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]).

Phototactic Poly(N-isopropyl acrylamide)Microgels with Photoresponsive Property

Smart functional microgels hold great potential in a variety of applications,especially in drug transportation.However,current drug carriers based on physiological internal stimuli cannot efficiently orientate to designated locations.Therefore,it is necessary to introduce the self-propelled particles to the drug release of the microgels.In order to study self-propulsion of microgels induced by light,it is also a challenge to prepare micronsized microgels so that they can be observed directly under optical microscopes.In this work,phototactic microgels with photoresponsive properties are prepared.The microgel particles can be observed by confocal laser scanning microscopy.The photoresponsive properties of microgels are fully investigated by various instruments.Light can also regulate the state of the microgel solution,making it switch between turbidity and clarity.The phototaxis of particles irradiated by UV light was studied,which may be used for microgels enrichment and drug transportation and release.

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.

Supramolecular photoresponsive polyurethane with movable crosslinks based on photoisomerization of azobenzene

Light-driven actuators are widely used for smart devices such as soft robots.One of the main challenges for actuators is achieving rapid responsiveness,in addition to ensuring favorable mechanical properties.Herein,we focused on photoresponsive polyurethane(CD-Azo-PU)based on controlling the crystallization of the hard segments in polyurethane(PU)by complexation between azobenzene(Azo)and cyclodextrins(CDs).CD-Azo-PU incorporated polyurethane as the main chain and a 1:2 inclusion complex between Azo andγCD as a movable crosslink point.Upon ultraviolet light(UV,λ=365 nm)irradiation,the photoresponsiveness of CD-Azo-PU bent toward the light source(defined as positive),while that of the linear Azo polyurethane(Azo-LPU)without peracetylatedγ-cyclodextrin diol(TAcγCD-diOH)as a movable crosslinker bent in the direction opposite the light source.The bending rates were determined to be 0.25◦/s for CD-Azo-PU and 0.083◦/s for Azo-LPU,indicating that the bending rate for CD-Azo-PU was faster than that for Azo-LPU.By incorporating movable crosslinks into CD-Azo-PU,we successfully achieved specific photoresponsive actuation with an enhanced rate.

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.

Photoresponsive nucleic acids for gene regulation

For the main purpose of manipulating the functions of molecules, researchers have made great achievements on photoresponsive molecules using light as a trigger. Light has become a promising scientific tool due to it being a clean and noninvasive external stimulant. By attachment of photoresponsive moieties to molecules, the biological activities of molecules can be attenuated by light activation. With wide applications of laser in life sciences, it will be possible to achieve high spatiotemporal resolution. In this review, we focus on photoresponsive nucleic acids for photomodulating gene expression with light activation. With incorporation of photoswitchable or photocleavable moieties, biological behaviors of nucleic acids are photoregulated reversibly or irreversibly. Recent development and applications of photoresponsive nucleic acid in vitro and in vivo have shown a very promising future for manipulation of specific functional genes or disease genes. We expect that photoresponsive nucleic acids will be powerful scientific tools for studying biological events as well as gene therapy agents for genetic diseases.

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.

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.

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.

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.

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.

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.

Enhancement of photoresponsive electrical characteristics of multilayer MoS2 transistors using rubrene patches

Multilayer MoS2 is a promising active material for sensing, energy harvesting, and optoelectronic devices owing to its intriguing tunable electronic band structure. However, its optoelectronic applications have been limited due to its indirect band gap nature. In this study, we fabricated a new type of phototransistor using multilayer MoS2 crystal hybridized with p-type organic semiconducting rubrene patches. Owing to the outstanding photophysical properties of rubrene, the device characteristics such as charge mobility and photoresponsivity were considerably enhanced to an extent depending on the thickness of the rubrene patches. The enhanced photoresponsive conductance was analyzed in terms of the charge results of the nanoscale laser confocal time-resolved PL measurements. transfer doping effect, validated by the microscope photoluminescence （PL） and

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.

Spontaneous Cracking of Graphite Oxide Sheet on Oxygen Deficient ZnO Film

Graphite oxide （GO） is an important material of wide applications. Owing to its good mechanical property, the GO sheet is always expected to be stable and remains flat on various substrates. Here we demonstrate for the first time an unexpected behavior of the GO sheet on oxygen deficient ZnO film, namely the spontaneous cracking of the entire GO sheet into many small pieces. This unusual behavior has been carefully investigated by a series of control experiments and SEM, XPS and PL measurements. It is anticipated that the oxygen vacancies in the oxygen deficient ZnO film can annihilate epoxy groups of the GO sheet, resulting in the unzipping of the aligned epoxy groups on GO sheet. A prototype of the white light detector made from the cracked GO sheet is fabricated and the device demonstrates high stability and good reproducibility.