Simple substituents make big differences in photophysical performances of 2,1,3-benzothiadizole-conjugated spiropyrans

Developing multifunctional spiropyran dyes is of particular importance in diverse applications.In the present study,we synthesized two 2,1,3-benzothiadiazole-conjugated spiropyrans(BT-SP-NO2and BTSP-NMe2)with distinct substituents.These donor-acceptor-structured spiropyrans exhibited typical twisted intramolecular charge transfer features and strong emissions in low-polarity solvents with fluorescence quantum yields(QYs)of up to 90.7%.Like traditional spiropyrans,the electron-acceptor-substituted BT-SP-NO2exhibited excellent photochromic behavior under multiple alternating UV—Vis irradiation,while the electron-donor-substituted BT-SP-NMe2was an acidochromic dye.In addition,the substituent groups distinctly affected the packing modes of these spiropyrans in the solid state.BTSP-NMe2showed a much stronger solid-state emission(QY of 59.0%)than BT-SP-NO2.Moreover,these two dyes were utilized as biocompatible probes for the specific light-up imaging of lipid droplets.

Spectral Properties and Photochromic Characteristics of Spiropyran Dyes

A bis-benzospiropyran（BBSP） and nitro-substituted indoline spirobenzopyrans（SBP） were prepared by following a simple procedure. The reaction mechanism of synthesizing bis-benzospiropyran is discussed. A comparative analysis of the spectral and photochromic properties between SBP and BBSP was carried out with the aid of a PMMA film. The results indicate that chemical structures and UV irradiation played an important role in the spectral and photochromic properties of SBP and BBSP, which would readily affect λmax of the colored forms and the reversibility. The IR spectra and ^1H NMR spectra of these compounds are used to interpret the photochromic phenomena under different UV irradiation and determine the configurations of SBP and BBSP.

Study on the Tautomerism of an Indoline Spiropyran in Compressed CO_2 and Ethanol Mixture

Thermodynamic and kinetic properties of the tautomerism of an indoline spiropyran in compressed CO2-ethanol mixture were studied by UV-Vis spectroscopy at 298.15 K, 303. 15 K, and 308.15 K. It was found that the composition of the mixture affects the equilibrium constant and the rate constant significantly.

Preparation of Photochromic Waterborne Polyurethane Films:Effect of Spiropyran Concentration on Photochromic Properties

Incorporation of photochromic compounds to the polymer through chemical bonding will result in an enhancement of photoactivity and stabilization of optical properties.Here,spiropyran(SP)was introduced into polyurethane(PU)through semi-continuous emulsion copolymerization to get waterborne polyurethane dispersion(SPU).Studies on photochromic properties by UV-vis technique demonstrated the absorption intensity increased with the increasing of SP concentration and the colorless film turned to purple under UV irradiation.The kinetics for ring-opening and ring-closing reaction against SP were both first order,but the rate constants decreased with the increasing of SP concentration.The prepared SPU films showed reasonable photostability and photoreversibility according to the convenient test methods under UV-vis irradiation.Temperature dependence studies demonstrated that the photobleaching rate increased at higher temperatures with the same SP concentration.The chemical combination between SP and isocyanate(NCO)end group of polyurethane was confirmed through swelling experiments.Morphology studies were conducted by scanning electron microscope(SEM)micrographs and showed good compatibility between SP and PU.

Synthesis and Photochromic Properties of the Derivatives of Spiropyrans Containing a Mesogenic Group

Two series of novel spiropyran derivatives containing a mesogenic group have been prepared. Their photochromic behaviors were first investigated with the aid of absorption spectral measurements.

Some Hybrid Systems of Chiral Schiff Base Zn(II) Complexes and Photochromic Spiropyrans for Environmental Ion Sensing

This is a review article including our recent results and some previous photo functional hybrid system having potential applications for environmental ion sensing. We have prepared several new and known chiral Schiff base Zn(II) complexes and measured (and also calculated) absorption and fluorescence spectra for sole complexes. After assembling hybrid systems with 1,3,3-trime- thylindolino-6’-nitrobenzopyrylospiran (SP) in methanol solutions, we measured spectral changes before and after alternate irradiation of UV and visible light. Intensity of fluorescence spectra for pale yellow Zn(II) complexes (λem = 450 nm, λex = 270 and 360 nm) was quenched by colorless SP (λem = 533 nm, λex = 612 nm). After UV light irradiation to form purple merocyanine (MC), photoisomerization resulted in changes of the intensity of absorption spectra as well as fluorescence spectra. Thus the hybrid systems could successfully act as molecular logic circuit by input (excitation by light) and output (intensity of fluorescence peaks). Moreover, we investigated concentration dependence of doped Zn(II) and Cu(II) ions to confirm quenching of intensity of fluorescence peaks by Zn(II) and Cu(II) MC complexes for metal ion sensing in solutions.

Photo-controllable antifouling hydrogels embedded with AgNPs coated spiropyran functionalized mesoporous silica for long-term antibacterial activity

Silver nanoparticles(AgNPs)are widely used in antimicrobial applications.However,its easy aggregation and rapid loss hinder the effective antifouling.To address this issue,a novel stimuli-responsive antibacterial nanocomposite(Ag@SP-MSN)was developed based on spiropyran covalently conjugated mesoporous silica nanoparticles(284.6 nm)and AgNPs(27.1 nm)via strong electrostatic attraction.Both transmission electron microscopy(TEM)and atomic force microscopy(AFM)images proved the successful modification of AgNPs onto SP-MSN.The light-induced maximum loading amount towards AgNPs was calculated to be 95.0 wt.%after ultraviolet irradiation,while the amount of AgNPs released from Ag@SP-MSN was 94.4 wt.%under visible light in the aid of ammonia(0.1%,v/v).Upon cycled light irradiation,Ag@SP-MSN could recover 84.5 wt.%of AgNPs even after four cycles.The proposed Ag@SP-MSN exhibited better antibacterial activity against both E.coli and S.aureus than Ag@MSN under visible light illumination,indicating the efficient photo-responsive isomerization of spiropyran.Furthermore,the Ag@SP-MSN embedded gel demonstrated outstanding antifouling ability even after 21 days when compared to AgNPs gel.The long-term photo-controllable antifouling property proved the excellent reversible absorption and release of Ag@SP-MSN towards AgNPs.This work provides new insights into the safe utilization of nanomaterials,offering promising advancements to meet clinical antibacterial requirements.

Novel elastomeric spiropyran‑doped poly(dimethylsiloxane)optical waveguide for UV sensing

Novel poly(dimethylsiloxane)(PDMS)doped with two diferent spiropyran derivatives(SP)were investigated as potential candidates for the preparation of elastomeric waveguides with UV-dependent optical properties.First,free-standing flms were prepared and evaluated with respect to their photochromic response to UV irradiation.Kinetics,reversibility as well as photofatigue and refractive index of the SP-doped PDMS samples were assessed.Second,SP-doped PDMS waveguides were fabricated and tested as UV sensors by monitoring changes in the transmitted optical power of a visible laser(633 nm).UV sensing was successfully demonstrated by doping PDMS using one spiropyran derivative whose propagation loss was measured as 1.04 dB/cm at 633 nm,and sensitivity estimated at 115%change in transmitted optical power per unit change in UV dose.The decay and recovery time constants were measured at 42 and 107 s,respectively,with an average UV saturation dose of 0.4 J/cm2.The prepared waveguides exhibited a reversible and consistent response even under bending.The sensor parameters can be tailored by varying the waveguide length up to 21 cm,and are afected by white light and temperatures up to 70℃.This work is relevant to elastomeric optics,smart optical materials,and polymer optical waveguide sensors.

Visible light responsive spiropyran derivatives based on dynamic coordination bonds

Spiropyrans(SPs) are a well-known class of photochromic compounds and have found widespread application due to their unique properties. However, for many conventional SPs, high energy ultraviolet(UV)light is commonly essential to drive photoisomerization, leading to poor fatigue resistance. Moreover, the practical application of spiropyrans is hindered by their fast fading speed due to the instability of closed forms(SP) or open forms(MC). Herein, we disclose a novel strategy to address these challenges through introducing both electron-donating substituents to stabilize the SP and dynamic coordination bonds to stabilize the MC. The resulting new spiropyrans complexes exhibit negative photochromic properties, with fast visible light response, good stability of both SP and MC, and significantly improved fatigue resistance.

Spiropyran isomerization triggering ESIPT for visualization of pH fluctuations during oxidative stress in living cells

Intracellular pH homeostasis is foundation of maintaining normal physiological functions.More and more evidences show that intracellular pH fluctuations were usually associated with many diseases(such as cancer,epilepsy and neurodegenerative diseases).It is very important to develop in situ real-time determination of pH.In recent years,it has been verified that pH can regulate the isomerization process of spiropyran.Thus,we report a pH fluorescent probe BSL,which is a closed loop spiropyran structure by coupling benzothiazole derivatives with indole salts.We utilizes the process of spiropyran isomerization as the trigger of excited state intramolecular proton transfer(ESIPT)effect,and adjust the process of spiropyran isomerization through pH,and then the molecular transformation from enol to ketone(enol:525 nm,ketone:677 nm)through the ESIPT effect.This process achieved accurate measurement of pH.The probe BSL showed sensitive and reversible fluorescence response to pH in vitro.Ultimately,BSL was successfully applied to detect pH fluctuations in cell oxidative stress model.

Two-photon photopolymerization directly initiated by spiropyran photochromic molecules

Here,we report the ability of spiropyrans to initiate two-photon polymerization(TPP)for the first time in the literature.The comparison and synergies between the spiropyran photochromic molecule of interest,namely 6-nitro-BIPS,and well-known photoinitiators of radical photopolymerization have been studied.The spiropyran(SPy)molecule can initiate TPP in the presence of trifunctional acrylic monomers and create true 3D structures.The comparison with Irgacure 819,a well-known Type-I photoinitiator,shows that SPy has a comparable capability for TPP.In addition,the combination of SPy with methyl diethanolamine increased the reactivity of both one-and two-photon polymerizations.In the last section,we discuss which SPy isomer is the active photochromic species capable of generating radicals for initiating two-photon polymerization.

螺吡喃类刺激响应变色聚合物的研究进展

螺吡喃是一类可以对各种外部刺激做出反应而表现出不同性质的化合物。这些刺激可以是物理的、化学的或生物的,它们会导致螺吡喃化合物的结构、形状和性质发生变化。螺吡喃具有两个异构体:闭环的螺吡喃结构(SP)和开环的部花菁结构(MC)。螺吡喃化合物因结构简单、易于修饰和能够对多种刺激做出反应的优点,被广泛应用于制备刺激响应型聚合物和化学传感器。这些聚合物和传感器可应用于各个领域,如建筑、变色织物、光学防伪和离子检测等。本文综述了螺吡喃的合成途径,包括传统的三步合成法、一锅法以及较新的超声和微波合成法,还对螺吡喃聚合物的光致变色、机械力致变色、溶剂致变色、酸致变色、压致变色和热致变色等进行了综述,详细讨论了这些性质的机理、影响因素和实际应用。最后,展望了螺吡喃在设计和开发新型刺激响应材料和化学传感器领域的前景。

Synthesis of novel chalcone derivatives and their stabilization effect of spiropyran in PMMA films

Three novel bis-chalcone derivatives with different alkyldioxy spacers were synthesized and dispersed into polymethyl methacrylate （PMMA） chloroform solution with 6-nitro-1＇-ethyl-3＇,3＇-dimethylspiro-2H-1-benzopyran-2,U-indoline （ESP） to prepare photochromic PMMA films in a facile way. After irradiation with 365 nm UV light, the photocrosslinking reaction between chalcone units was proved to retard the decolorization of merocyanine form of the photochromic spiropyran effectively, as results of the steric hindrance produced by photocycloaddition of chalcone groups. It has been found that the bis-chalcone molecule with the shortest spacer has the most effective stabilizing effect on retardation of decoloration of spiropyran. reserved.

A fluorescent probe based on a spiropyran for sensitive detection of Ce^3+ ion

A spiropyran-based probe was developed.It serves as a fluorescence turn-on probe for selective detection of Ce^3+in both ethanol and aqueous(water/ethanol,1:9 or 9:1,v/v)media.Ce3+can induce photochromism of the probe though the probe exhibits negligible photochromic property by itself.The probe is sensitive to Ce3+and the detection limit reaches 1.7μmol/L.It exhibits a high selectivity for Ce^3+ion over other common metal cations including Li^+,Na^+,Ag^+,Sr^2+,Ni^2+,Co^2+,Hg^2+,Zn^2+,Cr^3+,Al^3+,Fe^3+and Bi^3+and lanthanide ions Nd^3+,Yb^3+and La^3+.The probe may be used for quantitative determination of the concentration of Ce3+ion in a range of 1-10μmol/L and for application to environmental water samples.Sensing mechanism of the probe towards Ce3+ion is proposed.

A Multiresponsive Hydrophobic Associating Hydrogel Based on Azobenzene and Spiropyran

Summary of main observation and conclusion Stimuli-responsive hydrogels crosslinked by weak noncovalent bonds such as hydrogen bonds,ionic interactions,host-guest interactions and hydrophobic interactions have been extensively investigated.Herein,azobenzene and spiropyran acting as two hydrophobic pendant groups were introduced into a hydrophilic polyacrylamide (PAM) via free radical copolymerization to construct a hydrophobic interaction based thermo-,light-responsive polymer hydrogel.Its viscosity and color could be reversibly regulated by heating and cooling.Meanwhile,its color could be specifically switched by light without obvious viscosity change.The gel was also capable of being transited to sol by addition of β-cyclodextrin (β-CD),which encaged the hydrophobic groups and then increased the solubility of polymer in water.The hydrogel could be regained after UV irradiation at λ=365 nm,and after irradiation at λ=440 nm,the hydrogel changed into a clear sol again.

Synthesis of New Spiropyrans With a Polyaromatic or Heteroaromatic Pendant and Their Photochromic Behaviors

A series of spiropyrans with a polyaromatic or heteroaromatic pendant was synthesized conveniently. Their photochromic behaviors were investigated with the aid of absorption spectral measurements. The results indicated that the compounds with the same parent spiropyran but different aromatic pendant show significantly different photochromic properties. This may be due to the π-π orbital interaction between the polyaromatic pendant and the open photomerocyanine form of spiropyran. The results obtained are very useful in the molecule design area.

Dual sensitivity of spiropyran-functionalized carbon dots for full color conversions

Multicolor phosphors that respond rapidly to external stimuli are highly desirable for many applications, including lighting,optical displays and sensors. Herein, spiropyran(SP)-functionalized carbon dots(CDs) were synthesized with a broad-spectrum output that were responsive to both ultraviolet(UV)/visible light and pH. The SP-CDs possessed strong ester linkages between the UV-absorbing/blue-emitting CDs and blue-absorbing/red-emitting surface SP groups, allowing efficient F?rster resonance energy transfer(FRET) between the donor and acceptor. UV irradiation or acid addition cause the SP ring opening to merocyanine(MC) or protonated MCH+forms, respectively, together with the formation of sheet-like aggregates. These processes enhanced the red emissions by the SP groups and attenuated blue emissions from the CDs. These changes were fully reversible under visible light or basic conditions, respectively, allowing dynamic regulation of the fluorescence properties(emission colors from blue to red, photoluminescence(PL) intensity) under photoirradiation on the timescale of minutes. As proof-of concept, we demonstrate that the emission properties of the SP-CDs can be used to construct UV and pH sensing materials as well as light emitting diode(LED) with different colors.

Utilization of a spiropyran derivative in a polymeric film optode for selective fluorescent sensing of zinc ion

A new spiropyran derivative was synthesized and first utilized in a polymericfilm-based optical sensor for zinc ion. Spiropyrans, combining the characteristics of metal bindingand signal transduction, show potential function in the design of optical chemical sensors(optodes) toward metal ions. When embedded in a plasticized poly (vinyl chloride) (PVC) membrane,the newly synthesized spiropyran derivative 1 exhibits obvious fluorescence enhancement at 630 nm inthe presence of zinc ion in aqueous solution. With the optimum condition described, the optodemembrane responds to zinc ion over a dynamic range of 4.94x10^(-7) to 4.15x10^(-4)mol·L^(-1), witha detection limit of 1.51x10^(-7) mol·L^(-1). The membrane not only displays excellentphotostability, reproducibility and reversibility, but also exhibits high selectivity toward zincion over transition metal ions including Hg^(2+), Cd^(2+), Pb^(2+), Cu^(2+), Fe^(3+) and commoncationic ions presented in the physiological fluids.

Structure and photochromism of spiropyran assemblies

Nanocluster assemblies of spiropyran compounds have been prepared by means of LB technique, and the relations between the subphase, pH value, condition of preparation and the structure of the fabricated LB film are systematically investigated. The stability, photochromic fatigue properties of the spiropyran LB film, which are of primary importance in optic signal storage applications, are also studied in detail. A kind of supermolecular film with homogeneously distributed J aggregates of similar granular size has been obtained with the optical resolution in the order of micrometer. Finally, a nondestructive readout method for such an LB film to be used as the optic signal storage film is proposed.

In situ Observation of the Photochromism in the Langmuir Monolayer of a Non-typical Amphiphilic Spiropyran Derivative at the Air/Water Interface

In situ photochromic process in the monolayer of a photochromic spiropyran derivative without long alkyl chain, was investigated. The photochromism at the air/water interface under different surface pressures was studied by surface pressure area isotherms, surface pressure time curves, area time curves and Brewster angle microscopy. Both forms of the compound were found to form monolayers at the air/water interface although it does not have long alkyl chain. A large area expansion in the monolayer corresponding to a zero th order reaction was found at the initial stage of the UV light irradiation. A series of dynamic investigations revealed that at high pressure after phase transition in the monolayer, the surface pressure changes greatly under alternative irradiation of UV and visible light. An obvious morphological change accompanying with the photochromism was observed in situ .