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1.
    
Transforming molecular motions into the macroscopic scale is a topic of great interest to nanoscience. The photomechanical effect is a promising strategy to achieve this goal. Herein, we report an intriguing photomechanical luminescence driven by the photodimerization of 2-phenylbenzo[b]thiophene 1,1-dioxide (P-BTO) in molecular crystals and elucidate the working mechanism and substituent effect through crystallographic analysis and theoretical calculations. Striking splitting, hopping, and bending mechanical behaviors accompanied by a significant blue fluorescence enhancement are observed for P-BTO crystals under UV light, which is attributed to the formation of photodimer 2P-BTO. Although 2P-BTO is poorly π-conjugated because of the central cyclobutane ring, it exhibits prominent through-space conjugation and aggregation-induced emission (AIE), affording strong solid-state blue fluorescence at 415 nm with an excellent quantum yield of up to 96.2 %.  相似文献   

2.
    
Condensation of 1,8,13‐tris(mercaptomethyl)triptycene and tris(bromomethyl)methane yields an in,in‐cyclophane with two inwardly directed methine groups. Based on X‐ray analysis and DFT and MP2 calculations, the hydrogen–hydrogen non‐bonded contact distance is estimated to be 1.50–1.53 Å. Furthermore, the two in‐hydrogen atoms show obvious spin–spin coupling with J=2.0 Hz.  相似文献   

3.
    
It is a textbook knowledge that protein photoluminescence stems from the three aromatic amino acid residues of tryptophan(Trp), tyrosine (Tyr), and phenylalanine (Phe), with predominant contributions from Trp. Recently, inspired by the intrinsic emission of nonaromatic amino acids and poly(amino acids) in concentrated solutions and solids, we revisited protein light emission using bovine serum albumin (BSA) as a model. BSA is virtually nonemissive in dilute solutions (≤0.1 mg mL?1), but highly luminescent upon concentration or aggregation, showing unique concentration‐enhanced emission and aggregation‐induced emission (AIE) characteristics. Notably, apart from well‐documented UV luminescence, bright blue emission is clearly observed. Furthermore, persistent room‐temperature phosphorescence (p‐RTP) is achieved even in the amorphous solids under ambient conditions. This visible emission can be rationalized by the clustering‐triggered emission (CTE) mechanism. These findings not only provide an in‐depth understanding of the emissive properties of proteins, but also hold strong implications for further elucidating the basis of tissue autofluorescence.  相似文献   

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Constructing single-molecule parallel circuits with multiple conduction channels is an effective strategy to improve the conductance of a single molecular junction, but rarely reported. We present a novel through-space conjugated single-molecule parallel circuit (f-4Ph-4SMe) comprised of a pair of closely parallelly aligned p-quaterphenyl chains tethered by a vinyl bridge and end-capped with four SMe anchoring groups. Scanning-tunneling-microscopy-based break junction (STM-BJ) and transmission calculations demonstrate that f-4Ph-4SMe holds multiple conductance states owing to different contact configurations. When four SMe groups are in contact with two electrodes at the same time, the through-bond and through-space conduction channels work synergistically, resulting in a conductance much larger than those of analogous molecules with two SMe groups or the sum of two p-quaterphenyl chains. The system is an ideal model for understanding electron transport through parallel π-stacked molecular systems and may serve as a key component for integrated molecular circuits with controllable conductance.  相似文献   

6.
    
Aggregation‐induced emission (AIE), thermally activated delayed fluorescence (TADF), room‐temperature phosphorescence (RTP), and mechanoluminescence (ML) have attracted widespread interest. However, a multifunctional organic emitter exhibiting simultaneous AIE, TADF, RTP, and ML has not been reported. Now, two multifunctional blue emitters with very simple structures, mono‐DMACDPS and Me‐DMACDPS, exhibit typical AIE, TADF, and RTP properties but different behavior in mechanoluminescence. Crystal structure analysis reveals that large dipole moment and multiple intermolecular interactions with tight packing mode endow mono‐DMACDPS with strong ML. Combined with the data of crystal analysis and theoretical calculation, the separated monomer and dimer in the crystal lead to the typical TADF and RTP properties, respectively. Simple‐structure mono‐DMACDPS is the first example realizing TADF, RTP, AIE, and ML simultaneously.  相似文献   

7.
    
Carbon dots (CDs) with dual-emissive, robust, and aggregation-induced RTP characteristics are reported for the first time. The TA-CDs are prepared via hydrothermal treatment of trimellitic acid and exhibit unique white prompt and yellow RTP emissions in solid state under UV excitation (365 nm) on and off, respectively. The yellow RTP emission of TA-CDs powder should be resulted from the formation of a new excited triplet state due to their aggregation, and the white prompt emission is due to their blue fluorescence and yellow RTP dual-emissive nature. The RTP emission of TA-CDs powder was highly stable under grinding, which is very rare amongst traditional pure organic RTP materials. To employ the unique characteristics of TA-CDs, advanced anti-counterfeiting and information encryption methodologies (water-stimuli-response producing RTP) were preliminarily investigated.  相似文献   

8.
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Highly efficient detection in the aqueous phase for water‐insoluble organic molecule probes is challenging. The bright aggregated‐state electrochemiluminescence (ECL) of 1,1‐disubstituted 2,3,4,5‐tetraphenylsiloles by a co‐reactant approach was discovered, and a heterogeneous aggregation‐induced emission ECL (HAIE‐ECL) was constructed at the electrode surface, showing very high ECL efficiency (37.8 %) and selective recognition for industrially important DNBP plasticizer with a low detection limit of 0.15 nm in the water phase. A mechanistic study indicates that ECL is mainly generated due to the high electron affinity of siloles and restriction of the intramolecular motions caused by their propeller‐like noncoplanar structures. This system realizes the sensing of organic‐based ECL in the water phase by solving the crucial problems of water insolubility and aggregation‐caused quenching (ACQ), and demonstrates potential for further application because of its design and high efficiency.  相似文献   

10.
    
We report the first example of an AIEgen (DPP‐BO) with fluorescence–phosphorescence dual emission under mechanical stimulation. By carefully analyzing the crystal structure of DPP‐BO, the efficient intermolecular and intramolecular interactions should account for its unique mechanoluminescence (ML) properties, especially the abnormal phosphorescence, as further confirmed by controlled experiments and theoretical calculations for the presence of ISC transitions. These results provide important information for understanding the complex ML process, possibly opening up a new way to study the inherent mechanism of ML by broadening the application of AIEgens.  相似文献   

11.
    
Hydration water greatly impacts the color of inorganic crystals, but it is still unknown whether hydration water can be utilized to systematically manipulate the emission color of organic luminescent groups. Now, metal ions with different hydration ability allow fine-tuning the emission color of a fluorescent group displaying aggregation induced emission (AIE). Because the hydration water can be removed easily by gentle heating or mechanical grinding and re-gained by solvent fuming, rewritable materials can be fabricated both in the hot-writing and cold-writing modes. This hydration-facilitated strategy will open up a new vista in fine-tuning the emission color of AIE molecules based on one synthesis and in the design of smart luminescent devices.  相似文献   

12.
    
Enzymes contain several subunits to maintain different biological functions. However, it remains a great challenge for specific discrimination of one subunit over another. Toward this end, the fluorescent probe TPEMA is now presented for highly specific detection of the B subunit of cytosolic creatine (CK) kinase isoenzyme (CK-B). Owing to its aggregation-induced emission property, TPEMA shows highly boosted emission toward CK-B with a fast response time and very low interference from other analytes, including the M subunit of CK (CK-M). With the aid of a Job plot assay, ITC assay and molecular dynamics simulation, it was directly confirmed that the remarkably enhanced fluorescence of TPEMA in the presence of CK-B results from the restriction of single molecular motion in the cavity. Selective wash-free fluorescence imaging of CK-B in macrophages under different treatments was successfully demonstrated.  相似文献   

13.
    
The development of molecular machines requires new building blocks which are easy to characterize and visualize to realize a complexity comparable to their natural counterparts such as biological enzymes. Furthermore, with the desire to build functional nanobots capable of navigating living organisms, it is necessary that the building blocks show mobility even in the solid state. Herein we report a system which is emissive in the amorphous state but is non‐fluorescent in the crystalline state due to the formation of extensive π‐π interactions. This dual nature could be exploited for easy visualization of its solid‐state molecular rearrangement. The emission of the amorphous film was quenched as the molecules spontaneously formed π‐π interactions even in the solid state. Scratching the non‐emissive film destroyed the interactions and restored the emission of the film. The emission quickly disappeared with an average lifetime of 20 s as the compound reformed the π‐network even at room temperature.  相似文献   

14.
    
The abnormality of the plasma membrane (PM) is an important biomarker for cell status and many diseases. Hence, visualizing the PM, especially in complex systems, is an emerging field in the life sciences, especially in low-resource settings. Herein, we developed a water-soluble PM-specific probe utilizing electrostatic and hydrophobic interaction strategies with aggregation-induced emission as the signal output. The probe could image the PM with many advanced features (wash-free, ultrafast staining process, excellent PM specificity, and good biocompatibility), which were demonstrated by the PM imaging of neurons. The probe allowed for the first time the imaging of erythrocytes in the complex brain environment through a fluorescence-based method. Moreover, the PM of the epidermal and partial view of the eyeball structure of live zebrafish are also revealed.  相似文献   

15.
    
In vivo fluorescent monitoring of physiological processes with high-fidelity is essential in disease diagnosis and biological research, but faces extreme challenges due to aggregation-caused quenching (ACQ) and short-wavelength fluorescence. The development of high-performance and long-wavelength aggregation-induced emission (AIE) fluorophores is in high demand for precise optical bioimaging. The chromophore quinoline-malononitrile (QM) has recently emerged as a new class of AIE building block that possesses several notable features, such as red to near-infrared (NIR) emission, high brightness, marked photostability, and good biocompatibility. In this minireview, we summarize some recent advances of our established AIE building block of QM, focusing on the AIE mechanism, regulation of emission wavelength and morphology, the facile scale-up and fast preparation for AIE nanoparticles, as well as potential biomedical imaging applications.  相似文献   

16.
    
Restriction of intramolecular motion (RIM), as the working mechanism of aggregation‐induced emission (AIE), cannot fully explain some heteroatom‐containing systems. Now, two excited states are taken into account and a mechanism, restriction of access to dark state (RADS), is specified to elaborate RIM and complete the picture of AIE mechanism. A nitrogen‐containing molecule named APA is chosen as a model compound; its weak fluorescence in solution is ascribed to the easy access from the bright (π,π*) state to the close‐lying dark (n,π*) state. By either metal complexation or aggregation, the dark state is less accessible due to restriction of the molecular motion leading to the dark state and elevation of the dark state energy, thus the bright state emission is restored. RADS is powerful in elucidating the AIE effect of molecules with excited states favoring non‐radiative decay, including overlap‐forbidden states such as (n,π*) and CT states, spin‐forbidden triplet states, and so on.  相似文献   

17.
    
Fluorescent polymersomes with both aggregation‐induced emission (AIE) and CO2‐responsive properties were developed from amphiphilic block copolymer PEG‐b‐P(DEAEMA‐co‐TPEMA) in which the hydrophobic block was a copolymer made of tetraphenylethene functionalized methacrylate (TPEMA) and 2‐(diethylamino)ethyl methacrylate (DEAEMA) with unspecified sequence arrangement. Four block copolymers with different DEAEMA/TPEMA and hydrophilic/hydrophobic ratios were synthesized, and bright AIE polymersomes were prepared by nanoprecipitation in THF/water and dioxane/water systems. Polymersomes of PEG45b‐P(DEAEMA36co‐TPEMA6) were chosen to study the CO2‐responsive property. Upon CO2 bubbling vesicles transformed to small spherical micelles, and upon Ar bubbling micelles returned to vesicles with the presence of a few intermediate morphologies. These polymersomes might have promising applications as sensors, nanoreactors, or controlled release systems.  相似文献   

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New, biocompatible materials with favorable antibacterial activity are highly desirable. In this work, we develop a unique conjugated polymer featuring aggregation-induced emission (AIE) for reliable bacterial eradication. Thanks to the AIE and donor-π-acceptor structure, this polymer shows a high reactive oxygen species (ROS)-generation ability compared to a low-mass model compound and the common photosensitizer Chlorin E6. Moreover, the selective binding of pathogenic microorganisms over mammalian cells was found, demonstrating its biocompatibility. The effective growth inhibition of bacteria upon polymer treatment under light irradiation was validated in vitro and in vivo. Notably, the recovery from infection after treatment with our polymer is faster than that with cefalotin. Thus, this polymer holds great promise in fighting against bacteria-related infections in practical applications.  相似文献   

20.
Luminescent metal nanoclusters (NCs) are emerging as a new class of functional materials that have rich physicochemical properties and wide potential applications. In recent years, it has been found that some metal NCs undergo aggregation-induced emission (AIE) and an interesting fluorescence-to-phosphorescence (F-P) switching in solutions. However, insights of both the AIE and the F-P switching remain largely unknown. Now, gelation of water soluble, atomically precise Ag9 NCs is achieved by the addition of antisolvent. Self-assembly of Ag9 NCs into entangled fibers was confirmed, during which AIE was observed together with an F-P switching occurring within a narrow time scale. Structural evaluation indicates the fibers are highly ordered. The self-assembly of Ag9 NCs and their photoluminescent property are thermally reversible, making the metal–organic gels good candidates for luminescent ratiometric thermometers.  相似文献   

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