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Chemistry-An Asian Journal · 2019 ·Vol. 14 ·期 16 ·2838-2845 · IF 3.698

Photo-/Baso-Chromisms and the Application of a Dual-Addressable Molecular Switch

Danyang Liu,Binhong Yu,Xing Su,Xiaojun Wang,Yu-Mo Zhang,Minjie Li,Sean Xiao-An Zhang

Graphical Strong as an OX : A dual-addressable molecule (SP- OX-NO 2 ) containing spiropyran (SP) and benzoxazine (OX) was designed by sharing indole in a single molecular system. The bidirectional switching property could be controlled with the stimuli of visible light or base in solution. Further, SP-OX-NO 2 was applied in rewritable paper displaying multicolor with different stimuli including visible light, base and heat. Two typical molecular switches of spiropyran (SP) and benzoxazine (OX) were fused by sharing an indole to achieve a new dual-addressable molecular switch (SP-OX-NO 2 ). Through proper molecular modification with NO 2 , the transformation from merocyanine (MC) to ring-closed SP or ring-closed OX can be controlled separately with visible light or base stimuli in solution, respectively, and these processes are verified by UV-vis and NMR spectroscopy as well as control experiments. The cis -merocyanine ( cis -MC) form is involved in the basochromic process in solution. DFT calculation suggests that the bidirectional switching property of the fused SP-OX molecular switch can be controlled separately, when the OX isomer is more stable than the deprotonated SP isomer. Because of the significant color variations in solution, the simple dual-addressable switch has been further successfully applied to construct a multicolor reversible display on paper.

研究领域: 化学 · 材料科学
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Molecular Catalysis · 2019 · IF 2.938

Molecular switch manipulating Prelog priority of an alcohol dehydrogenase toward bulky-bulky ketones

Guochao Xu,Wei Dai,Yue Wang,Lu Zhang,Zewen Sun,Jieyu Zhou,Ye Ni

Structure-guided rational design revealed the molecular switch manipulating the Prelog and anti-Prelog priorities of an NADPH-dependent alcohol dehydrogenase toward prochiral ketones with bulky and similar substituents. Synergistic effects of unconserved residues at 214 and 237 in small and large substrate binding pockets were proven to be vital in governing the stereoselectivity. The ee values of E214Y/S237A and E214C/S237 G toward (4-chlorophenyl)-(pyridin-2-yl)-methanone were 99.3% ( R ) and 78.8% ( S ) respectively. Substrate specificity analysis revealed that similar patterns were also found with (4’-chlorophenyl)-phenylmethanone, (4’-bromophenyl)-phenylmethanone and (4’-nitrophenyl)-phenylmethanone. This study provides valuable evidence for understanding the molecular mechanism on enantioselective recognition of prochiral ketones by alcohol dehydrogenase.

研究领域: 生物化学 · 酶学
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TALANTA · 2018 · IF 4.244

A label-free triplex-to-G-qadruplex molecular switch for sensitive fluorescent detection of acetamiprid

Xiaomin Tang,Xiaotong Li,Dik-Lung Ma,Lihua Lu,Baohan Qu

The detection and monitoring of acetamiprid has drawn extensive attentions, due to their potential threat to human health. Herein, a simple, sensitive and label-free fluorescent assay based on triplex-to-G-qadruplex (TTGQ) molecular switch, was developed for the assay of acetamiprid in aqueous solution. In this detection, the proposed TTGQ molecule contained the acetamiprid aptamer sequence at its loop part and the triple-helix structure at its stem part. One single-stranded DNA grafted by two split G-rich DNA sequences at its two ends, participated in the assembly of the triplex part in TTGQ. In the presence of acetamiprid, TTGQ was dissociated, and the split G-rich DNA was released out to result in the fluorescent signal enhancement of a G-quadruplex's probe. By virtue of this TTGQ molecular switch, the proposed assay can sense acetamiprid at the concentration as low as 2.38 nM with excellent selectivity . Furthermore, the detection of acetamiprid in three kinds of foods extract demonstrated the high application potential of the detection platform in the field of food safety. Compared with the other reported strategies for acetamiprid assay, this triplex-to-G-qadruplex-based fluorescent molecular switch was just composed of two DNA probes without the labeling procedure, presenting a really simple and low-cost fluorescent detection for acetamiprid assay.

研究领域: 生物化学 · 食品安全 · 分析化学
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ANALYST · 2018 ·Vol. 143 ·期 8 ·1881-1889 · IF 3.864

Dynamic mapping of spontaneously produced H2S in the entire cell space and in live animals using a rationally designed molecular switch

Linlin Yang,Jun Zhao,Xinling Yu,Ruilong Zhang,Guangmei Han,Renyong Liu,Zhengjie Liu,Tingting Zhao,Ming-Yong Han,Zhongping Zhang

Hydrogen sulfide (H2S) is a key signaling molecule in the cytoprotection, vascular mediation and neurotransmission of living organisms. In-depth understanding of its production, trafficking, and transformation in cells is very important in the way H2S mediates cellular signal transductions and organism functions; it also motivates the development of H2S probes and imaging technologies. A fundamental challenge, however, is how to engineer probes with sensitivity and cellular penetrability that allow detection of spontaneous production of H2S in the entire cell space and live animals. Here, we report a rationally designed molecular switch capable of accessing all intracellular compartments, including the nucleus, lysosomes and mitochondria, for H2S detection. Our probe comprised three functional domains (H2S sensing, fluorescence, and biomembrane penetration), could enter almost all cell types readily, and exhibit a rapid and ultrasensitive response to H2S (≤120-fold fluorescence enhancement) for the dynamic mapping of spontaneously produced H2S as well as its distribution in the whole cell. In particular, the probe traversed blood/tissue/cell barriers to achieve mapping of endogenous H2S in metabolic organs of a live Danio rerio (zebrafish). These results open-up exciting opportunities to investigate H2S physiology and H2S-related diseases.

研究领域: 细胞生物学 · 生物化学 · 医学影像学
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ANALYST · 2019 ·Vol. 144 ·期 17 ·5245-5253 · IF 4.019

Triple-helix molecular-switch-actuated exponential rolling circular amplification for ultrasensitive fluorescence detection of miRNAs

Yihan Zhao,Yu Wang,Su Liu,Chonglin Wang,Jiaxu Liang,Shasha Li,Xiaonan Qu,Rufeng Zhang,Jinghua Yu,Jiadong Huang

We have formulated a rapid and high-efficiency fluorescent biosensing platform based on a target-activated triple-helix molecular switch (THMS)-conformation-change-induced exponential rolling circular amplification (RCA) strategy for the ultrasensitive detection of miR-21. In this strategy, there are several aspects that are worthwhile. First, the functionalized THMS, comprising a typical triplex structure (T-A·T), specific recognition sequence for nicking endonuclease, complementary sequence for miR-21, and RCA product-annealing sequence, was concurrently used to perform signal transduction with one fluorophore and one quencher. As compared to the traditional double-helix molecular switches or molecular beacons, one of the biggest differentiating factors is that the properties of THMSs are independent of any specific binding sequence that they may contain. As far as we know, this is the first time that an ingeniously designed THMS not only contains the primer for exponential RCA, but also functions as the tracer for fluorescence assay. In the presence of miR-21, targets can induce conformation changes in THMS with the release of the trapped DNA segment (P), which, in turn, can activate the first run of the RCA process. Meanwhile, the RCA reaction is also initiated by the formation of a similar primer (SP) as the trapped DNA through a continuous “extension-nicking” reaction. Secondly, the resultant first-generation RCA product consists of numerous tandem repeated regions that can attach to countless THMSs, resulting in the release of the trapped DNA segment (P) for initiating the second run of the RCA reaction. Significantly, a large amount of THMSs were continuously consumed to yield a remarkably strong fluorescent signal. In addition, this biosensor was demonstrated to exhibit improved sensitivity owing to the high efficiency and rapid amplification kinetics of the exponential RCA and high selectivity toward miR-21 with a limit of detection as low as 1.1 aM. Hence, the target-mediated THMS-conformation-change-initiated exponential RCA strategy presents an optimal detection performance toward analytes for potential applications in related fundamental research and clinical diagnosis.

研究领域: 分子生物学 · 生物化学 · 医学诊断
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JOURNAL OF PHYSICAL ORGANIC CHEMISTRY · 2016 ·Vol. 30 ·期 1 ·e3584 · IF 1.515

Design, syntheses and photochromic properties of dithienylcyclopentene optical molecular switches

Chuanming Yu,Bingcheng Hu,Cheng Liu,Jiting Li

A kind of basal diarylethene through an easy synthetic procedure was synthesized and characterized, and a Suzuki coupling reaction was frequently operated to obtain the diarylethenes derivatives with some vivid functional groups like bromo, amido and pyridine. Two methods for derivatives of these switches contain porphyrins were described. All of their spectroscopic and photochromic properties were studied and intercompared. It is indicated that the difference in electron densities of the π-conjugated system of the closed forms has effects upon the absorption maxima in visible region of UV–Vis spectra. Dithienylcyclopentenes linked to porphyrins could emit luminescence substantially that display potentials to be used in the applications of nondestructive readout upon binary data storage and smart materials.

研究领域: 有机化学 · 材料科学 · 光化学
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NEW JOURNAL OF CHEMISTRY · 2022 ·Vol. 46 ·期 40 ·19118-19123 · IF 3.925

A simple fluorescent switch with four states based on benzothiazole-spiropyran for reversible multicolor displays and anti-counterfeiting

Danyang Liu

A fluorescent molecular switch (SP-OX-HBT), designed by fusing spiropyran with 2-(2-hydroxyphenyl)benzothiazole (HBT), exhibited red, orange and dark emission color switching among four states in the solution and solid states. The transformation from merocyanine (SP-OX-HBT) to ring-closed spiropyran (SP-HBT-C) or deprotonated ring-closed spiropyran (SP-HBT-CN) could be controlled by visible light or base stimuli, respectively, and these processes are verified by UV-vis spectra. The deprotonated merocyanine form (MC-N) was briefly involved in the basochromic process in solution but stable in the solid state. Besides the significant visible and fluorescent color variations, the single molecular switch has been further successfully applied to construct reversible multicolor displays and for anti-counterfeiting.

研究领域: 化学 · 材料科学 · 光学
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ACS Applied Materials & Interfaces · 2024 · IF 8.3

Multistimuli-Responsive Soft Actuators with Controllable Bionic Motions

Xueting Wang,Wei Zhao,Xinlin Li,Liwu Liu,Jinsong Leng,Yanju Liu

Soft actuators with biomimetic self-regulatory intelligence have garnered significant scientific interest due to their potential applications in robotics and advanced functional devices. We present a multistimuli-responsive actuator made from a carbon nitride/carbon nanotube (CN/CNTs) composite film. This film features a molecular switch based on reversible hydrogen bonds, whose asymmetric distribution endows the film with the ability to absorb water unevenly and convert molecular motion into macroscopic movement. By incorporating carboxylated CNTs, the film demonstrates improved mechanical properties and actuation performance. Under ambient humidity stimuli, the actuator can autonomously generate walking and tumbling motions. The CN/CNTs composite film’s actuating behaviors are programmable, enabling diverse deformation modes and complex biomimetic movements. Additionally, the film exhibits excellent photothermal conversion efficiency (74.10 °C/s), allowing for temperature and light-responsive actuation, which can be remotely controlled in real time. These features have enabled the creation of soft robots capable of complex biomimetic actions such as jumping, directional movement, and transporting objects. This research broadens the potential applications of CN-based actuators and paves the way for the development of intelligent soft robots.

CAS / MDL: 593-85-1
研究领域: 材料科学 · 仿生学 · 智能机器人
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ELECTROCHIMICA ACTA · 2025 · IF 5.6

Electrochemical synthesis and photochromic properties of eight-member cyclic azobenzenes

Xinyuan Sun,Dan Li,Qianqian Niu,Yan Liu,Dandan Zhang,Longjiu Cheng,Baokang Jin

Cyclic azobenzenes are capable of undergoing reversible cis-trans isomerization upon visible light irradiation, making them promising candidates as molecular photoswitches for applications in biological systems. However, their synthesis remains challenging due to their unique structural features. In this study, two eight-membered cyclic azobenzenes, namely 12H-dibenzo[b,f][1,4,5]thiadiazocine ( 13 ) and 12H-dibenzo[b,f][1,4,5] oxadiazocine ( 14 ), were synthesized through electrochemical reduction of 2’-nitrobenzyl-2-nitrophenyl-sulfide ( 1 ) and 1-nitro-2-((2’-nitrobenzyl)oxy)benzene ( 2 ), respectively, in the presence of CO₂. The synthesis yielded high conversion rates ( 13 : 85.98%, 14 : 93.76%). Using in situ infrared spectroscopy, NMR, and MS, detailed reduction mechanisms were elucidated, revealing an irreversible 8-electron transfer process and CO₂ involvement in a four-step reaction pathway. UV-Vis spectroscopic analysis showed that both 13 and 14 undergo trans-to-cis isomerization upon exposure to yellow (520 nm) or red (630 nm) light, in agreement with theoretical calculations. Additionally, S0→S1 excitations of both cis and trans isomers are predominantly governed by n→π* transitions. It is found that the cis conformation of compounds 13 and 14 is more stable than the trans conformation. Under yellow or red light irradiation, they undergo rapid trans-to-cis isomerization. No photochemical fatigue was observed in the cyclic experiments at room temperature, indicating their excellent photostability and potential application in photopharmacology. This work offers a sustainable strategy for the synthesis of cyclic azobenzenes and CO₂ capture.

CAS / MDL: 1923-70-2
研究领域: 有机化学 · 材料科学 · 光化学
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Chemistry-An Asian Journal · 2018 ·Vol. 13 ·期 9 ·1206-1212 · IF 3.692

A Multi-Stimuli-Responsive Oxazine Molecular Switch: A Strategy for the Design of Electrochromic Materials

Xiaojun Wang,Chang Gu,Hongzhi Zheng,Yu-Mo Zhang,Sean Xiao-An Zhang

A multi-state and multi-stimuli-responsive oxazine molecular switch that combines an electro-base property and sensitive base/acid-responsive properties was designed and synthesized. The multi-state structures of the molecular switch, with different colors, were predicted by comparing the optical properties with reference molecules and confirmed by using NMR spectroscopy. The color-switching mechanism under stimulation with acids and bases was investigated by using DFT calculations. Three single states can be obtained and the switching is unidirectional under acid and base stimulation. The electrochromic phenomenon of the molecular switch, which combines its electro-base and base-sensitive properties, was demonstrated. An electrochromic device that exhibited good electrochromic properties with excellent reversibility (2000 cycles) and high coloration efficiency (804 cm 2 C −1 ) was successfully constructed.

研究领域: 材料科学 · 化学
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MICROCHEMICAL JOURNAL · 2023 · IF 4.8

CRISPR/Cas12a coupled with enzyme-DNA molecular switch photoelectrochemical assay for HIV nucleic acid

Lilin Qin,Fangxu Lou,Yan Wang,Yinhao Zhang,Shishi Liu,Xu Hun

Molecular switches formed by enzyme-DNA hybrid compounds combined with CRISPR-Cas12a cis -cleavage used for photoelectrochemical nucleic acid assay was fabricated. A compound, molecular switch, consisting of Taq DNA polymerase, aptamer, block DNA and methylene blue labeled primer (primer-Mb) is formed. Block DNA is assembled on the surface of MBs (block DNA-MBs), and hybridized with the primer-Mb. In the presence of Human Immunodeficiency Virus (HIV) target, molecular switches are turned on by hybridization of the target with block DNA. The Taq DNA polymerase is released and activated. The activated Taq DNA polymerase elongates the primer via the template, block DNA, which attached onto Magnetic beads (MBs). A dsDNA with Mb (dsDNA-Mb) was formed. With the assistance of Cas12a, a amplified photoelectrochemical signal was obtained and the HIV target DNA was qualified. Under the best conditions, the limit of detection (LOD) can be as low as 0.3 fM. This photoelectrochemical assay extends the tool kit of molecular nanotechnology.

CAS / MDL: 25952-53-8 6066-82-6
研究领域: 分子生物学 · 生物化学 · 纳米技术 · 病毒学
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Advanced Optical Materials · 2025 · IF 7.2

Light-Dynamic Chirality Inversion of Circularly Polarized Organic Ultralong Room-Temperature Phosphorescence Enabled by Soft Helical Superstructure

Jiao Liu,Zhen-Peng Song,Juan Wei,Jun-Jie Wu,Chi-Bo Feng,Xin-Yu Zhou,Jing-Xue Hu,Ruo-Chen Lan,Yun Ma,Bing-Xiang Li,Huai Yang,Yan-Qing Lu,Qiang Zhao

Dynamic and reversible manipulation of circularly polarized luminescence (CPL) in soft materials is highly desirable for advanced chiroptical devices, information encryption, and labeling technology. However, this remains a formidable challenge in circularly polarized organic ultralong room-temperature phosphorescence (CP-OURTP) materials. Herein, a bilayered chiral-switchable CP-OURTP system is presented, composed of a light-driven hydrazone photoswitch (M1)-doped soft helical superstructure layer and a room temperature phosphorescence (RTP) polymer layer, enabling dynamic chirality inversion in a reversible manner under alternating stimulation of 460 and 340 nm light irradiation. The obtained bilayered film exhibits CP-OURTP with a maximum absolute luminescence dissymmetry factor ( g lum ) value of 0.39 and a long-lived emission lifetime of 823 ms. Notably, the g lum values of the bilayered CP-OURTP film can be dynamically and reversibly modulated between +0.30 and−0.35 under the irradiation of light with different wavelengths over 50 cycles without fatigue, owing to the photoinduced configuration changes of M1, making the first example of dynamically and reversibly regulating the chirality inversion in CP-OURTP materials.

CAS / MDL: 9002-89-5
研究领域: 材料科学 · 光学 · 有机化学
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