Photochromic Spiropyran Research Articles

Hydrogen Bond-Associated Photofluorochromism for Time-Resolved Information Encryption and Anti-counterfeiting.

Time-resolved photofluorochromism constitutes a powerful approach to enhance information encryption security but remains challenging. Herein, we report a strategy of using hydrogen bonds to regulate the time for initiating photofluorochromism. In our strategy, copolymers containing negative photochromic spiropyran (NSP), naphthalimide, and multiple hydrogen-bonding (UPy) units are designed, which display photo-switchable fluorescence resonance energy transfer (FRET) process from naphthalimide donor to the NSP acceptor. Interestingly, the FRET is locked via the dynamic hydrogen-bonding interaction between ring-opened NSP and UPy moieties, resulting in time-dependent fluorescence. The change in fluorescence can be finely regulated via UPy fraction in the polymers. Besides the novel time-dependent fluorescence, the polymers also take advantage of visible-light triggerable, excellent photostability, photoreversibility, and processability. We demonstrate that these properties enable them many application opportunities such as fluorescent security labels and multilevel information encryption patterns.

Photochromic Spiropyran-Based Dual-Emitting Luminescent Hybrid Films for Dynamic Information Anticounterfeiting.

Photoluminescent materials are widely used for information storage and anticounterfeiting, while most of them have the disadvantages of static information performance and weak processability, which is still a challenging task in developing dynamic anticounterfeiting materials with high security levels. Herein, we fabricated a novel photostimuli-responsive dual-emitting luminescent material UPTES-SPn-Tb-hfa, which was obtained by introducing the photochromic molecule spiropyran (SP) and lanthanide complex (Tb-hfa) into a siloxane-polyether matrix using the sol-gel process. Due to the conformation-dependent photochromic fluorescence resonance energy transfer between the Tb-hfa donor and SP acceptor, the ring-closing (SP)/ring-opening (MC) isomerization of the SP unit leads to a reversible luminescence switching in UPTES-SPn-Tb-hfa. This composite material has great potential for advanced anticounterfeiting because of the advantage of rapidly repeatable encryption/decryption for at least 8 times and dynamic luminescent colors within 15 s. In addition, due to its two luminescent centers (Tb3+ and MC), the luminescent color of this material can be regulated by 254 and 365 nm UV-light irradiation, which facilitates the design of multicolored anticounterfeiting labels. Our work presents a novel design methodology to fabricate dynamic anticounterfeiting materials, significantly enhancing the security of anticounterfeiting applications.

Grafting photochromic spiropyran polymer brushes on natural rubber surface via surface-initiated ring-opening metathesis polymerization

The modification of stereoregulated functionalized polymers on the surface of natural rubber (NR) is a challenging task. This work provided a practicable grafting method to design photochromic polymer brushes on the NR surfaces using surface-initiated ring-opening metathesis polymerization (SI-ROMP). The designed photochromic polymer brushes were based on norbornenes with spiropyrin (SP) pendents, and grew from the surface of NR films in the presence of Grubbs 2nd catalyst. The results showed that the grafting rate of polymer brushes with photoisomerization structure reached up to 44.91 %. The modified natural rubber (NR-SP) films exhibited rapid coloring/decolorization property under UV irradiation and visible light. This photochromic property initiated by the light-induced isomerisation of the spiropyran structure and the increased surface energy under light stimuli. NR-SP films exhibited stable photochromic characteristics and outstanding anti-fatigue properties after exposing to over six cycles of consecutive UV/Vis irradiation. A simple and practical strategy for the preparation of highly sensitive photochromic natural rubber materials is proposed and provides a potential application in the fields of information storage and anti-counterfeiting.

Coordination and light modulated dynamic optical switches of terpyridine-derived spiropyran for time-resolved information encryption

The development of the light-controlled assembly of smart materials for advanced information encryption with time-dependent optical characteristics is essential to meet the increasing demand on fabricating multiple optical materials for encryption security. In this work, the integration of terpyridine-derived photochromic spiropyran (Tpy-SP) as Zn2+ ion chelating agent and photo-regulator building blocks endows the materials with dynamic assembly-induced optical functionality. Under UV light irradiation, the Tpy-Zn2+-SP will be transformed into Tpy-Zn2+-MC, which forms coordinated architecture with distinct optical properties from that of Tpy-MC form. Modulated by the coordination, Tpy-Zn2+-MC and Tpy-MC show obviously different fading rate with the achievement of time-resolved multicolor optical switches. The temporal multioptical features promote the light-controlled switches as a promising candidate for time-dependent confidential materials, including dynamic optical patterns and multilevel encryption, and the relative encrypted data that could only be identified at a specified time.

Light- and Solvent-Responsive Bilayer Hydrogel Actuators with Reversible Bending Behaviors.

Light-responsive hydrogel systems have gained significant attention due to their unique ability to undergo controlled and reversible swelling behavior in response to light stimuli. Combining light-responsive hydrogels with nonresponsive polymers offers a unique self-folding feature that can be used in soft robotic actuator designs. However, simple formulation of such systems with rapid response time is still a challenging task. Herein, we demonstrate a simple but versatile bilayer polymeric design combining light-responsive spiropyran-polyacrylamide (SP-PAAm) with polyacrylamide (PAAm) hydrogels. The photochromic spiropyran in our polymer design is a closed-ring, hydrophobic compound and turns into an open-ring, hydrophilic merocyanine isomer under light irradiation. The swelling degree of SP-PAAm and PAAm hydrogels was evaluated using LED lights with different wavelengths and solvent media (e.g., water, ethanol, DMF, and DMSO). We observed that SP-PAAm hydrogels reached a swelling ratio of ∼370% with the illumination of the blue LED in the DMF medium. By combining light-responsive SP-PAAm hydrogels with nonresponsive PAAm, a proof-of-concept demonstration was performed to demonstrate the applicability of our fabricated platforms. Although fabricated one-armed bilayer hydrogels possessed self-folding ability with a folding angle of ∼40° in 30 min, the four-armed bilayer platforms demonstrated more efficient and rapid folding behavior and reached a folding angle of ∼75° in ∼15 min. Given their simplicity and efficiency, we believe that such polymeric designs may offer new avenues for the fields of polymeric actuators and soft robotic systems.

Dynamic Fluorescence Materials Based on Naphthalimide-Functionalized Silica Aerogels and Applications in Advanced Information Encryption.

With the progress of forgery and decryption, the traditional encryption technology is apparent not enough, which strongly requires the development of advanced multidimensional encryption strategies and technologies. Photo-stimuli responsive fluorescent materials are promising as candidate materials for advanced information encryption. Here, we have reported new photo-stimuli responsive materials by encapsulating photochromic molecules spiropyrans (SPs) into naphthalimide-functionalized silica aerogels. By introducing different modification groups (dimethylamino) into 1,8-naphthalimide, we obtained two kinds of silica aerogels that emit blue and green colors. The naphthalimide-functionalized silica aerogels/dye composite exhibits a blue (dimethylamino-modified naphthalimide-functionalized silica aerogel showing green) emission from naphthalimide of silica aerogels at 450 nm (520 nm) and a red emission around 650 nm of SP. Under exposure to ultraviolet light, SP gradually transformed into the merocyanine (MC) form, and a strong absorption band appeared near 540 nm. At that time, the fluorescence resonance energy-transfer (FRET) process occurred between naphthalimide and the MC isomer. As the irradiation time is extended, the fluorescence color changes continuously from blue (green) to red through the FRET process. Using the time dependence of fluorescence, dynamic encryption patterns and multiple codes were successfully developed based on these functionalized silica aerogels. This work has provided important guidance for designing advanced information encryption materials.

Programmable Encryption Based on Photochromism of Spiropyrans and Donor–Acceptor Stenhouse Adducts

AbstractImproving information security is a persistent challenge for conventional secrecy approaches such as single and double encryption. In this work, programmable encryption is reported, involving multiple stimuli to independently control different encrypted information, to boost data security. The linear‐cyclic isomerization of donor–acceptor Stenhouse adducts (DASAs) and spirocyclic‐merocyanine (SC‐MC) isomerization of spiropyrans (SPs) on paper substrate surface are optimized by integration of ester‐contained functional molecules, making them be controlled by light irradiation and heat. By controlling the sequence of three inputs (UV light, visible light, heat), the hybrid encrypted message combining DASAs and SPs exhibits distinct outputs. The encrypted message can be recorded in various forms including characters, text, and figures. Because of the multiplied number of outputs, this method offers a straightforward and powerful solution for safeguarding data in different contexts, which enhances clarity and effectiveness, ensuring resistance to tampering and counterfeiting of the encrypted information.

New Triphenylphosphonium Salts of Spiropyrans: Synthesis and Photochromic Properties.

The most important area of modern pharmacology is the targeted delivery of drugs, and one of the most promising classes of chemical compounds for creating drugs of this kind are the photochromic spiropyrans, capable of light-controlled biological activity. This work is devoted to the synthesis and study of the photochromic properties of new triphenylphosphonium salts of spiropyrans. It was found that all the synthesized cationic spiropyrans have high photosensitivity, increased resistance to photodegradation and the ability for photoluminescence.

Research Progress on Photochromic Spiropyrans in the Solid State

Research Progress on Photochromic Spiropyrans in the Solid State

Coordination vs. oxidative rearrangement of photochromic spiropyrans upon reacting with FeIIICl3 and FeIIIBr3

Photochromic spiropyrans form complexes with FeIIICl3 or FeIIIBr3. They have intense absorption in the visible range. Planar TMNOY+ cations (shown on the right) were also obtained by the oxidation and deprotonation of spiropyran with FeIIIBr3.

A visible-light regulated luminescent switch based on a spiropyran-derived Pt(II) complex for advanced anti-counterfeiting materials.

A dual optical switch regulated by visible light has been developed through an integrated strategy, including luminescent Pt(II) and photochromic spiropyran (SP) as a triplet-sensitizer and photo-regulator building block, respectively. An efficient Förster resonance energy transfer (FRET) process is achieved, along with apparent and emissive color changes under visible light irradiation and temperature stimuli, which was utilized to develop advanced anti-counterfeiting materials.

Grafting photochromic spiropyran polymer brushes on graphene oxide surfaces via surface-initiated ring-opening metathesis polymerization.

A practical "grafting-from" strategy is described to grow photochromic polymer brushes bearing spiropyran (SP) functional groups on graphene oxide (GO) surfaces via surface-initiated ring-opening metathesis polymerization (SI-ROMP). The Grubbs II catalyst was fixed on the GO surface, and the norbornene derivatives functionalized using spiropyran were synthesized from this active site via the ROMP method. The results indicated that the spiropyran-modified polymer brushes were obtained on the GO surface in the form of thin films. The solubility of GO modified by spiropyran polymers (GO-SPs) in organic solvents was significantly improved. The GO-SPs exhibited excellent photochromic properties, including fast coloration/decoloration. The modified GO with an isomeric structure was colored in 90 s under ultraviolet irradiation and decolored in 360 s under white light. The fading kinetic rate in the dark was slow and the kinetic attenuation curve followed bi-exponential decay. The GO-SP composite materials took more than 2 h to return to thermodynamically stable forms. The reversible change in the water contact angle reached 8° after continuous cycling with ultraviolet and visible light. GO-SP maintained its photochromic performance and possessed excellent fatigue resistance after more than six successive UV/light cycles. This work describes a practical strategy for the preparation of photochromic polymer brush modified GO composite materials and extends the applications of GO in photochromic materials.

Slow magnetic relaxation in a complex of photochromic spiropyran in a merocyanine form and cobalt(II) hexafluoroacetylacetonate.

The interaction between photochromic 8-methoxy-1',3',3'-trimethyl-6-nitro-spiro[chromene-2,2'-indole] (MNSP) and cobalt(II) hexafluoroacetylacetonate yields a deep red-violet solution due to the coordination-induced transition of MNSP from a colorless closed state to a colored open merocyanine (MC) form. The resulting complex {CoII(hfac)2·MNSP} (1) is obtained as crystals, and its structure at 250 K shows the coordination of two oxygen atoms from MNSP with CoII, forming a distorted octahedral surrounding around CoII. The unit cell of 1 contracts below 170 K by 5.5%, which is accompanied by shortening O-Co bonds and altering O-Co-O angles in the structure solved at 150 K. The χMT value of 3.06 emu K mol-1 at 300 K indicates the formation of high-spin CoII (S = 3/2) with a large orbital contribution characteristic of the octahedral surrounding. The contraction of the unit cell of 1 below 170 K provides a reversible 2.2% change of χMT in the 170-160 K range during heating and cooling regimes without hysteresis. The electron paramagnetic resonance signal of 1 was simulated with g-values of gx = 2.342, gy = 2.364, and gz = 2.084, and an isotropic g-factor of 2.267. The temperature-dependent χMT and field-dependent magnetization of 1 allow us to determine a positive zero-field splitting parameter of +20.1 cm-1. A study of the dynamic properties of 1 shows slow magnetic relaxation for CoII in a static field of 1000 Oe. Magnetic hysteresis loops were observed for 1 at 0.5 and 2 K; these loops are closed in the zero field region but opened at fields higher than ±100 and 700 Oe, respectively. The collapse of the loop is observed at 5 K. Excitation of the solution of 1 with green light decreases partially the intensity of the bands of the complex, whereas subsequent exposure of this solution to UV light partially restores these intensities.

Dual-chromic cellulose paper modified with nanocapsules containing leuco dye and spiropyran derivatives: A colorimetric portable chemosensor for detection of some heavy metal cations

Heavy metal cations are important in our daily life and may cause serious disorders and diseases. Colorimetric portable cellulosic sensors with high selectivity and sensitivity toward metal cations are preferred relative to those based on small molecules which operate mostly in organic media and difficult test methods. Here, dual-chromic stimuli-responsive cellulose paper (TPL@T-Cell) was produced by modification of the paper with the designed and prepared epoxy-functionalized polyacrylic nanocapsules via dip-coating and subsequent heat treatment processes. The capsules contained thermochromic leuco-dye derivative and photochromic hydroxyl-functionalized spiropyran and were prepared through semi-continuous miniemulsion polymerization. Chemical structure of the synthesized dyes, nanocapsules and modified cellulose fibers were identified by FTIR and UV-Vis analyses. Spherical morphology of the prepared nanocapsules with average particles size of 121 nm were observed by SEM and DLS analyses. The effective wetting of the cellulose fibers by nanocapsules with proper diffusion and deposition through the establishment of physical and chemical interactions were evaluated by SEM and ATR-FTIR analyses, respectively. The prepared TPL@T-Cell sensor revealed distinct color changes toward Fe2+, Pb2+ and Sn2+ ions. Opto-chemical results indicated that detection limit of TPL@T-Cell for Sn2+ (0.0028 µM, 0.326 ppb), Fe2+ (0.0013 µM, 0.15 ppb), and Pb2+ (0.0023 µM, 0.268 ppb) are lower than their critical permitted levels announced by WHO. These exhibited applicability of TPL@T-Cell sensor for determining trace amount of some heavy metal ions with instant responsivity, wide linear detection range, high sensitivity, and low detection limit via colorimetric and spectroscopic responses.

Preparation and dynamic color-changing study of fluorescent polymer nanoparticles for individualized and customized anti-counterfeiting application

Preparing new fluorescent materials for individualized and customized anti-counterfeiting applications to meet needs from the rapid development of e-commerce is of great significance. This paper reports the preparation of dynamic color-changing fluorescent polymer nanoparticles (PNPs) by constructing a fluorescence resonance energy transfer (FRET) pair between aggregation-induced emission (AIE) structures and photochromic structures. At first, methyl methacrylate (MMA) was used as the main monomer and tetraphenylethylene (TPE, a typical AIE structure) modified methacrylate (TPE-MA) and photochromic spiropyran (SP) modified methacrylate (SP-MA) as minor monomers were copolymerized to obtain the ternary copolymer PMMA-TPE-SP. Then, two types of PNPs based on this terpolymer was prepared via the reprecipitation method, with and without the addition of an amphiphilic polymer as the surfactant. The photophysical study shows that the fluorescence color of PNPs dynamically changes from blue to light violet and finally to red under UV light irradiation, a process that can be reversed under visible light. The PNPs were alternately irradiated with UV light and visible light for 10 cycles, which proved their good photoswitching reproducibility. The PNPs prepared with addition of surfactant were found to have stronger fluorescence and better stability. Finally, the photochromic fluorescent inks were prepared based on these PNPs. Several anti-counterfeiting scenarios and modes were designed, exhibiting excellent photochromic behavior on cellulose paper, even after 120 days of long-term storage. With simple equipment, desirable anti-counterfeiting effects with dynamic fluorescence color changing was achieved. This study demonstrated a promising hard-to-imitate anti-counterfeiting encryption strategy, which can achieve multiple outputs with simple operation and can be personalized and customized as needed.

Synthesis and study of new photochromic halogen-substituted spiropyrans of the indoline series

Synthesis and study of new photochromic halogen-substituted spiropyrans of the indoline series

Dynamic Information Encryption Technology by Combining Photochromic Spiropyrans and Carbon Dots

Dynamic Information Encryption Technology by Combining Photochromic Spiropyrans and Carbon Dots

Visible‐Light‐Driven Photoswitchable Fluorescent Polymers for Photorewritable Pattern, Anti‐Counterfeiting, and Information Encryption

AbstractPhotoswitchable fluorescent polymers (PFPs) are emerging as a class of promising systems for photowritable pattern, optical anti‐counterfeiting, and information encryption. They typically use harmful UV light as the stimulus, which often leads to inevitable photobleaching and poor reversibility. To address this issue, visible‐light‐driven PFPs by copolymerization of novel negative photochromic spiropyran monomer and methyl acrylate are developed. The obtained copolymers display bright red fluorescence, which can be reversibly turned off by visible light irradiation. Many appealing features are observed in this system, including fast photo‐responsibility, prominent photo‐reversibility and photostability, simple preparation process, and processability. Their applications in photorewritable patterns, optical anti‐counterfeiting, and information encryption are also demonstrated.

Tuning the Photochromism of Spiropyran in Functionalized Nanoporous Silica Nanoparticles for Dynamic Anticounterfeiting Applications.

Here, we report a novel invisible ink with different decay times based on thin films with different molar ratios of spiropyran (SP)/Si, which allows the encryption of messages over time. Nanoporous silica has been found to be an excellent substrate to improve the solid photochromism of spiropyran, but the hydroxyl groups of silica have a serious effect on fade speeds. The density of silanol groups in silica has an influence on the switching behavior of spiropyran molecules, as they stabilize the amphiphilic merocyanine isomers and thus slow down the fading process from the open to the closed form. Here, we investigate the solid photochromic behavior of spiropyran by sol-gel modification of the silanol groups and explore its potential application in UV printing and dynamic anticounterfeiting. To extend its applications, spiropyran is embedded in organically modified thin films prepared by the sol-gel method. Notably, by using the different decay times of thin films with different SP/Si molar ratios, time-dependent information encryption can be realized. It provides an initial "false" code, which does not display the required information, and only after a given time will the encrypted data appear.

Achieving Enhanced Photochromism of Spiropyran in Pretreated Nanoporous Lanthanide Metal–Organic Frameworks for Information Storage Applications

Spiropyran and its derivatives are an important class of photochromic molecules that have a wide range of applications in information storage and anti-counterfeiting. However, the easy tight accumulation of molecules under the solid state of spiropyran affects its discoloration efficiency, which is still a challenge to improve the solid photochromic properties. In this paper, a method of loading spiropyran by pretreatment of a lanthanide metal–organic framework (MOF) to improve its photo-response ability is reported. The lanthanide MOF is pretreated by methanol activation and 330 °C calcination to remove the unwanted ligands and some unreacted impurities in the framework. Compared to the pore size of the untreated framework (2.06 nm), the pore sizes of the framework activated by methanol (2.5 nm) and sintering at 330 °C (4.23 nm) were increased. Then, the spiropyran was loaded into a lanthanide MOF by solvent adsorption. After pretreatment of the Tb-MOF, the loading content of spiropyran increased from the initial 4.3 to 9.08 and 12.13%. After 365 nm UV illumination, the difference value in UV absorbance of framework pretreated composites gradually increased from 0.24 to 0.36, accompanied by color transition from yellow to violet. Due to the fluorescence resonance energy transfer effect between the donor lanthanide ion and the acceptor spiropyran, the fluorescence emission transition of the composite material was realized within 10 min. Among them, the fluorescence emission of the untreated composite of the frame can only change from pale yellow to orange, and the maximum fluorescence intensity is 4.4 × 105 CPS, while the fluorescence emission can change from yellow to red after frameworks’ pretreatment, and the fluorescence intensity is significantly improved, which is 6.4 × 105 and 7.5 × 105 CPS, respectively. By applying a composite material to a filter paper, a pattern with high contrast can be made. The pattern can be irradiated with ultraviolet light to realize the physical and fluorescence changes and can be restored to the initial state after being irradiated with green light with a wavelength of 530 nm for 10 min. This not only improves the solid photochromic properties of spiropyran but also provides the application possibility for information storage.