Comparison of two thioxopeptide bond photoswitches in insect kinin

The photoisomerization abilities of secondary thioxopeptide bond(CS-NH) and thioxo prolyl bond(CS-N) incorporated into the C-terminal pentapeptide of insect kinin were compared.H-Phe-Phe-Ψ[CS-NH]-D-Ala-Trp-Gly-NH_2 and H-Phe-Tyr-Ψ[CS-N]- Pro-Trp-Gly-NH_2 were studied by UV-vis absorption.The isomerization energy barriers of the two segments,Ac-Phe-Ψ[CS-NH]- D-Ala-NH_2 and Ac-Tyr-Ψ[CS-N]-Pro-NH_2 picked from the two peptides,were calculated using ab initio method.The cis isomer of CS-N is more stable than th...

Modeling Structures and Spectra of Fluorescent Proteins in the Coordinate-Locking Cluster Approach: Application to the Photoswitchable Protein AsFP595

An interest in the fluorescent protein asFP595 is due to unexplained puzzles in its photophysical behavior. We report the results of calculations of structures, absorption, and emission bands in asFP595 by considering model molecular clusters in the coordinate-locking scheme. Both trans and cis conformations of the anionic chromophore are considered. Equilibrium geometry coordinates on the ground potential energy surface were optimized in the density functional theory approaches by considering both large- and reduced-size clusters. The cluster size was reduced to locate positions of the minimum energy points on the excited-state potential surface by using the configuration interaction singles approach. Vertical excitation energies and oscillator strengths were computed by using the ZINDO method. We show that consideration of large clusters mimicking the protein-containing pocket is an essential issue to calculate positions of absorption and emission bands with the accuracy compatible to experiments.

Enhancing tetraphenylethene cyclization as photoswitch

Tetraphenylethene(TPE),a star building block with promising aggregationinduced emission,has received much interest.Given that its intramolecular Woodward-Hoffmann cyclic intermediate instantaneously converts back to the original state within several picoseconds,the essentially photochromic characteristic of TPE is little investigated.Achieving a visible photocyclization of TPE is still an unsolved issue and considered as the bottleneck in the further advancement of applications.We report a strategy of attaching carbonate ester onto the TPE skeleton(TPE-4C)to enhance TPE photocyclization stability.As demonstrated,the incorporated cholesteryloxycarbonyloxy substituents in TPE-4C can increase the energy barrier for cycloreversion,thereby exhibiting extremely thermal stability of photocyclic intermediate upon UV irradiation,prolonging its lifetime from 63 picoseconds to 46 s by 7.2×10^(11)-fold.The photoinduced cyclization of TPE-4C could be monitored with naked eyes,and the photocyclization/cycloreversion is achieved by turning on/off UV light along with a relative fatigue resistance.Encapsulation of TPE-4C into the liquid crystal can induce a striking phase transformation(achiral↔chiral),which can be applicable to encode optical information.Employing carbonate ester into the TPE unit plays a vital role in enhancing the unprecedented TPE photocyclization stability,providing a toolbox to allow TPE-based photocyclization to be visually monitored.

Photoswitchable Molecular Recognition Enabled by Dithienylethene-Mediated Structural Changes of Dynamic Covalent Hydrazone Bonds

Light-induced recognition,assemblies,and materials are intensive areas of research due to their high spatiotemporal resolution.Herein,we demonstrated photoswitchable molecular recognition via dithienylethene-triggeredreversible structural regulation of dynamic covalent hydrazone bonds.By combining dithienylethenes and cyclic hemiacetals,the photochemical open-ring and closed-ring forms enabled turningoff and on the creation of awide range of hydrazones when desired.Light-induced bidirectional switching between hydrazones and their cyclization structures promoted by a neighboring carboxyl group was further achieved.By taking advantage of reversible structural changes totoggleon andoff the binding pocket,photoswitchable recognitionofmetal ionswas realized.Finally,the construction of an acylhydrazone polymer offered a facile way for light-mediated selective extraction/release.The strategies and results reported here should find applications in many contexts,such asdynamicassemblies,molecular switches,and smart materials.

A New Chirality Invertible Photoswitch:Light-Driven Axially Chiral Hydrazone Enabling Dynamic Handedness Inversion of Self-Organized Helical Superstructure

Inspired by nature,dynamic self-organized helical superstructures are becoming attractive as building blocks in soft photonic crystals and advanced chiroptical devices.Herein,a chirality invertible hydrazone photoswitch,possessing high helical twisting power(HTP)was judiciously designed and synthesized.Due to the photoinduced configuration changes of the hydrazone photoswitch,it displayed superior thermal stability and strikingly reversible HTP changes.By incorporating a novel chiral hydrazone(CH)into the liquid crystal(LC)host,a handedness invertible cholesteric liquid crystal(CLC)helical superstructure with high thermal stability and light-modulated photonic bandgap was prepared.We inferred that the mechanism of chirality inversion of the novel CH photoswitch derived from changes in the dihedral angle between the two naphthalene rings induced by hydrazone isomerization.Therefore,the influence of chemical structures on its photoresponsiveness was explored.Finally,the potential applications of this advanced light-driven CLC in soft photonic crystals,showing erasable and rewritable colorful patterns and chiroptical templates to induce handedness invertible circularly polarized luminescence were illustrated.

Rational construction of self-assembly azobenzene derivative monolayers with photoswitchable surface properties

Photo-responsive azobenzene （ABZ） derivatives with different end groups （R） as photoswitchable molecules were employed to construct self-assembled monolayers （SAMs） on silicon substrate by using 3-glycidoxypropyltrimethoxysilane （GPTS） as the bridging molecules. The assembly process was optimized by changing various parameters, including the type and concentration of ABZ derivatives, reaction time, etc. The obtained SAMs were fully characterized and evaluated using UV spectroscopy, atomic force microscope （AFM）, elllipsometer, static contact angle and X-ray photoelectron spectroscopy （XPS）. It is found that the end group property of azobenzene derivatives is critical to the obtained SAMs＇ photoresponsive properties. Compared with hydrophobic compounds （4-（4＇-aminophenylazo） benzoic acid, ABZ-CF3）, the hydrophilic compounds （4-（4＇-aminophenylazo） benzoic acid, ABZ-COOH） show excellent reversible photoswitching performance with a large contact angle change of 35° under oDtimized process, and the SAMs are removable bv thermal treatment at 240 ℃ in air for onlv 5 min.

Synthesis and photoswitching properties of azobenzene liquid crystals with a pentafluorobenzene terminal

The fluorine-substituted benzoate ester rod-shaped liquid crystals containing an azobenzene side chain linked with terminal double bonds were synthesized and characterized.The mesophase and photoswitching properties were determined by polarizing optical microscopy（POM）,differential scanning calorimetry（DSC） and UV-visible spectrometry.The rod-shaped compound 4a having an odd number of carbon atoms in the alkyl chains exhibits nematic phase and SmA type phase whereas compound 4b having an even number of carbon atoms showed only nematic phase.Both fluorinecontaining compounds 4c and 4d showed only SmA type phases.The photoswitching properties of these compounds showed a rate of trans to cis isomerization ranging 19-20 s,whereas reverse process took around 230 min in solution.These materials may be ideal in the field of optically rewritable applications where both on and off rates should be crucial.

Photoswitchable vibrational nanoscopy with sub-100-nm optical resolution

Stimulated Raman scattering(SRS)microscopy has shown superior chemical resolution due to the much narrower vibrational spectral bandwidth than its fluorescence counterpart.However,breaking the diffraction-limited spatial resolution of SRS imaging is much more challenging because of the intrinsically weak scattering cross section and inert/stable nature of molecular bond vibrations.We report superresolution SRS(SR-SRS)nanoscopy based on reversible-switchable vibrational photochromic probes integrated with point spread function engineering strategy.By introducing a Gaussian-shaped ultraviolet excitation beam and a donut-shaped visible depletion beam in addition to the pump and Stokes beams,SR-SRS could reach sub-100 nm resolution on photoswitchable nanoparticles(NPs).Furthermore,NP-treated live cell imaging was demonstrated with resolution improvement by a factor of∼4.Our proof-of-principle work provides the potential for SR vibrational imaging to assist research on complex biological systems.

Preparation and study of photoswitchable fluorescence nanoparticles based on spirobenzopyran

The preparation and performance characterization of〈50 nm spirobenzopyran-based photochromic nanocomposites with photoswitchable fluorescence are presented.The nanocomposites were fabricated by means of a modifed miniemulsion polymerization process,in which the hydrophobic spirobenzopyran was covalently attached to the polymer chains and the matched fluorescent dyes were noncovalently embedded in the nanoscale cross-linked polymeric matrix,respectively.The obtained nanocomposites with a high relative fluorescence quantum yield（Q）exhibited superior fluorescent photoswitchable performance due to the effective photo-induced intermolecular energy transfer.The stability of photomerocyanine was also improved.

A New Set of Reversibly Photoswitchable Fluorescent Proteins for Use in Transgenic Plants

Fluorescent reporter proteins that allow repeated switching between a fluorescent and a non-fluorescent state in response to specific wavelengths of light are novel tools for monitoring of protein trafficking and super-resolu- tion fluorescence microscopy in living organisms. Here, we describe variants of the reversibly photoswitchable fluores- cent proteins rsFastLime, bsDronpa, and Padron that have been codon-optimized for the use in transgenic Arabidopsis plants. The synthetic proteins, designated rsFastLIME-s, bsDRONPA-s, and PADRON C-s, showed photophysical properties and switching behavior comparable to those reported for the original proteins. By combining the ＇positively switchable＇ PADRON C-s with the ＇negatively switchable＇ rsFastLIME-s or bsDRONPA-s, two different fluorescent reporter proteins could be imaged at the same wavelength upon transient expression in Nicotiana benthamiana cells. Thus, co-localiza- tion analysis can be performed using only a single detection channel. Furthermore, the proteins were used to tag the RNA-binding protein AtGRP7 （Arabidopsis thaliana glycine-rich RNA-binding protein 7） in transgenic Arabidopsis plants. Because the new reversibly photoswitchable fluorescent proteins show an increase in signal strength during each pho- toactivation cycle, we were able to generate a large number of scans of the same region and reconstruct 3-D images of AtGRP7 expression in the root tip. Upon photoactivation of the AtGRP7：rsFastLIME-s fusion protein in a defined region of a transgenic Arabidopsis root, spreading of the fluorescence signal into adjacent regions was observed, indicating that movement from cell to cell can be monitored. Our results demonstrate that rsFastLIME-s, bsDRONPA-s, and PADRON C-s are versatile fluorescent markers in plants, Furthermore, the proteins also show strong fluorescence in mammalian cells including COS-7 and HeLa cells.

Optical control of neuronal activities with photoswitchable nanovesicles

Precise modulation of neuronal activity by neuroactive molecules is essential for understanding brain circuits and behavior.However,tools for highly controllable molecular release are lacking.Here,we developed a photoswitchable nanovesicle with azobenzene-containing phosphatidylcholine(azo-PC),coined‘azosome’,for neuromodulation.Irradiation with 365 nm light triggers the trans-to-cis isomerization of azo-PC,resulting in a disordered lipid bilayer with decreased thickness and cargo release.Irradiation with 455 nm light induces reverse isomerization and switches the release off.Real-time fluorescence imaging shows controllable and repeatable cargo release within seconds(<3 s).Importantly,we demonstrate that SKF-81297,a dopamine D1-receptor agonist,can be repeatedly released from the azosome to activate cultures of primary striatal neurons.Azosome shows promise for precise optical control over the molecular release and can be a valuable tool for molecular neuroscience studies.

Photoisomerization,assembling and fluorescence photoswitching behaviors of a water-soluble stiff-stilbene with cucurbit[7]uril

Photoresponsive supramolecular systems have merited extensive attention for their applications in materials science and life science.Here,we synthesized a water-soluble stiff-stilbene molecular photoswitch,exhibiting outstanding photoisomerization reaction between its(E)-and(Z)-configurations upon irradiation at distinct light.The photoswitch can assemble with cucurbit[7]uril(CB[7])to form a superior fluorescent supramolecular complex(compared to the only guest)with excellent water solubility,which manifested dramatic photoluminescence enhancement caused by restriction of intramolecular rotation and remained good photochromic characteristics.Furthermore,introduction of CB[7]influence photoreaction quantum yield(Φ)of the stiff-stilbene,leading to reduction ofΦ_(E→Z) and increase ofΦ_(Z→E) of the stiff-stilbene.Importantly,the photoadjustable supramolecular assembly can act as a fluorescence switch,and the phototunable guest further selectively modulate G-quadruplex structure of Tel22 upon light irradiation or with addition of CB[7].The study provides a new simple way for accurately regulating photochromic properties of molecular switches and developing smart materials with potential applications in controlled modulation of G-quadruplex,targeted biological imaging and so on.

Photoswitchable molecular dipole antennas with tailored coherent coupling in glassy composite

Here,we introduce the first experimental proof of coherent oscillation and coupling of photoswitchable molecules embedded randomly in a polymeric matrix and acting cooperatively upon illumination with UV light.In particular,we demonstrate the specular reflection and Brewster phenomenon alteration of photochromic molecular dipole antennas.We successfully demonstrate the concept of Brewster wavelength,which is based on the dipolar interaction between radiating dipoles and the surrounding matrix possessing a net dipole moment,as a key tool for highly localized sensing of matrix polarity.We also introduce the concept of‘tailored molecular photonic coupling’while highlighting the role of interferences for the design of optically active media by adjusting the photonic response of the medium with the real and imaginary refractive index of photoswitchable molecules in the‘ON’state.Our results enhance our fundamental understanding of coherent dipole radiation and open a new vein of research based on glassy disordered dipolar composites that act as macroscopic antenna with cooperative action;furthermore,these results have important implications for new design rules of tailored photonics.

螺吡喃类光致变色材料的改性与应用进展

有机光致变色材料通过紫外光与可见光照射能够发生可逆的光异构化过程,进而实现颜色的可逆变化。螺吡喃类材料作为一类光致变色性能优异的有机材料,备受研究者的关注与青睐。通过对光照、温度、酸碱度(pH)和机械压力等多种条件的调控,螺吡喃类材料能实现高效、灵敏的变色行为。基于螺吡喃类材料的光致变色聚合物、金属有机框架和微胶囊等多种变色材料在光电信息存储、智能传感器、防伪与加密、靶向药物和荧光探针等领域具备广泛的应用前景。该文综述了螺吡喃类化合物的合成与分子结构、设计与功能化,阐明了螺吡喃类材料设计与功能化的构效关系,介绍了螺吡喃类光致变色材料的应用及最新研究热点。最后,展望了螺吡喃类材料未来的应用与发展前景。

光-电协同调控的高反射率全彩色液晶器件

本文利用光-电协同调控的方法获得了具有高反射率、全彩色显示的倾斜螺旋胆甾相(ChOH)器件。在液晶体系中引入一种具有左旋旋向的手性光开关switch 1,并基于相反旋向手性添加剂的手性抵消原则,使用R811来平衡switch 1发生光致Z/E异构化前后螺旋扭曲力上的差异,使体系在光照前后对其施加相同的电场强度可以反射具有相反旋向且相同波段的红-绿-蓝三色光。在此基础上,构筑了双层结构的液晶器件,对材料进行分层光-电刺激,诱导上层螺旋结构翻转,可在双层结构中分别形成左右旋结构,从而具有全反射效应,在双层ChOH液晶器件中反射率提升约60%。本研究为制备具有高反射率的全彩色电子纸器件提供了新思路,同时也为光开关材料在液晶器件中的应用提供了有益的探索。

双键型分子光开关的E/Z异构化

适当取代的双键X=Y双键型分子能够在光的作用下发生E型和Z型之间的异构化。目前已报道的分子光开关大多是基于偶氮苯(ABs)、二芳烃乙烯(DAEs)和螺吡喃(SPs)等结构,但新的有趣的结构正在不断被报道。本文将讨论围绕C=C、C=N和N=N双键异构化的各种类型的光开关,重点介绍常用的光开关双键结构和极性质子溶剂等外界因素对其E/Z异构化的影响。

含硝基一代光致变色液晶树枝状大分子的光化学研究

研究了树外围含12个硝基偶氮苯基元新型一代碳硅烷光致变色液晶树枝状大分子G1和基元小分子M1在溶液中的最大吸收波长、摩尔消光系数、反-顺光化学异构化反应速率常数、热回复异构化反应速率常数、光化学回复异构化反应平衡常数及速率常数.G1的光致变色反应速率常数的数量级为10-1s-1,而含偶氮基元液晶聚硅氧烷的光致变色反应速率常数的数量级为10-8s-1,因此液晶树枝状大分子的光响应速率比后者快107倍.G1的光回复异构化反应平衡常数kt/kc为1.76～1.77,有作为光控开关材料的应用前景.

树形聚合物及功能化结构设计研究新进展

综述了树形聚合物的最新研究进展 ,重点介绍了近年来树形聚合物功能化结构设计及其在光、电信息及生物技术等新领域中的应用研究、发展趋势和应用前景。

亲水性二芳基乙烯荧光分子开关的研究进展

二芳基乙烯荧光分子开关因具有优良的抗疲劳性和双稳态特征而被广泛地研究与应用,亲水化成为其作为荧光开关探针走向应用的关键点之一。本文综述了亲水性二芳基乙烯荧光分子开关当前的研究进展,归纳了实现亲水性的几种重要途径和结构,分析了各种亲水化方法的优缺点,并着重介绍了亲水性二芳基乙烯荧光分子开关作为荧光开关探针在化学传感、生物传感、生物成像以及超分辨成像等领域的应用现状,并指出当前应用研究中存在的一些问题,同时也对其未来的应用前景进行了展望。

含硝基二代光致变色液晶树枝状大分子的光化学研究

研究了树外围含36个硝基偶氮苯端基新型二代碳硅烷光致变色液晶树枝状大分子(G2)在溶液中的最大吸收波长,摩尔消光系数,反-顺光异构化反应速率常数,热回复异构化反应速率常数,光化学回复异构化反应平衡常数及速率常数.G2的光致变色反应速率常数的数量级为10-1s-1,而含偶氮端基侧链聚硅氧烷的光致变色反应速率常数的数量级为10-8s-1,因此,液晶树枝状大分子的光响应速率比后者快107倍.G2的光化学回复异构化反应平衡常数kt/kc为1.77～1.97,有作为光控开关材料的应用前景.