) mechanophores that change color and fluorescence under mechanical stimuli are functionalized at the interface between SiO2 nanoparticles and polymers. Successful mechanical activation of SP at the interface is confirmed in both solution and solid states. Compared with SP-linked in bulk polymers, interfacial activation induces greater conversion of SP to its colored merocyanine form and also significantly decreases the activation threshold under tension. Experimental observations are supported by finite element simulation of the interfacial stress state. The interfacial force-focusing strategy opens a new way to control the reactivity of mechanophores and also potentially indicates interfacial damage in composite materials.
Project description:A redox- and light-sensitive, T(1)-weighted magnetic resonance imaging (MRI) contrast agent which tethers a spiropyran(SP)/merocyanine(MC) motif to a Gd-DO3A moiety was synthesized and characterized. When in the dark, the probe is in its MC form which has an r(1) relaxivity of 2.51 mM(-1)s(-1) (60MHz, 37°C). After irradiation with visible light or mixing with NADH, the probe experiences an isomerization and the r(1) relaxivity decreased 18% and 26%, respectively. Additionally, the signal intensity in MRI showed an observable decrease after the compound was mixed with NADH.
Project description:In this report, antibacterial peptides 1-3 were prepared with a spiropyran fluorescence probe. The probe exhibits a change in fluorescence when isomerized from a colorless spiro-form (spiropyran, Sp) to a colored open-form (merocyanine, Mc) under different chemical environments, which can be used to study the mechanism of antimicrobial activity. Peptides 1-3 exhibit a marked decrease in antimicrobial activity with increasing alkyl chain length. This is likely due to the Sp-Mc isomers in different polar environments forming different aggregate sizes in TBS, as demonstrated by time-dependent dynamic light scattering (DLS). Moreover, peptides 1-3 exhibited low cytotoxicity and hemolytic activity. These probe-modified peptides may provide a novel approach to study the effect of structural changes on antibacterial activity, thus facilitating the design of new antimicrobial agents to combat bacterial infection.
Project description:By modifying the surface of nanoporous alumina membranes using mixtures of a photochromic spiropyran and hydrophobic molecules, it is possible to control the admission of water into the membrane using light. When the spiropyran is in the thermally stable, relatively hydrophobic closed form, the membrane is not wet by an aqueous solution. Upon exposure to UV light, the spiropyran photoisomerizes to the more polar merocyanine form, allowing water to enter the pores and cross the membrane. Thus, the photosensitive membrane acts as a burst valve, allowing the transport of water and ions across the membrane. If the aqueous solution contains ions, then the membrane acts as an electrical switch; photoisomerization leads to a two-order-of-magnitude increase in ionic conductance, allowing a current to flow across the membrane. Exposure to visible light causes photoisomerization of the merocyanine back to the closed, spiro form, but dewetting of the membrane does not occur spontaneously, due to a high activation barrier.