STUDY ON PHOTODYNAMIC AND PHOTORESPONSIVE AZO POLYELECTROLYTES

Several kinds of novel azobenzene-containing polyelectrolytes with special molecular design have been developed from acryloyl chloride or epoxy based precursor polymers. The acryloyl chloride based precursor polymer, poly(acryloyl chloride), was prepared by free radical polymerization of acryloyl chloride. The azo polyelectrolytes were prepared by an esterification reaction between the precursor polymer and corresponding azo chromophores containing a reactive hydroxyl group, followed by hydrolysis of the unreacted acyl chloride groups. The epoxy based precursor polymer was prepared by the reaction between 1,4-cyclohexanedimethanol diglycidyl ether and aniline, and postfunctionalized by azo coupling reaction to form azo polymers containing chromophores with ionizable groups. The polyelectrolytes were characterized by elemental analysis, H-1-NMR, IR and UV-Vis spectroscopy. The photodynamic and photoresponsive properties, as well as self-assembly of these azo polyelectrolytes are reported in this paper([1]).

Photoresponsive characteristics of thin film transistors with perovskite quantum dots embedded amorphous InGaZnO channels

Photodetectors based on amorphous InGaZnO(a-IGZO)thin film transistor(TFT)and halide perovskites have attracted attention in recent years.However,such a stack assembly of a halide perovskite layer/an a-IGZO channel,even with an organic semiconductor film inserted between them,easily has a very limited photoresponsivity.In this article,we investigate photoresponsive characteristics of TFTs by using CsPbX3(X=Br or I)quantum dots(QDs)embedded into the a-IGZO channel,and attain a high photoresponsivity over 10^3A·W^-1,an excellent detectivity in the order of 10^16 Jones,and a light-to-dark current ratio up to 10^5 under visible lights.This should be mainly attributed to the improved transfer efficiency of photoelectrons from the QDs to the a-IGZO channel.Moreover,spectrally selective photodetection is demonstrated by introducing halide perovskite QDs with different bandgaps.Thus,this work provides a novel strategy of device structure optimization for significantly improving the photoresponsive characteristics of TFT photodetectors.

Synthesis, Characterisation and Photoresponsive Studies of Lignin Functionalised with 2-(5-(4-dimethylamino-benzylidin)-4-oxo-2-thioxo- thiazolidin-3-yl)-acetic Acid

A chromophoric system 2-(5-(4-dimethylamino-benzylidin)-4-oxo-2-thioxo-thiazoli din-3-yl)acetic acid with push-pull electron modulation was synthesised and incorporated onto lignin core (technical lignin, lignin sulphonic acid M.W. 52,400) and the photo responsive behaviour was investigated. The product was characterised by UV-visible, fluores-cence, FT-IR, and NMR spectroscopic methods. The results of the studies show that the incorporation of the chromo-phoric system on to the lignin core enhanced the light absorption and light stabilization properties of the chromophoric system. The remarkable stability on irradiation provides a novel photo responsive system with excellent light fastening properties which would find application in coating materials, dyes, paints etc.

Enhancing photoresponsiveness of metal-organic polyhedra by modifying microenvironment

Photoresponsiveness of materials is critical to their tunability and efficiency in terminal applications.Photoresponsive metal-organic polyhedra(PMOPs)feature intrinsic pores and remote controllability,but aggregation of PMOPs in solid state hampers their photoresponsiveness seriously.Herein,we report the construction of a new PMOP(Cu_(24)(C_(16)H_(12)N_(2)O_(4))_(12)(C_(18)H_(22)O_(5))12,denoted as MOP-PR-LA),where long alkyl(LA)chains act as the intermolecular poles,propping against adjacent PMOP molecules to create individual microenvironment benefiting the isomerization of photoresponsive(PR)moieties.Upon ultraviolet(UV)-and visible-light irradiation,MOP-PR-LA is much easier to isomerize than the counterpart MOP-PR without LA.For propylene adsorption,MOP-PR has a low change of adsorption capacity(9.9%),while that of MOP-PR-LA reaches 58.6%.Density functional theory calculations revealed that PR in the cis state has a negative effect on adsorption,while the trans state of PR favors adsorption.This work might open an avenue for the construction of photoresponsive materials with high responsiveness and controllability.

Photoresponsive Supramolecular Hydrogel Co-assembled from Fmoc-Phe-OH and 4,4′-Azopyridine for Controllable Dye Release

Photoresponsive hydrogels have been attractive because they can provide precise spatial and temporal control for molecule release, whereas the conventional preparation of photoresponsive hydrogels generally involves complex chemical synthesis steps or specific conditions which limits their practical applications. Herein, a new photoresponsive hydrogel is facilely prepared via co-assembly of two simple molecules, Fmoc-Phe-OH and Azp, without chemical synthesis. The co-assembly mechanism, morphology, and photoresponsiveness of(Fmoc-Phe-OH)-Azp hydrogel are investigated by circular dichroism(CD), ultraviolet-visible(UV-Vis), fluorescence, ~1 H nuclear magnetic resonance(~1 H-NMR), attenuated total internal reflection Fourier transform Infrared(ATR-FTIR) spectroscopy, and scanning electron microscopy(SEM). Furthermore, the enhanced release of encapsulated sulforhodamine B(SRB) dye molecules can be achieved via UV light irradiation. The enhanced dye release amount can be controlled by manipulating photoirradiation time. This study provides a facile way to prepare photoresponsive hydrogel which holds great potential for controllable drug release.

Organic photoresponsive materials for information storage:a review

Organic photoresponsive materials can undergo various reversible variations in certain physical and chemical properties,such as optical properties,electrochemical properties,conformation,and conductivity,upon photoirradiation.They have been widely applied in various optoelectronic fields,especially in information storage.We summarize research progress on organic photoresponsive materials for information storage.First,the design strategies and photoswitching mechanisms for various kinds of organic photoresponsive materials,including small organic molecules,metal complexes,polymers,supramolecules,and cholesteric liquid crystals,are systematically summarized.These materials exhibit reversible changes of absorption and/or emission properties in response to different wavelengths of light.Subsequently,the applications of these organic materials in information storage,such as data(re)writing and erasing,encryption and decryption,and anticounterfeiting,are introduced in detail.Finally,the current challenges and future directions in this rapidly growing research field are discussed.The review will provide important guidance on the future works about the design of excellent organic photoresponsive materials for optoelectronic applications.

Photoresponsive organic field-effect transistors involving photochromic molecules

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.

Photoresponsive aggregation-induced emission polymer film for anti-counterfeiting

The development of solid-state smart materials, in particular those showing photoresponsive luminescence, is highly desirable for their cutting edge applications in displays, sensors, data-storage, and anticounterfeiting. However, to achieve both excellent photoresponsive performance and bright luminescence in solid state remains challenge. Herein, we integrate a novel photochromic fluorophore YL into flexible polymer chains, thereby enabling the resultant polymer PYL with reversible photoisomerization upon aggregation. Remarkably, the polymer PYL possesses excellent photochromic properties and aggregationinduced emission(AIE) activity, which can be attributed to the photoactive YL moiety. Upon light exposure, its film exhibits reversibly off-to-on fluorescent modulation with quick response, high emission efficiency and signal contrast, sharply different from the weak emission in solution. The novel photoresponsive AIE polymer with invisible/visible color and fluorescence transformation allows for advanced anti-counterfeiting applications. This work provides an efficient platform for constructing solid-state photocontrollable luminescent materials.

Preparation of Photoresponsive PAN-NH_(2)@EPESP Fiber Films with Mechanical Stability for Regulating Wettability and Micro-environment Humidity

In view of the current living micro-environment and requirements of green economy,intelligent light-responsive humidification materials have become a hot spot in intelligent polymer materials.In this work,reversible photoresponsive films with a mechanical stability and an excellent humidity adjustment performance are developed by modifying epoxy-ether-spiropyran(EPESP)on amino-nanofibers(PAN-NH2),which was produced through electrospinning.Such smart films for regulating wettability and micro-environment humidity can be reversibly manipulated by the simple switch of UV and visible light irradiation because of the unique transformation between polar ring-opened status and nonpolar ring-closed status of the spiropyran units.The effects of EPESP modification amount on the morphology,wettability,tensile strength and the ability to regulate humidity were investigated in detail.The results show that with the increase of modification amount of EPESP,both the humidity regulation and tensile strength increased;when the modification amount exceeds 7 mg,the range of regulating humidity increases slowly.

Host–Guest Interaction Driven Peptide Assembly into Photoresponsive Two-Dimensional Nanosheets with Switchable Antibacterial Activity

Selectively controlling the bioactivity of antimicrobial peptides is not only a fascinating scientific challenge but also a necessity in localized antibacterial therapy.Here,a smart antimicrobial system has been fabricated via host–guest driven dynamic selfassembly between a branched cyclodextrin and cationic linear peptides appended with azobenzene side chains.The self-assembly structure of the host–guest system could be controlled reversibly through the photoresponsive isomerization of azobenzene moieties.

Azopyridine-imidacloprid derivatives as photoresponsive neonicotinoids

A series of imidacloprid derivatives containing an azopyridine motif as a photoswitchable functional group were designed and synthesized. The new version of photoresponsive imidacloprid analogues showed improved solubility in comparison with their azobenzene analogues. 1.2 to 2-fold activity difference was observed for these azopyridine-imidacloprids against house fly （Musca domestica） and cowpea aphid （Aphis craccivora） upon irradiation.

Construction of Photoresponsive Supramolecular Micelles Based on Ethyl Cellulose Graft Copolymer

In this work, a UV-Visible light controlled supramolecular system based on ethyl cellulose （EC） was constructed, combining the host-guest interaction of β-cyclodextrin （β-CD） group and trans-isomer of azobenzene （tAzo） group. To link β-CD to the hydrophobic section, renewable EC was used as macroinitiator to initiate the polymerization of ε-caprolactone （ε-CL） to form biocompatible and biodegradable comb copolymer EC-g-PCL, and β-CD was attached to the end of PCL side chain via click reaction. Meanwhile, hydrophilic PEG-tAzo was obtained by N,N＇-dicyclohexylcarbodiimide （DCC） coupling. Then, the structures of the products were characterized by nuclear magnetic resonance （NMR） and gel permeation chromatography （GPC）. Subsequently, with the formation of inclusion complexes by β-CD and tAzo groups, the obtained EC-g-PCL-β-CD/PEG-tAzo supramolecular system self-assembled in water with hydrophobic EC-g-PCL-β-CD as core and hydrophilic PEG-tAzo as shell. Furthermore, dynamic light scattering （DLS） and transmission electron microscopy （TEM） were utilized to investigate the particle size and size distribution, while NMR and UV-Vis spectra were applied to explore the UV-Visible light stimuli-responsiveness of the micelles.

Significant enhancement of photoresponsive characteristics and mobility of MoS2-based transistors through hybridization with perovskite CsPbBr3 quantum dots

Inorganic perovskite CsPbBr3 quantum dots (QDs) are potential nanoscale photosensitizers;moreover,two-dimensional (2-D) molybdenum disulfide (MoS2) has been intensively studied for application in the active layers of optoelectronic devices.In this study,heterostructures of 2D-monolayered MoS2 with zero-dimensional functionalized CsPbBr3 QDs were prepared,and their nanoscale optical characteristics were investigated.The effect of n-type doping on the MoS2 monolayer after hybridization with perovskite CsPbBr3 QDs was observed using laser confocal microscope photoluminescenca (PL) and Raman spectra.Field-effect transistors (FETs) using MoS2 and the MoS2-CsPbBr3 QDs hybrid were also fabricated,and their electrical and photoresponsive characteristics were investigated in terms of the charge transfer effect.For the MoS2-CsPbBr3 QDs-based FETs,the field effect mobility and photoresponsivity upon light irradiation were enhanced by ~ 4 times and a dramatic ~ 17 times,respectively,compared to the FET prepared without the parovskite QDs and without light irradiation.It is noteworthy that the photoresponsivity of the MoS-2-CsPbBr3 QDs-based FETs significantly increased with increasing light power,which is completely contrary to the behavior observed in previous studies of MoS2-based FETs.The increased mobility and significant enhancement of the photoresponsivity can be attributed to the n-type doping effect and efficient energy transfer from CsPbBr3 QDs to MoS2.The results indicate that the optoelectronic characteristics of MoS2-based FETs can be significantly improved through hybridization with photosensitive parovskite CsPbBr3 QDs.

On Radioactivity–Exposed Nanophotodetector Optoreliability

The optoelectronic reliability of representative radioactivity-exposed nanophotodetectors and the degree of functionally tolerable radioactivity-induced responsivity de-emphasis, against increasing cumulative radioactivity-dose, is notionally considered and modelled, with a view towards experimental findings concerning p-i-n photosensors being exposed to regulated successive (α, β)-particle bombardments.

Synthesis, Characterization and Photoinduced Cis-Trans Isomerisation Studies on Lignin Modified with 4-[(E)-2-(3-hydroxynaphthalen-2-yl)diazen-1-yl] Benzoic Acid

In the present study, a photoresponsive chromophoric system such as 4-[(E)-2-(3-hydro xynaphthalen-2-yl)diazen-1-yl] benzoic acid was incorporated on to lignin core by functional transformation reactions and the photoresponsive beha-vior of the green, environment friendly product was investigated. The end hydroxyl group of lignin was modified with the chromophoric systems by DCC coupling. The chromophoric systems as well as the chromophore-bound biopolymer core systems were purified by column chromatography. The products were characterized by UV-visible, fluorescence, FT-IR and NMR spectroscopic methods. The results of the studies show that incorporation of the chromophoric system on to the lignin core enhanced the light absorption, emission and light stabilization properties of the chromophoric system. The light fastening properties of chromophoric system and the modified product were compared. It shows that stability of the chromophoric system greatly enhanced on attaching to the polymeric system. The trans-cis photoisomerisation and the reverse cis-trans thermal conversions were also assisted by the lignin core. The remarkable stability on irradiation shows that this is a novel photoresponsive system with excellent light fastening properties which would find application in coating materials, dyes, paints, inks, therapeutic agents and many more.

Effects of surface adsorbed oxygen, applied voltage, and temperature on UV photoresponse of ZnO nanorods

The ultraviolet（UV） photoresponses of ZnO nanorods directly grown on and between two micro Au-electrodes by using electric-field-assisted wet chemical method are measured comprehensively under different conditions, including ambient environment, applied bias voltage, gate voltage and temperature. Experimental results indicate that the photoresponses of the ZnO nanorods can be modulated by surface oxygen adsorptions, applied voltages, as well as temperatures. A model taking into account both surface adsorbed oxygen and electron-hole activities inside ZnO nanorods is proposed. The enhancement effect of the bias voltage on photoresponse is also analyzed. Experimental results shows that the UV response time（to 63%） of ZnO nanorods in air and at 59°C could be shortened from 34.8 s to 0.24 s with a bias of 4 V applied between anode and cathode.

Analysis of optoelectronic properties of TiO_2 nanowiers/Si heterojunction arrays

The optoelectronic properties of n-TiO2NW/p-Si heterojunction fabricated by depositing TiO2 nanowires on a p-Si substrate are studied. Under excitation at a wavelength of 370 nm, the TiO2 nanowires produce a light emission at 435 nm due to the emission of free excitons. The I-V characteristics are measured to investigate the heterojunction effects under the dark environment and ultraviolet （UV） illumination, n-TiOzNW/p-Si has a p-n junction formed in the n-TiOz/p-Si beterojunction. TiO2NW/Si photodiode produces a pbotocurrent larger than dark current under UV illumination. It is observed that UV photons are absorbed in TiO2 and the heterojunction shows a 0.034-A/W responsivity at 4-V reverse bias.

Fabrication of azobenzene-functionalized porous polymers for selective CO_(2) capture

Many solid adsorbents have been prepared for the CO_(2)capture.In particular,the photoresponsive adsorbents have attracted extensive interests because of their tunable pore structure and variable responsive behaviors provoked by the external light.However,it is challenging to fabricate the photoresponsive adsorbents featured the big CO_(2)capacity and high CO_(2)selectivity.Herein,copolymerized between 4-phenylazobenzoyl chloride,2,4,6-trichloro-1,3,5-triazine and melamine,a series of azobenzenefunctionalized porous polymers(PTM-AZOs)are successfully synthesized.The PTM-AZOs are verified in possession of proper pore structures,large surface area and photoconductive properties through a series of characterization.The PTM-AZO-2 with the trans-isomerization exhibits the best CO_(2)adsorption amount of 2.7 mmol·g^(-1)(273 K and 0.1 MPa),while the CO_(2)/N_(2)selectivity can reach 2459 and 607 on the trans-and cis-isomerization,respectively.The regulatable pore structures controlled by the photoresponsive azobenzene groups affect the CO_(2)capture performance of the PTM-AZOs.

Photoresponse Characteristics of Chamaenerion spp. in Mount Shergyla

Chamaenerion spp.( Onagraceae) are a class of ecological restoration medicinal herbs. Mount Shergyla has three species and one variant of Chamaenerion. Studying their photoresponse characteristics and elucidating their adaptation and physiological response to the photosynthetic characteristics of the environment is the basis for the development and protection of the plant resources of the genus Chamaenerion. In this experiment,Li-6400 portable photosynthesis instrument was used to study the photoresponse characteristics of C. spp. in Mount Shergyla,and the photoresponse curves were fitted using a right-angle hyperbolic correction model. The results showed that Chamaenerion conspersum has low light compensation point[4. 931 μmol/( m^2·s) ],high light saturation point[1 000 μmol/( m^2·s) ],and strongest adaptability to light,which is one of the determinants of its distribution at each elevation of Mount Shergyla. Chamaenerion angustifolium subsp. circumvagum has higher light compensation point [11. 848 μmol/( m^2·s) ],low light saturation point[800 μmol/( m^2·s) ],and weakest adaptability to light,and it is a typical sciophilous plant. This result is consistent with the habitats( Rhododendron wardii shrub and spruce forest margin) that C. angustifolium are distributed in Mount Shergyla. C. angustifolium and Chamaenerion latifolium have higher light compensation points and higher light saturation points,suggesting that the adaptability of C. angustifolium and C. latifolium to the light environment is weak. This can also explain the narrow distribution of C. angustifolium and C. latifolium in Mount Shergyla. There are certain degree of differences in the responses of net photosynthetic rate( Pn),intercellular CO_2 concentration( Ci),stomatal conductance( Gs) and transpiration rate( Tr) of the three species and one variant of Chamaenerion to different photosynthetically active radiation( PAR). With the increase of light intensity,the Pn,Gs and Tr of Chamaenerion spp. increased significantly,and the Ci decreased. The Pn of C. conspersum and C. latifolium differed insignificantly,but they were both higher than that of C. angustifolium. The Pn of C. angustifolium subsp. circumvagum was the lowest. The Gs of C. conspersum and C. latifolium differed insignificantly,but they were both higher than that of C. angustifolium subsp. circumvagum. The Gs of C. angustifolium was the lowest. There was no obvious difference in Ci between C. angustifolium and C. latifolium,of which the Ci was both higher than that of C. conspersum. The Ci of C. angustifolium subsp. circumvagum was the lowest. C. angustifolium subsp. circumvagum had the highest Tr,followed by C. angustifolium and C. conspersum( no obvious difference),and C. latifolium had the lowest Tr. The light utilization efficiency of C. spp. ranked as C. angustifolium subsp. circumvagum < C. angustifolium < C. latifolium < C. conspersum. The light suppression phenomenon was evident in C. angustifolium,C. angustifolium subsp. circumvagum and C. latifolium. C. conspersum is most suitable for application under high light intensity conditions in Tibet. C. angustifolium,C. angustifolium subsp. circumvagum and C. latifolium should be shaded properly under conditions of high light intensity in the cultivation process,while C. conspersum needs to be supplemented with light during the cultivation process.

Enhanced ultraviolet photoresponse based on ZnO nanocrystals/Pt bilayer nanostructure

The development of solution strategies for Zinc oxide （ZnO） quantum dots provides a pathway to utilizing ZnO nanocrystal thin films in optoelectronic devices. In this work, quasi-spherical ZnO quantum dots with a diameter of 5 nm are synthesized by using ethanol as a solvent. ZnO nanocrystal thin film is obtained by spin-coating ZnO quantum dots on a Au interdigital electrode （IDE）/AI203 substrate and annealing at different temperatures in order to yield the optimal pho- tosensitive on/off ratio of ZnO. For further enhancing the responsivity, ion sputtering is utilized to deposit Pt nanoparticles on the surface of ZnO nanocrystal thin film, the responsivity of the ZnO/Pt bilayer nanostructure increases from 0.07 A/W to 54 A/W, showing that the metal/inorganic nanocrystal bilayer nanostructure can be used to improve the performance of optoelectronic devices. The excellent properties of ZnO/Pt bilayer nanostructure have important applications in future electronic and optoelectronic devices.