Spiropyran Moiety Research Articles

Dynamic monitoring of SO2 changes during ferroptosis using a light-controlled lipid droplets-targeting probe

During the process of ferroptosis, the generation of toxic lipid peroxides triggers severe inflammatory responses. Despite sulfur dioxide (SO2) being recognized as an important signal molecule and antioxidant, its specific physiological mechanism in ferroptosis remains unclear. Here, we developed a novel probe, SP-TB, tailored for detecting SO2 within lipid droplets (LDs). SP-TB features a triphenylamine moiety for LD targeting, coupled with a spiropyran serving as both the SO2 reaction site and a light-responsive switch. Under normal conditions, SP-TB exhibits yellow fluorescence at 570 nm with its SO2 reaction site closed. Upon UV light activation, the spiropyran moiety undergoes isomerization to the merocyanine form (MC-TB), resulting in red fluorescence emission at 634 nm. During this photoisomerization, the exposed CC-CN+ fragment enables specific Michael addition reactions with SO2, quenching the red fluorescence of MC-TB and enhancing yellow fluorescence. The probe exhibits stable photoreversibility and excellent LDs targeting, along with remarkable SO2 selectivity with a low detection limit of 3.5 μM. Notably, the controllability of the SO2 reaction site minimizes false positives. This probe was successfully used to monitor the changes of SO2 concentrations in LDs during ferroptosis.

Photosensitive polyimide enabled simple, reversible and environmentally friendly selective metallization on diverse substrates

For breaking through the limitation of metal patterning in constructing conductive pathways of electronic devices, which is proposed to be an upgrade of traditional etching technique, a photo-reversible, transparent and soluble polyimide carrying spiropyran side chains is synthesized. The merocyanine isomers produced from the spiropyran moieties under digitalized ultraviolet irradiation bind the silver−histidine complexes in water, while the absorbed silver ions are in-situ reduced into metal silver seeds by the photo-generated radicals from histidine molecules, catalyzing copper deposition and yielding the desired copper patterns. Accordingly, the conventional time-consuming steps (like surface modification, immobilization of catalytic ions and (photo)chemical reduction) are simplified to a single one, and the environmentally unfriendly solvent and costly/toxic palladium reagent are excluded. The Cu patterns deposited on the polyimide show high resolution, electrical conductivity (1.785 × 10−6 Ω‧cm), adhesion strength (18.14 MPa) and fatigue resistance (> 2.6 million cycles of bending). Due to the absence of invasive surface treatments (e.g., surface hydrolysis and laser direct structuring), extremely low surface roughness of 7.83 nm is achieved. Besides, the developed strategy can be easily expanded to stretchable elastomer and other organic/inorganic substrates with irregular surfaces, showing promising application prospects. The solubility of the polyimide and ultraviolet/visible light triggered reversibility of the included spiropyran groups further enable repeated recycling, erasing and re-patterning.

An Orthogonal Conductance Pathway in Spiropyrans for Well-Defined Electrosteric Switching Single-Molecule Junctions.

While a multitude of studies have appeared touting the use of molecules as electronic components, the design of molecular switches is crucial for the next steps in molecular electronics. In this work, single-molecule devices incorporating spiropyrans, made using break junction techniques, are described. Linear spiropyrans with electrode-contacting groups linked by alkynyl spacers to both the indoline and chromenone moieties have previously provided very low conductance values, and removing the alkynyl spacer has resulted in a total loss of conductance. An orthogonal T-shaped approach to single-molecule junctions incorporating spiropyran moieties in which the conducting pathway lies orthogonal to the molecule backbone is described and characterized. This approach has provided singlemolecule conductance features with good correlation to molecular length. Additional higher conducting states are accessible using switching induced by UV light or protonation. Theoretical modeling demonstrates that upon (photo)chemical isomerization to the merocyanine, two cooperating phenomena increase conductance: release of steric hindrance allows the conductance pathway to become more planar (raising the mid-bandgap transmission) and a bound state introduces sharp interference near the Fermi level of the electrodes similarly responding to the change in state. This design step paves the way for future use of spiropyrans in single-molecule devices and electrosteric switches.

Construction of photo-responsive lignin as a broad-spectrum sunscreen agent

Lignin has potential to serve as promising sunscreen agents as it has good ultraviolet (UV) absorption and antioxidant properties. However, the weak absorption capacity of lignin in the long-wave UV region (UVA, 320–400 nm) limits its further development. In this work, a spiropyran-modified lignin (DLSP) with photo-responsive property was prepared by in-situ construction of spiropyran (SP) structure in the demethylated lignin (DL). Due to the presence of SP moiety, the absorption of DLSP in the UVA region was significantly improved. Under UV irradiation, its absorption peak was redshifted as unconjugated SP form isomerized to conjugated merocyanine (MC) form, and the UVA/UVB ratio increased from 0.62 to 0.74. The free-radical scavenging ability of lignin could protect SP from photodegradation, which provided DLSP excellent fatigue resistance. DLSP were blended into creams to investigate its sunscreen performance. Results indicated that DLSP exhibited radiation-enhanced sunscreen performance, the sun protection factor (SPF) of cream containing 10 wt% of DLSP improved from 20 to 67 after 8 h of UV irradiation. Moreover, DLSP showed low skin penetration and good biocompatibility. These results provide a useful guideline for the rational design of sunscreens with special functionalities.

Electrochemical investigation of a photochromic spiropyran containing a pyrrolidinofullerene moiety

Reversible transformations of a hybrid molecule based on [60]fullerene and a spiropyran moiety under conditions of combined photo- and electrochemical exposure were found. It has been established that the electrochemical oxidation of the UV-photoinduced colored form of the hybrid spiropyran in solution significantly accelerates the discoloration process and does not affect the fullerene part of the hybrid molecule. The research results are promising for designing a photo-electrochromic device that modulates electromagnetic radiation in the visible range of the spectrum.

Supramolecular assembly of dendronized spiropyrans in aqueous solutions into nanospheres with photo- and thermo-responsive chiralities.

Tailoring the amphiphilicity of a molecule through external stimuli can alter the balance between self-association and repulsion, resulting in different propensities for its assembly. Here we report on the supramolecular assembly of a series of dendronized spiropyrans (DSPs) in water. These DSPs carry 3-fold dendritic oligoethylene glycols (OEGs) with either methoxyl or ethoxyl terminals for different hydrophilicities, and contain an Ala-Gly dipeptide to provide the chirality. These dendronized amphiphiles form supramolecular nanospheres in aqueous solutions with remarkable induced chirality to a level of 1.0 × 106 deg cm2 dmol-1. They can be tuned reversibly through photoisomerization of the spiropyran moieties from the hydrophobic SP form into the hydrophilic MC form, and can even become chirally silent through thermally mediated collapse of the dendritic OEGs. Photoisomerization of the spiropyran moieties in these DSPs is accompanied by simultaneous changes of UV absorption, fluorescence emission, supramolecular chirality and aqueous solution colors. These supramolecular nanospheres exhibit characteristic thermoresponsive behavior due to thermal collapse of the dendritic OEGs with their cloud point temperatures (Tcps) being dependent on the overall hydrophilicity of the molecules and also the aggregate morphologies resulting from how dendritic OEGs are wrapped around the aggregates. Both photo-irradiation-mediated isomerization of the spiropyran moieties and thermally mediated dehydration and collapse of the dendritic OEGs influence the amphiphilicity of these DSPs and their solvation by water, leading to varied driving forces for their assembly. NMR, circular dichroism (CD) and fluorescence spectroscopy techniques, as well as DLS and AFM techniques are combined to follow the supramolecular assembly and illustrate the aggregation mechanism. All experimental results demonstrate that the reversible chirality of the aggregates originates from the balance between dendritic OEGs and spiropyran moieties against water solvation.

Spiropyran-Merocyanine Based Photochromic Fluorescent Probes: Design, Synthesis, and Applications.

Due to ever-increasing insights into their fundamental properties and photochromic behaviors, spiropyran derivatives are still a target of interest for researchers. The interswitching ability of this photochrome between the spiropyran (SP) and merocyanine (MC) isoforms under external stimuli (light, cations, anions, pH etc.) with different spectral properties as well as the protonation–deprotonation of its MC form allows researchers to use it suitably in sensing purposes by developing different colorimetric and fluorometric probes. Selective and sensitive recognition can be achieved by little modification of its SP moiety and functional groups. In this review, we emphasize the recent advancements (from 2019 to 2022) of spiropyran–merocyanine based fluorogenic and chromogenic probes for selective detection of various metal ions, anions, neutral analytes, and pH. We precisely explain their design strategies, sensing mechanisms, and biological and environmental applications. This review may accelerate the improvements in designing more advanced probes with innovative applications in the near future.

Effect of Molecular Structure of Photoswitchable Surfactant on Light-Responsive Shape Transition of Block Copolymer Particles

Photoactive shape-changing particles offer a promising platform for smart materials with tunable properties at high spatiotemporal resolutions. Herein, a series of spiropyran-based surfactants with different alkyl spacer lengths are developed to achieve photoactive, shape-changing particles through confined self-assembly of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) within an evaporative emulsion. The length of the alkyl chain spacer between the spiropyran headgroup and ionic chain-end is modulated from hexyl to ethyl decanoate to provide surfactants with tunable amphiphilicity. Under UV light, the hydrophilic ring-opened merocyanine surfactants produce onion-like microspheres with a P4VP surface. Conversely, by exposure to visible light, the ring-closure reaction of the spiropyran moieties shifts their hydrophobicity and yields striped ellipsoids with axially stacked PS and P4VP blocks. This sphere-to-ellipsoid transition is observed only for surfactants that contain spacers longer than or equal to octyl. The effects of photoswitchable surfactants on their interfacial properties and corresponding morphological evolution of the particles are investigated to elucidate the mechanism of the shape transition of the photoactive particles.

Controlled Synthesis and Photoresponsive Properties of Spiropyran End-Functionalized Poly(vinyl ether)s

Due to the need to develop smart materials for a variety of applications such as catalysts and drug delivery, the development of photoresponsive polymers is receiving increasing attention. In particular, the photoisomerization of spiropyran (SP), unlike many other photoresponsive compounds, has attracted attention because it dramatically changes not only the molecular structure but also the polarity of the molecule. However, in most cases where SP is used as a photoresponsive functional group, SP is introduced in the side chain of the polymer, and few cases have been reported in which SP is introduced at the end of the polymer chain. Therefore, we designed a new amphipathic poly(vinyl ether) with an SP moiety at the end of the polymer chain. First, an initiator having an SP moiety was synthesized and used for living cationic polymerization to synthesize a poly(vinyl ether) bearing an SP moiety at the end of the polymer chain. Furthermore, we investigated the photoresponsive properties of the obtained polymers, we found that self-assembly of the amphiphilic polymers could be controlled by photoirradiation.

Reversible Three-Color Fluorescence Switching of an Organic Molecule in the Solid State via "Pump-Trigger" Optical Manipulation.

In photoswitches that undergo fluorescence switching upon ultraviolet irradiation, photoluminescence and photoisomerization often occur simultaneously, leading to unstable fluorescence properties. Here, we successfully demonstrated reversible solid-state triple fluorescence switching through "Pump-Trigger" multiphoton manipulation. A novel fluorescence photoswitch, BOSA-SP, achieved green, yellow, and red fluorescence under excitation by pump light and isomerization induced by trigger light. The energy ranges of photoexcitation and photoisomerization did not overlap, enabling appropriate selection of the multiphoton light for "pump" and "trigger" photoswitching, respectively. Additionally, the large free volume of the spiropyran (SP) moiety in the solid state promoted reversible photoisomerization. Switching between "pump" and "trigger" light is useful for three-color tunable switching cell imaging, which can be exploited in programmable fluorescence switching. Furthermore, we exploited reversible dual-fluorescence switching in a single molecular system to successfully achieve two-color super-resolution imaging.

Reversible Three‐Color Fluorescence Switching of an Organic Molecule in the Solid State via “Pump–Trigger” Optical Manipulation

AbstractIn photoswitches that undergo fluorescence switching upon ultraviolet irradiation, photoluminescence and photoisomerization often occur simultaneously, leading to unstable fluorescence properties. Here, we successfully demonstrated reversible solid‐state triple fluorescence switching through “Pump–Trigger” multiphoton manipulation. A novel fluorescence photoswitch, BOSA‐SP, achieved green, yellow, and red fluorescence under excitation by pump light and isomerization induced by trigger light. The energy ranges of photoexcitation and photoisomerization did not overlap, enabling appropriate selection of the multiphoton light for “pump” and “trigger” photoswitching, respectively. Additionally, the large free volume of the spiropyran (SP) moiety in the solid state promoted reversible photoisomerization. Switching between “pump” and “trigger” light is useful for three‐color tunable switching cell imaging, which can be exploited in programmable fluorescence switching. Furthermore, we exploited reversible dual‐fluorescence switching in a single molecular system to successfully achieve two‐color super‐resolution imaging.

Engineering highly efficient Li+ responsive nanochannels via host–guest interaction and photochemistry regulation

Artificial nanochannels have seen great progress in energy storage, molecular filters, nanofluidic diodes, and biosensors. Precisely recognizing and transporting molecules or ions underpin the basis of artificial nanochannels. Here, we report highly efficient Li+ responsive nanochannels by design of functionalized porous anodic aluminum oxide (AAO) membranes. The 12-crown-4 unit was tethered to the synthesized spiropyran molecule, creating a smart Li+ responsive element, photochromic crowned spiropyran (CE-SP). The crown unit can specifically bind with Li+ while exempting the harassment of other metallic cations; and importantly, the spiropyran moiety possesses reversible photochemistry response, adding the flexibility to regulate ion transport behaviors. Upon the ultraviolet light stimulus, hydrophobic CE-SP molecules transform to positively charged crowned merocyanine (CE-MC), which can further convert to oxygen-negative ions in weak alkaline environment, thereby forming O--Li+ interaction. Such structural evolutions enable to deftly tune the surface charge and wettability of the nanochannels, and thus ingeniously manipulate Li+ recognition profiled by ionic current signal. Moreover, electrically-driven release of the captured Li+ can be realized in an amiable condition, showing controllable capture-to-release ability. Finite element simulation unveils the fundamental mechanisms of ion transport pertaining to Li+ recognition events in the nanoconfinement. This work thus paves a way to construct high-performance Li+-selective nanodevice, and holds promise for Li+-related electrochemistry energy research.

Paper without a Trail: Time-Dependent Encryption using Pillar[5]arene-Based Host-Guest Invisible Ink.

A stimuli-responsive invisible ink for time-dependent encryption of information is reported. Consisting of a pillar[5]arene-based supramolecular network grafted with spiropyran moieties, these materials display time-dependent photochromic behavior with tailorable fading rates. Ultraviolet (UV) light results in isomerization of the colorless spiropyran to the corresponding colored merocyanine, while visible light or heat causes the reverse isomerization with a rate that is dependent on the density of host-guest crosslinks. The kinetics of discoloration are a function of merocyanine aggregation, which becomes more pronounced as the host-guest crosslink density is increased, leading to a reduced conversion rate and slower time-dependent fading. The degree of crosslinking, and hence the fading rate, may be modulated via the addition of unbound pillar[5]arene host or nitrile guest as competitors. Time-dependent information encryption is enabled by combining selective placement of host and guest competitors and UV patterning. UV patterning provides an initially "false" image that does not reveal the desired information, and it is only after a given time that the encrypted data appears. This work provides a unique approach to enhance the security of information storage associated with offline portable data encryption.

Heterogeneous Fluorescent Organohydrogel Enables Dynamic Anti‐Counterfeiting

AbstractFluorescent patterns showing the unique color change in response to external stimuli are of considerable interest for their applications in anti‐counterfeiting. However, there is still a lack of intelligent fluorescent patterns with high‐security levels, presenting a dynamic display of encrypted information. In this study, a fluorescent organohydrogel is fabricated through a two‐step interpenetrating technique, leading to the co‐existence of naphthalimide moieties (DEAN, green‐yellow fluorescent monomer) contained Poly(N,N‐dimethylacrylamide) (PDMA) hydrogel network and Polyoctadecyl methacrylate (PSMA) organogel network bearing spiropyran moieties (SPMA, photochromic monomer). Due to the unique heterogeneous networks, the fluorescence color goes through a continuous change from green to yellow to red via the fluorescence resonance energy transfer (FRET) process with the extension of irradiation time. In addition, when H+ is introduced into the system, SP units exhibit transformation into the protonated merocyanine (MCH+) rather than merocyanine (MC) under UV light, which inhibits the FRET process. By selectively being treated with H+, the fluorescent organohydrogel can act as an effective platform for encrypting secret information, making them more difficult to forge.

Dual photochromics-contained photoswitchable multistate fluorescent polymers for advanced optical data storage, encryption, and photowritable pattern

Stimuli-responsive fluorescent materials that can alternate their emission states on-demand are always desired in many applications. In this study, novel photoswitchable multistate fluorescent polymer (PMFP) was prepared via simple free-radical copolymerization of butyl acrylate (BA) and styrene (St) with two photochromic fluorescent monomers, i.e. sulfonyl diarylethylene-linked 4-hydroxybutyl acrylate (SDTE) and spiropyran-linked methacrylate (SP8). The PMFP displays excellent processability, due to its rational feed ratio of BA and St which result in the relative low glass transition temperature. By changing irradiation light, the non-fluorescent ring-closed spiropyran units and ring-opened diarylethylene moieties in PMFP can be selectively converted into their corresponding luminescence states. Furthermore, as a result of the controllable fluorescence resonance energy transfer (FRET) from the excited diarylethylene to the spiropyran moieties, the emission of the polymer in solution or film can be reversibly switched among distinguishable no-emission, red, and green fluorescence states. Moreover, the PMFP exhibits high brightness, high contrast, rapid photoresponse, and excellent photoreversibility. We also demonstrated that PMFP can be directly used for advanced high-density data storage, multilevel information encryption, and multicolor photorewritable pattern, as well as high-level anticounterfeiting.

Bioinspired Synergistic Photochromic Luminescence and Programmable Liquid Crystal Actuators.

Bioinspired smart materials with synergistic allochroic luminescence and complex deformation are expected to play an important role in many areas of science and technology. However, it is still challenging to fabricate such soft actuators with high programmability that can be manipulated in situ with high spatial resolution. Herein, we have incorporated terminally functionalized aggregation-induced emission active tetraphenylethene derivative and photochromic spiropyran moieties into the networks of liquid crystal elastomers through covalent bonding to obtain the synergistic photochromic luminescence and programmable soft actuators. Bio-mimic functions and light-induced auxetic metamaterial-like devices were shown to be feasible based on the combination of assembly and origami-programming strategy. These bioinspired devices with synergistic photochromic luminescence and complex photodeformation abilities provide an elegant strategy to design multi-functional liquid crystal actuators.

Bioinspired Synergistic Photochromic Luminescence and Programmable Liquid Crystal Actuators

AbstractBioinspired smart materials with synergistic allochroic luminescence and complex deformation are expected to play an important role in many areas of science and technology. However, it is still challenging to fabricate such soft actuators with high programmability that can be manipulated in situ with high spatial resolution. Herein, we have incorporated terminally functionalized aggregation‐induced emission active tetraphenylethene derivative and photochromic spiropyran moieties into the networks of liquid crystal elastomers through covalent bonding to obtain the synergistic photochromic luminescence and programmable soft actuators. Bio‐mimic functions and light‐induced auxetic metamaterial‐like devices were shown to be feasible based on the combination of assembly and origami‐programming strategy. These bioinspired devices with synergistic photochromic luminescence and complex photodeformation abilities provide an elegant strategy to design multi‐functional liquid crystal actuators.

Photoswitchable surface wettability of ultrahydrophobic nanofibrous coatings composed of spiropyran-acrylic copolymers

HypothesisLight-controlling of surface characteristics in polymeric coatings has been a significant research area because of its potential application in development of smart surfaces. Wettability of light-responsive polymeric coatings based on spiropyran photochromic compound could be tuned by light irradiation. This is mainly because of spiropyran isomerization between the hydrophobic and hydrophilic states. ExperimentsLight-responsive latex nanoparticles containing spiropyran moieties were synthesized by semi-continuous emulsion copolymerization of acrylate monomers, which have different chain flexibility depending on the copolymer composition. Photochromic properties of spiropyran in stimuli-responsive latex nanoparticles displayed dependence of photochromism intensity and its kinetics to flexibility of the polymer chains in addition to the polarity of media. Photoswitchable surface wettability of the spiropyran-containing acrylic copolymer coatings was investigated, where the photo-responsive coatings were prepared by solution casting and electrospinning methods. FindingsThe photoswitchable coatings prepared by solution casting and electrospinning methods showed significant differences in their physical characteristics and especially surface wettability. The polymeric coatings displayed water droplet contact angles in the range of 60-93°, which could reversibly be switched to 55-86° upon UV light (365 nm) illumination as a result of isomerization of the hydrophobic spiro form to the zwitterionic merocyanine form. The nanofibrous coatings prepared by electrospinning method displayed higher contact angles in the range of 120-136°, which was switched to 78-105° upon UV light irradiation. The developed photo-responsive coatings displayed highly-efficient photoswitching between the two hydrophobic and hydrophilic states as a response to UV and visible light irradiation. The photoswitchable nanofibrous coatings displayed ultrahydrophobic characteristics, where the colored water droplets were stable on their surface and could easily be adsorbed by a cellulosic tissue. In summary, the photoswitchable nanofibrous coatings could be applied for design and development of ultrahydrophobic materials with the ability of photo-controlling of surface wettability by light irradiation with tunable intensity.

Fabrication of super-high transparent cellulose films with multifunctional performances via postmodification strategy

A transparent versatile cellulose platform film was prepared from Eucalyptus pulp in this work. Based on such cellulose platform, multifunctional cellulose films with ultraviolet-shielding, photochromism, and strong mechanical strength were fabricated via nucleophilic postmodification strategy by introducing a versatile spiropyran moiety into cellulose molecules. The fabricated cellulose films exhibited super-high transmittance up to 96% and performed notable ultraviolet-shielding capacity at 200–400 nm. Moreover, the photochromic performance of cellulose films with color changes could be clearly observed by the naked eyes, and the fluorescent blue could be excited. Besides, the tensile stress of multi-functional cellulose film was about 80 MPa, which was almost 8 times stronger than that of the commercial polyethylene film at the same thickness. It is noteworthy that these superior performances promote such a cellulose platform to be a versatile precursor for fabricating various multi-functional cellulose used in the fields of out-door coating, transparent packaging, optical screen,etc.

Re-usable colorimetric polymeric gel for visual and facile detection of multiple metal ions

For fast and visual detection of multiple metal ions, herein, a re-usable colorimetric polymeric gel with spiropyran moiety was fabricated. Under ultraviolet light, the spiropyran (SP) moiety could isomerize into the colored merocyanine (MC) isomer and chelate with divalent metal ion (M2+) and form MC-M2+ complexes. Chelated with different metal ions (Ca2+, Co2+, Zn2+, and Cu2+ions), the UV–Vis spectra of the gels could display the specific colorimetric response. When the metal-ions chelated gel was irradiated with Vis light, ions dissociated from MC and released from gel due to the MC moiety isomerized to the SP form. Furthermore, after 7 cycles of alternative UV–Vis irradiations, the gel showed excellent reversible chelation/dissociation of metal ion. The competitive tendency of metal ions to chelate with gel was as following: Cu2+ > Co2+ ≈ Zn2+ > Ca2+, which was in accordance with the density functional theory modeling. Using ionoprinting technology, the gel could achieve repeatability simultaneous detection of multiple metal ions. The light-triggered metal ion chelation/dissociation capability of the gel could be harnessed to construct reusable onsite platform for visual, fast, easy detection of multiple metal ions.