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...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.展开更多
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.
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 ...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.展开更多
Donor-acceptor Stenhouse adducts(DASAs)as a species of novel photochromic molecules,have been developing rapidly and attracting broad researchers’sights since 2014.DASAs show visible/near-infrared(NIR)light induced l...Donor-acceptor Stenhouse adducts(DASAs)as a species of novel photochromic molecules,have been developing rapidly and attracting broad researchers’sights since 2014.DASAs show visible/near-infrared(NIR)light induced linear-to-cyclic isomerization and heat induced cyclic-to-linear isomerization,therefore they are attractive in photoresponsive hydrogels,drug delivery,cell culturing and tissue engineering.As a series of well-known photoresponsive molecules,spiropyrans(SPs)show similar molecular properties and comparable photoswitching with DASAs.UV light triggers closed-to-open(also known as spirocyclic(SC)-to-merocyanine(MC))isomerization of SPs,while the reversed open-to-closed isomerization occurs under visible light or heat.Light irradiation switches the molecular color,scale,geometry,and polarity of SPs and DASAs reversibly.Since the researches on DASAs are still in the infancy,the chemical structures,isomerization mechanisms and potential applications need to be further investigated and explored.The well-studied SPs have important reference values to the comprehensive developments of DASAs.In the present review,we summarized,compared and discussed SPs and DASAs with regards to their molecular structures,synthesis,photoswitching and applications.We also make our perspective on the developments of DASA in future.展开更多
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 indicate...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.展开更多
It remains a big challenge to develop solid-state stimuli-responsive materials for time-dependent information encryption and inkless erasable printing with long retention times.Herein,a 2D Cu_(2)I_(2)-based MOF with p...It remains a big challenge to develop solid-state stimuli-responsive materials for time-dependent information encryption and inkless erasable printing with long retention times.Herein,a 2D Cu_(2)I_(2)-based MOF with photoresponsive spiropyran(SP)groups orderly installed on its skeleton is developed.The structural isomerization from SP to colored merocyanine(MC)form can be triggered by removing the CH_(3)CN vips.Besides,the degree of structural isomerization and the retention time can be adjusted by controlling the amount of CH_(3)CN vips,exhibiting dynamic photochromic behavior with multicolor states and tunable retention time.Based on these advantages,time-dependent information encryption is successfully achieved.Furthermore,the long retention time(>72 h)of the MC form under daylight conditions in the CH_(3)CN-removed Cu_(2)I_(2)-based MOF and good repeatability make it promising in various applications,such as temporary calendars,price-cards,billboards,and reusable identity cards.This work provides a novel design strategy to fabricate multi-functional MOF-based smart materials for challenging applications of time-dependent information encryption and inkless erasable printing.展开更多
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-benzopy...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.展开更多
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...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.展开更多
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,epilep...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.展开更多
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 comparativ...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.展开更多
Photochromic and photoluminescence materials show bright colors under different excitation conditions,and thus,these functional materials have been applied in many fields.Based on the photochromic and photoluminescenc...Photochromic and photoluminescence materials show bright colors under different excitation conditions,and thus,these functional materials have been applied in many fields.Based on the photochromic and photoluminescence theories,a block copolymer,which could be directly processed into nanofibers by electrospinning,was successfully prepared through atom transfer radical polymerization(ATRP).To synthesize the block copolymer,a vinyl monomer containing a spiropyran unit was employed to prepare the photochromic chain segment,and a polymethyl methacrylate(PMMA)chain segment was introduced to improve the processability of the block copolymer.Acting as the photoluminescence unit,the rare earth complex was linked to the side chain through coordination bonding between the rare earth ions and the ester groups of PMMA.When the photochromic and photoluminescence block copolymer was exposed to different wavelengths of ultraviolet(UV)light and visible(Vis)light,it could show white,red,green,yellow,and blue-purple.These results provide the potential of the as-prepared photochromic and photoluminescence block copolymer for application in fibers and fabrics.展开更多
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 ...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.展开更多
In recent years,organic field-effect transistors（OFETs） with high performance and novel multifunctionalities have attracted considerable attention.Meanwhile,featured with reversible photoisomerization and the corres...In recent years,organic field-effect transistors（OFETs） with high performance and novel multifunctionalities have attracted considerable attention.Meanwhile,featured with reversible photoisomerization and the corresponding variation in color,chemical/physical properties,photochromic molecules have been applied in sensors,photo-switches and memories.Incorporation of photochromic molecules to blend in the device functional layers or to modify the interfaces of OFETs is common way to build photo-transistors.In this review,we focus on the recent advantages on the study of photoresponsive transistors involving one of three typical photochromic compounds spiropyran,diarylethene and azobenzene.Three main strategies are demonstrated in detail.Firstly,photochromic molecules are doped in active layers or combined with semiconductor structure thus forming photoreversible active layers.Secondly,the modification of dielectric layer/active layer interface is mainly carried out by bilayer dielectric.Thirdly,the photo-isomerization of self-assembled monolayer（SAM） on the electrode/active layer interface can reversibly modulate the work functions and charge injection barrier,result in bifunctional OFETs.All in all,the combination of photochromic molecules and OFETs is an efficient way for the fabrication of organic photoelectric devices.Photoresponsive transistors consisted of photochromic molecules are potential candidate for real applications in the future.展开更多
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 compo...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.展开更多
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 polyurethan...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.展开更多
The title compound of 4-（2-methylene-1-ethyl-3,3-dimethylindoline-2＇-yl）-6,8-dibro-mo-1＇-ethyl-3＇,3＇-dimethylspiro[3,4-dihydro-2H-1-benzopyran-2,2＇-indoline],C33H36Br2N2O,as a dicondensed spiropyran（DC） has b...The title compound of 4-（2-methylene-1-ethyl-3,3-dimethylindoline-2＇-yl）-6,8-dibro-mo-1＇-ethyl-3＇,3＇-dimethylspiro[3,4-dihydro-2H-1-benzopyran-2,2＇-indoline],C33H36Br2N2O,as a dicondensed spiropyran（DC） has been synthesized by indoline in ethanol with 3,5-dibromo-salicyaldehyde.The compound was characterized by elemental analysis and IR spectra.Meanwhile,the crystal of the compound was obtained and determined by X-ray single-crystal diffraction.Crystal data：monoclinic system,space group P21/n,a=12.9699（15）,b=12.5196（13）,c=19.327（2）,β=106.493（3）°,Mr=636.46,V=3009.1（6） 3,Z=4,F（000）=1304,Dc=1.405 g/cm3,μ=2.722 mm-1,R=0.0554 and wR=0.1176 for 6892 independent reflections（Rint=0.0354） and 5699 observed reflections（Ⅰ〉 2σ（Ⅰ））.展开更多
The photochromic ring-opening reaction of spiropyran（SP） has been investigated by a realistic semiclassical dynamics simulation,accompanied by SA3-CASSCF（12 10）/MS-CASPT2 potential energy curves（PECs） of S0–S2....The photochromic ring-opening reaction of spiropyran（SP） has been investigated by a realistic semiclassical dynamics simulation,accompanied by SA3-CASSCF（12 10）/MS-CASPT2 potential energy curves（PECs） of S0–S2.The main simulation results show the dominate pathway corresponds to the ringopening process of trans-SP to form the most stable merocyanine（MC） product.These findings provide more important complementarity for interpreting experimental observations.展开更多
Photosensitive fluorescent probes have become powerful tools in chemical biology and molecular biophysics,which are used to investigate cellular processes with high temporal and spatial resolution.Accordingly,photosen...Photosensitive fluorescent probes have become powerful tools in chemical biology and molecular biophysics,which are used to investigate cellular processes with high temporal and spatial resolution.Accordingly,photosensitive fluorescent probes,including photoactivatable,photoconvertible,and photoswitchable fluorophores,have been extensively developed during the past decade.The photoswitchable fluorophores have received much attention because they highlight cellular events clearly.This minireview summarizes recent advances of using reversibly photoswitchable fluorophores and their applications in innovative bioimaging.Photoswitchable fluorophores include photoswitchable fluorescent proteins,photoswitchable fluorescent organic molecules(dyes),and photoswitchable fluorescent nanoparticles.Several strategies have been developed to synthesize photoswitchable fluorophores,including engineering combination proteins,chemical synthesis,polymerization,and self-assembly.Here we concentrate on polymer nanoparticles with optically switchable emission properties:either fluorescence on/offor dualalternating-color fluorescence photoswitching.The essential mechanisms of fluorescence photoswitching enable different types of photoswitchable fluorophores to change emission intensity or wavelength(color)and thus validating the basis of the fluorescence on/offor dual-color photoswitching design.Generally the possible applications of any fluorophores are to label biological targets,followed by specific imaging.The newly developed photoswitchable fluorophores enable super-resolution fluorescence imaging because of their photosensitive emission.Finally,we summarize the important area regarding future research and development on photoswitchable fluorescent nanoparticles.展开更多
Photochromic polymer is defined as a series of materials based on photochromic units in polymer chains,which produces reversible color changes under irradiation with a particular wavelength.Currently,as the research p...Photochromic polymer is defined as a series of materials based on photochromic units in polymer chains,which produces reversible color changes under irradiation with a particular wavelength.Currently,as the research progresses,it shows increasing potential applications in various fields,such as anti-counterfeiting,information storage,super-resolution imaging,and logic gates.However,there is a paucity of published reviews on the topic of photochromic polymers.Herein,this review discusses and summarizes the research progress and prospects of such materials,mainly summarizing the basic mechanisms,classification,and applications of azobenzene,spiropyran,and diarylethene photochromic polymers.Moreover,3-dimensional(3D)printable photochromic polymers are worthy to be summarized specifically because of its innovative approach for practical application;meanwhile,the developing 3D printing technology has shown increasing potential opportunities for better applications.Finally,the current challenges and future directions of photochromic polymer materials are summarized.展开更多
Dynamic fluorescent materials capable of stimulus-responsive emission modulation have emerged as pivotal components in next-generation information security systems.This study presents a novel photoresponsive fluoresce...Dynamic fluorescent materials capable of stimulus-responsive emission modulation have emerged as pivotal components in next-generation information security systems.This study presents a novel photoresponsive fluorescent composite system in which spiropyran(SP)was covalently grafted onto naphthalimide-functionalized silica aerogel matrices.These architectures exhibit reversible fluorescence resonance energy transfer between the naphthalimide donors and merocyanine-form of SP acceptors under ultraviolet irradiation,enabling dynamic emission shifting from green(blue)to red.The aggregation-induced emission characteristics of SP were used to engineer a smart material system that can reversibly regulate its distinct red fluorescence by precisely controlling the dispersion of amino groups on naphthalimide-functionalized silica aerogels.This spatial manipulation directly governs the molecular packing state of SP,enabling dynamic fluorescence modulation.A programmable control over the fluorescence chromatic transitions in the composite material was achieved by systematically adjusting the SP grafting densities(1%,2%,and 3%w/w).A unique mode of dynamic information encryption technology was developed by utilizing dynamic fluorescence variations.These materials can substantially enhance information encryption levels due to their precisely adjustable fluorescence properties in response to external stimuli over time.This makes the encryption process even more unpredictable and complex,thereby exponentially increasing the difficulty for unauthorized parties to replicate or decode the encrypted information.展开更多
基金supported by the National Natural Science Foundation of China(62105184)the Natural Science Foundation of Shandong Province,China(2022HWYQ-007 and ZR2021QB043)the Special Fund of Taishan Scholars Project of Shandong Province,China(tsqn201909012)。
文摘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.
基金The auth ors thank the National Natural Science Foundation of China for the financial support．(Grant Nos．20402009 and 20372039)．
文摘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.
文摘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.
基金the financial support from the National Natural Science Foundation of China(61805034)Guangdong Basic and Applied Basic Research Foundation(2019A1515110678)Opening Project of State Key Laboratory of Polymer Materials Engineering(Sichuan University)(Grant No.sklpme2018-4-28).
文摘Donor-acceptor Stenhouse adducts(DASAs)as a species of novel photochromic molecules,have been developing rapidly and attracting broad researchers’sights since 2014.DASAs show visible/near-infrared(NIR)light induced linear-to-cyclic isomerization and heat induced cyclic-to-linear isomerization,therefore they are attractive in photoresponsive hydrogels,drug delivery,cell culturing and tissue engineering.As a series of well-known photoresponsive molecules,spiropyrans(SPs)show similar molecular properties and comparable photoswitching with DASAs.UV light triggers closed-to-open(also known as spirocyclic(SC)-to-merocyanine(MC))isomerization of SPs,while the reversed open-to-closed isomerization occurs under visible light or heat.Light irradiation switches the molecular color,scale,geometry,and polarity of SPs and DASAs reversibly.Since the researches on DASAs are still in the infancy,the chemical structures,isomerization mechanisms and potential applications need to be further investigated and explored.The well-studied SPs have important reference values to the comprehensive developments of DASAs.In the present review,we summarized,compared and discussed SPs and DASAs with regards to their molecular structures,synthesis,photoswitching and applications.We also make our perspective on the developments of DASA in future.
文摘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.
基金supported by the National Natural Science Foundation of China(Nos.21825106,92061201,22105175)Postdoctoral Research Grant in Henan Province(No.202102001)。
文摘It remains a big challenge to develop solid-state stimuli-responsive materials for time-dependent information encryption and inkless erasable printing with long retention times.Herein,a 2D Cu_(2)I_(2)-based MOF with photoresponsive spiropyran(SP)groups orderly installed on its skeleton is developed.The structural isomerization from SP to colored merocyanine(MC)form can be triggered by removing the CH_(3)CN vips.Besides,the degree of structural isomerization and the retention time can be adjusted by controlling the amount of CH_(3)CN vips,exhibiting dynamic photochromic behavior with multicolor states and tunable retention time.Based on these advantages,time-dependent information encryption is successfully achieved.Furthermore,the long retention time(>72 h)of the MC form under daylight conditions in the CH_(3)CN-removed Cu_(2)I_(2)-based MOF and good repeatability make it promising in various applications,such as temporary calendars,price-cards,billboards,and reusable identity cards.This work provides a novel design strategy to fabricate multi-functional MOF-based smart materials for challenging applications of time-dependent information encryption and inkless erasable printing.
基金the financial support from the National High Technology Research and Development Program of China(No.2005AA320030)SJTU-Aeronautics Industry Joint Program(No.0304)
文摘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.
文摘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.
基金the National Natural Science Foundation of China(No.22074084)One Hundred People Plan of Shanxi Province,Shanxi Province“1331 Project”Key Innovation Team Construction Plan Cultivation Team(No.2018-CT-1)+6 种基金Research Project Supported by Shanxi Scholarship Council of China(No.2022-002)Shanxi Province Foundation for Returness(No.2017-026)Shanxi Collaborative Innovation Center of High Value-added Utilization of Coalrelated Wastes(No.2015-10-B3)the Shanxi Province Foundation for Selected(2019),Innovative Talents of Higher Education Institutions of Shanxi,Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(No.2019L0031)Key R&D Program of Shanxi Province(No.201903D421069),the Shanxi Province Science Foundation(No.201901D111015)Key R&D and Transformation Plan of Qinghai Province(No.2020-GX-101)Graduate Innovation Project of Shanxi Province and Scientific Instrument Center of Shanxi University(No.201512)。
文摘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.
基金Supported by the Scientific Research Foundation for the Returned Overseas Chinese Scholars, Ministry of Education(No. SRF-2004-527)
文摘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.
基金Application Fundamental and Advanced Technology Research Proposal Project of Tianjin,China(No.18JCZDJC38300)。
文摘Photochromic and photoluminescence materials show bright colors under different excitation conditions,and thus,these functional materials have been applied in many fields.Based on the photochromic and photoluminescence theories,a block copolymer,which could be directly processed into nanofibers by electrospinning,was successfully prepared through atom transfer radical polymerization(ATRP).To synthesize the block copolymer,a vinyl monomer containing a spiropyran unit was employed to prepare the photochromic chain segment,and a polymethyl methacrylate(PMMA)chain segment was introduced to improve the processability of the block copolymer.Acting as the photoluminescence unit,the rare earth complex was linked to the side chain through coordination bonding between the rare earth ions and the ester groups of PMMA.When the photochromic and photoluminescence block copolymer was exposed to different wavelengths of ultraviolet(UV)light and visible(Vis)light,it could show white,red,green,yellow,and blue-purple.These results provide the potential of the as-prepared photochromic and photoluminescence block copolymer for application in fibers and fabrics.
基金supported by the National Natural Science Foundation of China (Nos. 21631006 and 21771100)。
文摘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.
基金supported financially by the National Natural Science Foundation of China(Nos.21302212 and 21522209)the "Strategic Priority Research Program"(No.XDB12010100)
文摘In recent years,organic field-effect transistors（OFETs） with high performance and novel multifunctionalities have attracted considerable attention.Meanwhile,featured with reversible photoisomerization and the corresponding variation in color,chemical/physical properties,photochromic molecules have been applied in sensors,photo-switches and memories.Incorporation of photochromic molecules to blend in the device functional layers or to modify the interfaces of OFETs is common way to build photo-transistors.In this review,we focus on the recent advantages on the study of photoresponsive transistors involving one of three typical photochromic compounds spiropyran,diarylethene and azobenzene.Three main strategies are demonstrated in detail.Firstly,photochromic molecules are doped in active layers or combined with semiconductor structure thus forming photoreversible active layers.Secondly,the modification of dielectric layer/active layer interface is mainly carried out by bilayer dielectric.Thirdly,the photo-isomerization of self-assembled monolayer（SAM） on the electrode/active layer interface can reversibly modulate the work functions and charge injection barrier,result in bifunctional OFETs.All in all,the combination of photochromic molecules and OFETs is an efficient way for the fabrication of organic photoelectric devices.Photoresponsive transistors consisted of photochromic molecules are potential candidate for real applications in the future.
文摘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.
基金Construction of High-Level Teachers of Beijing Institute of Fashion Technology,China(No.BIFT201808)。
文摘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.
基金supported by the Natural Science Foundation of Anhui Provincial Education Department (No. KJ2010B463)the Key Subject Program of Jiangsu Province (No. S1109001)
文摘The title compound of 4-（2-methylene-1-ethyl-3,3-dimethylindoline-2＇-yl）-6,8-dibro-mo-1＇-ethyl-3＇,3＇-dimethylspiro[3,4-dihydro-2H-1-benzopyran-2,2＇-indoline],C33H36Br2N2O,as a dicondensed spiropyran（DC） has been synthesized by indoline in ethanol with 3,5-dibromo-salicyaldehyde.The compound was characterized by elemental analysis and IR spectra.Meanwhile,the crystal of the compound was obtained and determined by X-ray single-crystal diffraction.Crystal data：monoclinic system,space group P21/n,a=12.9699（15）,b=12.5196（13）,c=19.327（2）,β=106.493（3）°,Mr=636.46,V=3009.1（6） 3,Z=4,F（000）=1304,Dc=1.405 g/cm3,μ=2.722 mm-1,R=0.0554 and wR=0.1176 for 6892 independent reflections（Rint=0.0354） and 5699 observed reflections（Ⅰ〉 2σ（Ⅰ））.
基金supported by the National Natural Science Foundation of China (Nos. 21003100 and 21073242)Natural Science Basic Research Plan in Shaanxi Province of China (No. 2011JQ2013)Special Fund of Education Department of Shaanxi Province (No. 12JK0619)
文摘The photochromic ring-opening reaction of spiropyran（SP） has been investigated by a realistic semiclassical dynamics simulation,accompanied by SA3-CASSCF（12 10）/MS-CASPT2 potential energy curves（PECs） of S0–S2.The main simulation results show the dominate pathway corresponds to the ringopening process of trans-SP to form the most stable merocyanine（MC） product.These findings provide more important complementarity for interpreting experimental observations.
基金This work was supported in part by the Fundamental Research Funds for the Central Universities(HUST2010MS101),the NSFC(20874025)the Program for New Century Excellent Talents(NCET-07-00273)+1 种基金National Key Basic Research Program of China(2007CB310500)the National Science Foundation(NSF)Chemistry Division(CHE-0805547).
文摘Photosensitive fluorescent probes have become powerful tools in chemical biology and molecular biophysics,which are used to investigate cellular processes with high temporal and spatial resolution.Accordingly,photosensitive fluorescent probes,including photoactivatable,photoconvertible,and photoswitchable fluorophores,have been extensively developed during the past decade.The photoswitchable fluorophores have received much attention because they highlight cellular events clearly.This minireview summarizes recent advances of using reversibly photoswitchable fluorophores and their applications in innovative bioimaging.Photoswitchable fluorophores include photoswitchable fluorescent proteins,photoswitchable fluorescent organic molecules(dyes),and photoswitchable fluorescent nanoparticles.Several strategies have been developed to synthesize photoswitchable fluorophores,including engineering combination proteins,chemical synthesis,polymerization,and self-assembly.Here we concentrate on polymer nanoparticles with optically switchable emission properties:either fluorescence on/offor dualalternating-color fluorescence photoswitching.The essential mechanisms of fluorescence photoswitching enable different types of photoswitchable fluorophores to change emission intensity or wavelength(color)and thus validating the basis of the fluorescence on/offor dual-color photoswitching design.Generally the possible applications of any fluorophores are to label biological targets,followed by specific imaging.The newly developed photoswitchable fluorophores enable super-resolution fluorescence imaging because of their photosensitive emission.Finally,we summarize the important area regarding future research and development on photoswitchable fluorescent nanoparticles.
基金supported by the Fundamental Science Center Funds(62288102)the NSF of China(62275217)+1 种基金Natural Science Basic Research Program of Shaanxi(2024JC-JCQN-51)the Postgraduate Innovation Fund of Northwestern Polytechnical University(PF2024125).
文摘Photochromic polymer is defined as a series of materials based on photochromic units in polymer chains,which produces reversible color changes under irradiation with a particular wavelength.Currently,as the research progresses,it shows increasing potential applications in various fields,such as anti-counterfeiting,information storage,super-resolution imaging,and logic gates.However,there is a paucity of published reviews on the topic of photochromic polymers.Herein,this review discusses and summarizes the research progress and prospects of such materials,mainly summarizing the basic mechanisms,classification,and applications of azobenzene,spiropyran,and diarylethene photochromic polymers.Moreover,3-dimensional(3D)printable photochromic polymers are worthy to be summarized specifically because of its innovative approach for practical application;meanwhile,the developing 3D printing technology has shown increasing potential opportunities for better applications.Finally,the current challenges and future directions of photochromic polymer materials are summarized.
基金supported by the Zhejiang Sci-Tech University Shengzhou Innovation Research Institute(SYY2.023C000005)the National Natural Science Foundation of China(51803184)。
文摘Dynamic fluorescent materials capable of stimulus-responsive emission modulation have emerged as pivotal components in next-generation information security systems.This study presents a novel photoresponsive fluorescent composite system in which spiropyran(SP)was covalently grafted onto naphthalimide-functionalized silica aerogel matrices.These architectures exhibit reversible fluorescence resonance energy transfer between the naphthalimide donors and merocyanine-form of SP acceptors under ultraviolet irradiation,enabling dynamic emission shifting from green(blue)to red.The aggregation-induced emission characteristics of SP were used to engineer a smart material system that can reversibly regulate its distinct red fluorescence by precisely controlling the dispersion of amino groups on naphthalimide-functionalized silica aerogels.This spatial manipulation directly governs the molecular packing state of SP,enabling dynamic fluorescence modulation.A programmable control over the fluorescence chromatic transitions in the composite material was achieved by systematically adjusting the SP grafting densities(1%,2%,and 3%w/w).A unique mode of dynamic information encryption technology was developed by utilizing dynamic fluorescence variations.These materials can substantially enhance information encryption levels due to their precisely adjustable fluorescence properties in response to external stimuli over time.This makes the encryption process even more unpredictable and complex,thereby exponentially increasing the difficulty for unauthorized parties to replicate or decode the encrypted information.
