Silicon-substituted rhodamines for stimulated emission depletion fluorescence nanoscopy

As an essential part in the toolbox of super-resolution microscopy, stimulated emission depletion(STED)nanoscopy has been widely explored in revealing the substructure and bioactivities in fluorescence imaging. Among the applied STED fluorophores, silicon-substituted rhodamines(SiRs) belong to one of the most extensively employed fluorophores. The carboxy-SiR was favored in STED bioimaging with many advantages, including reliable photostability, cell permeability, tunable fluorogenicity, feasibl...     

Far Red-Shifted CdTe Quantum Dots for Multicolour Stimulated Emission Depletion Nanoscopy

Stimulated emission depletion (STED) nanoscopy is a widely used nanoscopy technique. Two-colour STED imaging in fixed and living cells is standardised today utilising both fluorescent dyes and fluorescent proteins. Solutions to image additional colours have been demonstrated using spectral unmixing, photobleaching steps, or long-Stokes-shift dyes. However, these approaches often compromise speed, spatial resolution, and image quality, and increase complexity. Here, we present multicolour STED nanoscopy with far red-shifted semiconductor CdTe quantum dots (QDs). STED imaging of the QDs is optimized to minimize blinking effects and maximize the number of detected photons. The far-red and compact emission spectra of the investigated QDs free spectral space for the simultaneous use of fluorescent dyes, enabling straightforward three-colour STED imaging with a single depletion beam. We use our method to study the internalization of QDs in cells, opening up the way for future super-resolution studies of particle uptake and internalization.     

Self-trapped exciton emission and piezochromism in conventional 3D lead bromide perovskite nanocrystals under high pressure

Developing single-component materials with bright-white emission is required for energy-saving applications. Self-trapped exciton (STE) emission is regarded as a robust way to generate intrinsic white light in halide perovskites. However, STE emission usually occurs in low-dimensional perovskites whereby a lower level of structural connectivity reduces the conductivity. Enabling conventional three-dimensional (3D) perovskites to produce STEs to elicit competitive white emission is challenging. Here, we first achieved STEs-related emission of white light with outstanding chromaticity coordinates of (0.330, 0.325) in typical 3D perovskites, Mn-doped CsPbBr₃ nanocrystals (NCs), through pressure processing. Remarkable piezochromism from red to blue was also realized in compressed Mn-doped CsPbBr₃ NCs. Doping engineering by size-mismatched Mn dopants could give rise to the formation of localized carriers. Hence, high pressure could further induce octahedra distortion to accommodate the STEs, which has never occurred in pure 3D perovskites. Our study not only offers deep insights into the photophysical nature of perovskites, it also provides a promising strategy towards high-quality, stable white-light emission.

We first achieved self-trapped exciton emission with outstanding white-light chromaticity coordinates of (0.330, 0.325) in conventional 3D halide perovskite nanocrystals through pressure engineering.     

Synthesis of double perovskite and quadruple perovskite nanocrystals through post-synthetic transformation reactions

Lead-free halide perovskite nanocrystals (NCs) represent a group of emerging materials which hold promise for various optical and optoelectronic applications. Exploring facile synthetic methods for such materials has been of great interest to not only fundamental research but also technological implementations. Herein, we report a fundamentally new method to access lead-free Bi-based double perovskite (DP) and quadruple perovskite (or layered double perovskite, LDP) NCs based on a post-synthetic transformation reaction of Cs₃BiX₆ (X = Cl, Br) zero-dimensional (0D) perovskite NCs under mild conditions. The produced NCs show good particle uniformity, high crystallinity, and comparable optical properties to the directly synthesized NCs. The relatively slow kinetics and stop-on-demand feature of the transformation reaction allow real-time composition–structure–property investigations of the reaction, thus elucidating a cation-alloyed intermediate-assisted transformation mechanism. Our study presented here demonstrates for the first time that post-synthetic transformation of 0D perovskite NCs can serve as a new route towards the synthesis of high-quality lead-free perovskite NCs, and provides valuable insights into the crystal structures, excitonic properties and their relationships of perovskite NCs.

Lead-free perovskite nanocrystals are synthesized by post-synthetic transformation reactions. The post-synthetic transformations show the structural flexibility of zero-dimensional perovskite nanocrystal materials.     

A Multi-responsive Fluorescent Probe Reveals Mitochondrial Nucleoprotein Dynamics with Reactive Oxygen Species Regulation through Super-resolution Imaging

Understanding the biomolecular interactions in a specific organelle has been a long-standing challenge because it requires super-resolution imaging to resolve the spatial locations and dynamic interactions of multiple biomacromolecules. Two key difficulties are the scarcity of suitable probes for super-resolution nanoscopy and the complications that arise from the use of multiple probes. Herein, we report a quinolinium derivative probe that is selectively enriched in mitochondria and switches on in three different fluorescence modes in response to hydrogen peroxide (H₂O₂), proteins, and nucleic acids, enabling the visualization of mitochondrial nucleoprotein dynamics. STED nanoscopy reveals that the proteins localize at mitochondrial cristae and largely fuse with nucleic acids to form nucleoproteins, whereas increasing H₂O₂ level leads to disassociation of nucleic acid–protein complexes.     

Enzyme-activatable fluorescent probes for β-galactosidase: from design to biological applications

β-Galactosidase (β-gal), a typical hydrolytic enzyme, is a vital biomarker for cell senescence and primary ovarian cancers. Developing precise and rapid methods to monitor β-gal activity is crucial for early cancer diagnoses and biological research. Over the past decade, activatable optical probes have become a powerful tool for real-time tracking and in vivo visualization with high sensitivity and specificity. In this review, we summarize the latest advances in the design of β-gal-activatable probes via spectral characteristics and responsiveness regulation for biological applications, and particularly focus on the molecular design strategy from turn-on mode to ratiometric mode, from aggregation-caused quenching (ACQ) probes to aggregation-induced emission (AIE)-active probes, from near-infrared-I (NIR-I) imaging to NIR-II imaging, and from one-mode to dual-mode of chemo-fluoro-luminescence sensing β-gal activity.

This review highlights the molecular design strategy of β-galactosidase-activatable probes from turn-on mode to ratiometric mode, from ACQ to AIE-active probes, from NIR-I to NIR-II imaging and dual-mode of chemo-fluoro-luminescence imaging.     

Chiral assembly of organic luminogens with aggregation-induced emission

Chirality is important to chemistry, biology and optoelectronic materials. The study on chirality has lasted for more than 170 years since its discovery. Recently, chiral materials with aggregation-induced emission (AIE) have attracted increasing interest because of their fascinating photophysical properties. In this review, we discussed the recent development of chiral materials with AIE properties, including their molecular structures, self-assembly and functions. Generally, the most effective strategy to design a chiral AIE luminogen (AIEgen) is to attach a chiral scaffold to an AIE-active fluorophore through covalent bonds. Moreover, some propeller-like or shell-like AIEgens without chiral units exhibit latent chirality upon mirror image symmetry breaking. The chirality of achiral AIEgens can also be induced by some optically active molecules through non-covalent interactions. The introduction of an AIE unit into chiral materials can enhance the efficiency of their circularly polarized luminescence (CPL) in the solid state and the dissymmetric factors of their helical architectures formed through self-assembly. Thus, highly efficient circularly polarized organic light-emitting diodes (CPOLEDs) with AIE characteristics are developed and show great potential in 3D displays. Chiral AIEgens are also widely utilized as “turn on” sensors for rapid enantioselective determination of chiral reagents. It is anticipated that the present review can entice readers to realize the importance of chirality and attract much more chemists to contribute their efforts to chirality and AIE study.

This review highlights the recent development of chiral materials with aggregation-induced emission properties, including their molecular structures, self-assembly and functions.     

A universal route with fine kinetic control to a family of penta-twinned gold nanocrystals

Some of the major difficulties hindering the synthesis of different types of colloidal nanocrystals are their complex synthetic methods and the lack of a universal growth mechanism in one system. Herein, we propose a general strategy of kinetically controlled seed-mediated growth to synthesize a family of penta-twinned gold nanocrystals. Specifically, different kinds of penta-twinned nanocrystals (truncated penta-twinned decahedra, truncated bipyramids, bipyramids, truncated bipyramids with tips, star-like penta-twinned nanocrystals, decahedra with concave edges, and decahedra) with tunable sizes and high purity were readily achieved in one system solely by tailoring the deposition kinetics of adatoms on different sites of decahedral seeds. The controllable deposition kinetics can be realized by changing the ratio of reductant/gold precursors (R), which dictates whether horizontal or vertical features along the 5-fold axis direction of Au decahedral seeds are produced. Additionally, the selective growth of a second metal (silver) on penta-twinned gold seeds can be reached through minor modification of R, which opens a new avenue for mechanistic investigation by visualizing the seed localization within the final particles. The present work demonstrates a general paradigm for the kinetic growth of penta-twinned crystals and would be extended to the synthesis of other families of nanocrystals.

We report the synthesis of linear ADPr oligomers of defined length up to a pentamer using an improved solid phase method. Binding study with human oncogenic helicase ALC1 shows that ADPr oligomers bind to ALC1 in a length-dependent manner.     

Donor-Acceptor Typed AIE Luminogens with Near-infrared Emission for Super-resolution Imaging

Aggregation-induced emission(AIE)luminogens(AIEgens)with high brightness in aggregates exhibit great potentials in biological imaging,but these AIEgens are seldom applied in super-resolution biological imaging,especially in the imaging by using the structural illumination microscope(SIM).Based on this consideration,we synthesized the donor-acceptor typed AIEgen of DTPA-BTN,which not only owns high brightness in the near-infrared(NIR)emission region from 600 nm to 1000 nm(photoluminescence quantum yield,PLQYs=11.35%),but also displays excellent photo-stability.In addition,AIE nanoparticles based on 4,7-ditriphenylamine-[1,2,5]-thiadiazolo[3,4-c]pyridine(DTPA-BTN)were also prepared with highly emissive features and excellent biocompatibility.Finally,the developed DTPA-BTN-based AIE nanoparticles were applied in the super-resolution cellular imaging via SIM,where much smaller full width at half-maximum values and high signal to noise ratios were obtained,indicating the superior imaging resolution.The results here imply that highly emissive AIEgens or AIE nanoparticles can be promising imaging agents for super-resolution imaging via SIM.     

Facile fabrication of aggregation-induced emission based red fluorescent organic nanoparticles for cell imaging

A cyano-substituted diarylethlene derivative aggregation-induced emission （ALE） dye with two amino end-groups and 4,4＇-（hexafluoroisopropylidene）diphthalic anhydride were facilely incorporated into red fluorescent organic nanoparticles （FONs） via room temperature anhydride ring-opening polymerization under an air atmosphere. These obtained RO-HFDA FONs were characterized by a series of techniques including gel permeation chromatography, Fourier transform infrared spectroscopy, size distribution and zeta potential measurements, UV-Vis absorption spectrum, fluorescent spectroscopy and transmission electron microscopy. Biocompatibility evaluation and cell uptake behavior of RO-HFDA FONs were further investigated to explore their potential biomedical application. We demonstrated that such FONs showed high water dispersibility, stable uniform spherical morphology （150-200 nm）, broad excitation band （350-605 nm）, intense red fluorescence （627 nm） and excellent biocompatibility, making them promising for cell imaging applications.     

Tuning molecular aggregation to achieve highly bright AIE dots for NIR-II fluorescence imaging and NIR-I photoacoustic imaging

Currently, bright aggregation-induced emission luminogens (AIEgens) with high photoluminescence quantum yields (PLQYs) in the NIR-II region are still limited, and thus an efficient strategy to enhance NIR-II fluorescence performance through tuning molecular aggregation is proposed here. The synthesized donor–acceptor tailored AIEgen (DTPA-TBZ) not only exhibits an excellent absorptivity in the NIR-I region, but also good fluorescence signals in the NIR-II region with an emission extending to 1200 nm. Benefiting from such improved intramolecular restriction and aggregation, a significant absolute PLQY value of 8.98% was obtained in solid DTPA-TBZ. Encouragingly, the resulting AIE dots also exhibit a high relative PLQY of up to 11.1% with IR 26 as the reference (PLQY = 0.5%). Finally, the AIE dots were applied in high performance NIR-II fluorescence imaging and NIR-I photoacoustic (PA) imaging: visualization of abdominal vessels, hind limb vasculature, and cerebral vessels with high signal to background ratios was performed via NIR-II imaging; Moreover, PA imaging has also been performed to clearly observe tumors in vivo. These results demonstrate that by finely tuning molecular aggregation in DTPA-TBZ, a good NIR-I absorptivity and a highly emissive fluorescence in the NIR-II region can be achieved simultaneously, finally resulting in a promising dual-modal imaging platform for real-world applications to achieve precise cancer diagnostics.

A highly efficient dual-modal imaging platform by using bright AIE dots was constructed to achieve precise cancer diagnostics.     

Fluorescein-labeled fluoroapatite nanocrystals codoped with Yb(III) and Ho(III) for trimodal (downconversion,upconversion and magnetic resonance) imaging of cancer cells

The authors report on upconversion nanocrystals (NCs) based on a fluoroapatite (FAp) support that was engineered to enable multimodal imaging by fluorescence imaging (FI), magnetic resonance imaging (MRI), and upconversion luminescence imaging. A fluorescein based fluorophore (FITC) was incorporated into the FAp nanocrystals and then doped with Yb(III) and Ho(III) by microwave-assisted solution combustion synthesis. The hexagonal phase nanocrystals (FITC-FAp:Yb/Ho) exhibit spindle like morphology with an average diameter and length of 15 nm and 196 nm, respectively. The doping concentration of the Yb (5 %) and Ho (0.6 %) was determined by ICP-MS. The nanocrystals exhibit upconversion luminescence when irradiated with NIR light of wavelength 980 nm. The emission spectrum consists of two bands centered at 542 nm (green emission) and 654 nm (red emission) corresponding to two transitions of Ho(III). The pump power dependence of upconversion luminescence intensity confirmed the 2-photon process. The presence of FITC in the nanocrystal imparts green fluorescence (peaking at 521 nm) by a conventional downconversion process. The presence of Ho(III) endows the NCs with paramagnetism. The magnetization is 21.063 emu?g^?1 at room temperature. The NCs exhibit a longitudinal relaxivity (r1) of 0.12 s^?1?mM^?1, and a transverse relaxivity (r2) of 29 s^?1?mM^?1, which makes the system suitable for developing T2 MRI contrast agents. The nanocrystals are surface aminized using polyethyleneimine (PEI) and covalently conjugated to folic acid (FA) in order to target the folate receptors that are overexpressed in many cancer cells. The FA-conjugated nanocrystals have been tested for their applicability in fluorescence imaging of HeLa cells. Their biocompatibility, upconversion and downconversion luminescence, and magnetism render these NCs potentially powerful nanoprobes for trimodal imaging.

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Graphical abstract Fluorescein-labeled fluorapatite nanocrystals codoped with Yb(III) and Ho(III) ions (FITC-FAp:Yb/Ho) have been prepared through microwave route. The up and downconversion luminescence, biocompatibility and magnetism are explored. The folic acid conjugated nanocrystals are promising candidates for trimodal imaging (up- and downconversion imaging and magnetic resonance imaging)

     

A functional conjugated hyperbranched polymer derived from tetraphenylethene and oxadiazole moieties: Synthesis by one-pot “a4+b2+c2” polymerization and applicaion as explosive chemosensor and pled

A new conjugated hyperbranched polymer (hb-TFO) containing tetraphenylethylene (TPE) units, a famous aggregation-induced emission (AIE) active group, as the core, was synthesized successfully with modest yield via one-pot Suzuki polymerization reaction. Thanks to the introduction of TPE moieties, hb-TFO exhibited aggregation-enhanced emission (AEE) property, and could work as explosive chemosensor with high sensitivity. The polymeric light-emitting diode (PLED) device was fabricated to investigate its electroluminescent property, and hb-TFO demonstrated a maximum luminance efficiency of 0.22 cd/A and a maximum brightness of 545 cd/m² at 15.9 V.     

Aggregation-induced delayed fluorescence luminogens: the innovation of purely organic emitters for aqueous electrochemiluminescence

Due to overcoming the limitation of aggregation caused quenching (ACQ) of solid-state emitters, aggregation-induced emission (AIE) organic luminogens have become a promising candidate in aqueous electrochemiluminescence (ECL). However, restricted by the physical nature of fluorescence, current organic AIE luminogen-based ECL (AIECL) faces the bottleneck of low ECL efficiency. Here, we propose to construct de novo aqueous ECL based on aggregation-induced delayed fluorescence (AIDF) luminogens, called AIDF-ECL. Compared with the previous organic AIE luminogens, purely organic AIDF luminogens integrate the superiorities of both AIE and the utilization of dark triplets via thermal-activated spin up-conversion properties, thereby possessing the capability of close-to-unity exciton utilization for ECL. The results show that the ECL characteristics using AIDF luminogens are directly related to their AIDF properties. Compared with an AIECL control sample based on a tetraphenylethylene AIE moiety, the ECL efficiency of our AIDF-ECL model system is improved by 5.4 times, confirming the excellent effectiveness of this innovative strategy.

Electrochemiluminescence (ECL) using an aggregation-induced delayed fluorescence (AIDF) organic luminogen, i.e. AIDF-ECL, was reported for the first time, featuring “lighting” dark triplets (ca. 75% in total) for all-exciton-harvesting ECL applications.     

AIE-based nanoaggregate tracker: high-fidelity visualization of lysosomal movement and drug-escaping processes

High-fidelity imaging and long-term visualization of lysosomes are crucial for their functional evaluation, related disease detection and active drug screening. However, commercial aggregation-caused quenching probes are not conducive to precise lysosomal imaging because of their inherent drawbacks, like easy diffusion, short emission and small Stokes shift, let alone their long-term tracing due to rapid photobleaching. Herein we report a novel aggregation-induced emission (AIE)-based TCM-PI nanoaggregate tracker for direct visualization of lysosomes based on the building block of tricyano-methylene-pyridine (TCM), wherein introduced piperazine (PI) groups behave as targeting units to lysosomes upon protonation, and the self-assembled nanostructure contributes to fast endocytosis for enhanced targeting ability as well as extended retention time for long-term imaging. The piperazine-stabilized TCM-PI nanoaggregate shifts the emission maximum to 677 nm in an aqueous environment, and falls within the desirable NIR region with a large Stokes shift of 162 nm, thereby greatly reducing biological fluorescent background interference. In contrast with the commercially available LysoTracker Red, the essential AIE characteristic of high photostability can guarantee three-dimensional high-fidelity tracing with low photobleaching, and little diffusion from lysosomes, and especially overcome the AIE bottleneck to target specificity. Consequently, the AIE-based nanoaggregate tracker successfully achieves the high-fidelity and long-term tracing of lysosomal movement and even monitors the drug-escaping process from lysosomes to cell nuclei, which provides a potential tool to benefit drug screening.

Well-formed AIE nanoaggregates with good stability can achieve high-fidelity visualization of lysosomal movement and drug-escaping processes.     

Selective formation of [Au23(SPhtBu)17]0, [Au26Pd(SPhtBu)20]0 and [Au24Pt(SC2H4Ph)7(SPhtBu)11]0 by controlling ligand-exchange reaction

To use atomically precise metal nanoclusters (NCs) in various application fields, it is essential to establish size-selective synthesis methods for the metal NCs. Studies on thiolate (SR)-protected gold NCs (Au_n(SR)_m NCs) revealed that the atomically precise Au_n(SR)_m NC, which has a different chemical composition from the precursor, can be synthesized size-selectively by inducing transformation in the framework structure of the metal NCs by a ligand-exchange reaction. In this study, we selected the reaction of [Au₂₅(SC₂H₄Ph)₁₈]⁻ (SC₂H₄Ph = 2-phenylethanethiolate) with 4-tert-butylbenzenethiol (^tBuPhSH) as a model ligand-exchange reaction and attempted to obtain new metal NCs by changing the amount of thiol, the central atom of the precursor NCs, or the reaction time from previous studies. The results demonstrated that [Au₂₃(SPh^tBu)₁₇]⁰, [Au₂₆Pd(SPh^tBu)₂₀]⁰ (Pd = palladium) and [Au₂₄Pt(SC₂H₄Ph)₇(SPh^tBu)₁₁]⁰ (Pt = platinum) were successfully synthesized in a high proportion. To best of our knowledge, no report exists on the selective synthesis of these three metal NCs. The results of this study show that a larger variety of metal NCs could be synthesized size-selectively than at present if the ligand-exchange reaction is conducted while changing the reaction conditions and/or the central atoms of the precursor metal NCs from previous studies.

This study succeeded in obtaining three new thiolate protected metal nanoclusters by changing the ligand-exchange condition from previous studies.     

Fluorescent polymer cubosomes and hexosomes with aggregation-induced emission

Fluorescent polymer cubosomes and hexosomes with aggregation-induced emission (AIE) were prepared from amphiphilic block copolymers PEG-b-PTPEMA where the hydrophobic block PTPEMA was a polymethacrylate with tetraphenylethene (TPE) as the AIE side group. Four highly asymmetric block copolymers with hydrophilic block weight ratio f_PEG ≤ 20% were synthesized. Cubosomes and hexosomes with strong fluorescence emission were obtained by nanoprecipitation of polymers with f_PEG < 9% in dioxane/water and THF/water systems. Their ordered internal structures were studied by electron microscopy (cryo-EM, SEM and TEM) and the X-ray scattering technique (SAXS). To elucidate the formation mechanisms of these inverted colloids, other parameters influencing the morphologies, like the water content during self-assembly and the organic solvent composition, were also investigated. This study not only inspires people to design novel building blocks for the preparation of functional cubosomes and hexosomes, but also presents the first AIE fluorescent polymer cubosome and hexosome with potential applications in bio-related fields.

Fluorescent Im$\bar{3}$m cubosome and P6mm hexosome with aggregation-induced emission (AIE) were reported, which were formed by amphiphilic block copolymers PEG-b-PTPEMA. The length of hydrophobic block PTPEMA was adjusted to control morphology formation.     

Precision photothermal therapy and photoacoustic imaging by in situ activatable thermoplasmonics

Phototherapy holds great promise for disease treatment; however, traditional “always-on” photoagents have been restricted to clinical translation due to their nonspecific response and side effects on normal tissues. Here, we show a tumor microenvironment activated photothermal and photoacoustic agent as an activatable prodrug and probe that allows precise cancer diagnosis and treatment. Such an in situ revitalized therapeutic and contrast agent is achieved via controllable plasmonic heating for thermoplasmonic activation. This enables monitoring of signal molecule dynamics, real-time photothermal and photoacoustic imaging of tumors and lymph node metastasis, and targeted photothermal therapy without unwanted phototoxicity to normal tissues. Our study provides a practical solution to the non-specificity problem in phototherapy and offers precision cancer therapeutic and theranostic strategies. This work may advance the development of ultrasensitive disease diagnosis and precision medicine.

A tumor microenvironment-activated photoagent is reported for precise photothermal therapy and photoacoustic imaging via controllable thermoplasmonics. The agent can sensitively image tumors and lymph node metastasis and specifically ablate tumors.     

A general strategy to the intracellular sensing of glycosidases using AIE-based glycoclusters

Glycosidases, which are the enzymes responsible for the removal of residual monosaccharides from glycoconjugates, are involved in many different biological and pathological events. The ability to detect sensitively the activity and spatiotemporal distribution of glycosidases in cells will provide useful tools for disease diagnosis. However, the currently developed fluorogenic probes for glycosidases are generally based on the glycosylation of the phenol group of a donor–acceptor type fluorogen. This molecular scaffold has potential drawbacks in terms of substrate scope, sensitivity because of aggregation-caused quenching (ACQ), and the inability for long-term cell tracking. Here, we developed glycoclusters characterized by aggregation-induced emission (AIE) properties as a general platform for the sensing of a variety of glycosidases. To overcome the low chemical reactivity associated with phenol glycosylation, here we developed an AIE-based scaffold, which is composed of tetraphenylethylene conjugated with dicyanomethylene-4H-pyran (TPE–DCM) with a red fluorescence emission. Subsequently, a pair of dendritic linkages was introduced to both sides of the fluorophore, to which six copies of monosaccharides (d-glucose, d-galactose or l-fucose) were introduced through azide–alkyne click chemistry. The resulting AIE-active glycoclusters were shown to be capable of (1) fluorogenic sensing of a diverse range of glycosidases including β-d-galactosidase, β-d-glucosidase and α-l-fucosidase through the AIE mechanism, (2) fluorescence imaging of the endogenous glycosidase activities in healthy and cancer cells, and during cell senescence, and (3) glycosidase-activated, long-term imaging of cells. The present study provides a general strategy to the functional, in situ imaging of glycosidase activities through the multivalent display of sugar epitopes of interest onto properly designed AIE-active fluorogens.

We report a general strategy for the fluorogenic sensing of glycosidases in cells based on aggregation-induced emission of glycoclusters.     

Mechanically induced single-molecule helicity switching of graphene-nanoribbon-fused helicene on Au(111)

Helicene is a functional material with chirality caused by its characteristic helical geometry. The inversion of its helicity by external stimuli is a challenging task in the advanced control of the molecular chirality. This study fabricated a novel helical molecule, specifically a pentahelicene-analogue twisted aromatic hydrocarbon fused with a graphene nanoribbon, via on-surface synthesis using multiple precursors. Noncontact atomic force microscopy imaging with high spatial resolution confirmed the helicity of the reaction products. The helicity was geometrically converted by pushing a CO-terminated tip into the twisted framework, which is the first demonstration of helicity switching at the single-molecule scale.

Graphene nanoribbon-fused helicene was fabricated via on-surface synthesis. The helicity of the product was reversibly switchable by pushing a CO-terminated scanning-probe-microscopy tip into the protruding helical terminal.