Aggregation-induced Emission Enhancement Research Articles

A ratiometric fluorescence nanosensor for glutathione detection based on spatially confined dual-emission of α-lipoic acid-modified gold nanoclusters and silicon nanoparticles.

The development of dual-emission ratiometric fluorescent probes with aggregation-induced emission enhancement (AIEE) overcomes the limitations of gold nanocluster (Au NC)-based probes, particularly their weak intrinsic fluorescence, in real-world applications. These AIEE probes also exhibit superior detection limits and enhanced sensitivity. A novel combination for the reliable fluorometric detection of glutathione (GSH) was proposed, utilizing aggregation-induced emission enhancement (AIEE) facilitated by electrostatic interaction and spatial confinement. The probe consists of a ratiometric combination of negatively charged α-lipoic acid-modified Au NCs (LA@Au NCs) and positively charged silicon nanoparticles (SiNPs). The addition of SiNPs causes aggregation of LA@Au NCs, enhancing the fluorescence of LA@Au NCs through the AIE effect under electrostatic interaction and spatial confinement. The addition of Cu2+ quenched the emission of LA@Au NCs as a result of charge transfer. The fluorescence emissions of LA@Au NCs were restored upon the addition of GSH due to the interaction between GSH and Cu2+. Simultaneously, the emission signal of SiNPs remains unchanged, serving as an internal reference signal during GSH measurement. It was found that the fluorescence ratio (F680/F465) is directly proportional to the concentration of GSH in the range of 0.05-100 μM, with a detection limit of 1.7 nM (S/N = 3). The proposed system was applied to detect GSH in real samples, including dietary supplements, human serum, and saliva samples. This work opens new avenues for constructing novel sensors based on AIEE for detecting biomolecules.

Dual aggregation-induced emission enhancement (AIEE) and crosslink-enhanced emission (CEE) driven via halogen-bond-assisted cocrystallization and radical solid-phase polymerization

Concurrent emission enhancement was attained by halogen-bond-driven cocrystallization (aggregation-induced emission enhancement, AIEE), followed by halogen-bond-driven (non)covalent crosslinking of polymer (crosslink-enhanced emission, CEE).

Aminoguanidine-based bioactive proligand as AIEE probe for anticancer and anticovid studies.

The emission features of a novel bioactive compound, 1,3-bis(2-hydroxy-3,5-diiodophenyl-methylideneamino)guanidine is found impressive with aggregation induced emission enhancement. The nitrogen and iodine rich multidentate proligand was characterized physicochemically. SCXRD and Hirshfeld surface investigation have revealed the presence of significant triangular iodine bonding apart from hydrogen bonding, weak C-H⋯π and π⋯π intermolecular interactions. These interactions collectively contribute to the solid-state packing arrangement of the molecules within the crystal lattice. The band gap of the compound was estimated experimentally and is supported with theoretical calculations. The solid-state fluorescence quantum yield of Φ = 0.36 emphasizes the utility of the proligand and the AIEE characteristics is attributed to restricted intramolecular motions as indicated by fluorescence lifetime decay studies. Strong interaction of the compound with calf thymus DNA was explored experimentally and found to align with in silico docking results. Notably, in vitro anticancer assessment on MCF-7 breast cancer cells show an IC50 value of 181.05 μg mL-1 and signifying its potent cytotoxic properties. Also, the compound is found to have lesser cytotoxicity against L929 normal cell line with an IC50 value of 356.54 μg mL-1. Computational studies further underscore the exceptional binding affinity with active sites in the SARS-CoV-2 main protease 3CLpro, surpassing established repurposed drugs. Furthermore, the proligand demonstrates excellent putative affinity towards the SARS-CoV-2 spike glycoprotein, accompanied by its distinctive AIEE attributes, drug likeness and DNA binding capability rendering it a valuable tool for prospective research investigations.

Fluorescence emission modification of triphenylamine derivatives by aggregate formation in solution or by mechanical stress in solid state

Two derivatives of triphenylamine, 4-(diphenylamino)benzaldehyde and 2-(4- (diphenylamino)benzylidene)malononitrile, with acceptor mesomeric groups, an aldehyde moiety and a dicyanovinyl group respectively, were synthesized and found to have aggregation-induced emission (AIE) or aggregation-induced enhanced emission (AIEE) properties in several DMF/H2O mixtures. The size of the formed aggregates was studied with Dynamic Light Scattering (DLS) and a significant change of approximately 200 nm was observed according to the water fraction in DMF. Mechanoluminochromism characteristics in the solid state were also observed. A shift in the emission bands was noticed when comparing the solid before and after grinding, as well as when comparing the crystalline and amorphous form.

Aggregation-induced enhanced fluorescence emission of chiral Zn(II) complexes coordinated by Schiff-base type binaphthyl ligands.

A pair of novel chiral Zn(II) complexes coordinated by Schiff-base type ligands derived from BINOL (1,1'-bi-2-naphthol), R-/S-Zn, were synthesized. X-ray crystallography revealed the presence of two crystallographically independent complexes; one has a distorted trigonal-bipyramidal structure coordinated by two binaphthyl ligands and one disordered methanol molecule (molecule A), while the other has a distorted tetrahedral structure coordinated by two binaphthyl ligands (molecule B). Numerous CH⋯π and CH⋯O interactions were identified, contributing to the formation of a 3-dimensional rigid network structure. Both R-/S-Zn exhibited fluorescence in both CH2Cl2 solutions and powder samples, with the photoluminescence quantum yields (PLQYs) of powder samples being twice as large as those in solutions, indicating aggregation-induced enhanced emission (AIEE). The AIEE properties were attributed to the restraint of the molecular motion arising from the 3-dimensional intermolecular interactions. CD and CPL spectra were observed for R-/S-Zn in both solutions and powders. The dissymmetry factors, gabs and gCPL values, were within the order of 10-3 to 10-4 magnitudes, comparable to those reported for chiral Zn(II) complexes in previous studies.

Fluorometric and colorimetric dual-mode sensing of α-glucosidase based on aggregation-induced emission enhancement of AuNCs.

Herein, a fluorometric and colorimetric dual-mode assay platform used for α-glucosidase (α-Glu) activity sensing based on aggregation-induced emission enhancement (AIEE) of AuNCs was developed for the first time. The quantum yield (QY) and fluorescence lifetime of AuNCs were successfully ameliorated by Ce3+-triggered AIEE (Ce@AuNCs). Subsequently, on the basis of the inner filter effect (IFE) and dynamic quenching effect (DQE) between 2,6-dichlorophenolindophenol (DCIP) and Ce@AuNCs as well as the reduction of DCIP by ascorbic acid (AA) generated from α-Glu-catalyzed hydrolysis of L-ascorbic acid-2-O-α-D-glucopyranosyl (AA2G), the marriage of fluorometric and colorimetric modes applied for α-Glu activity monitoring was achieved. Besides, the feasibility of this dual-mode sensing system was confirmed by the assays versus potential interfering substances and in real samples. In particular, this system was further applied to evaluate natural α-Glu inhibitors (AGIs) including luteolin, apigenin, and hesperidin. Overall, the multi-mode optical sensor newly designed here has the potential for the accurate discovery of natural anti-diabetes drugs and the therapy of diabetes.

A difluoroboron compound with latent fingerprint detection and inkless writing based on aggregation-induced emission enhancement and mechanofluorochromic behavior

A pyridine-based difluoroboron compound with the TPA group displayed excellent AIEE activity and MFC behavior, which was applied for latent fingerprint detection and inkless writing.

Exploring structural and optical properties of a new series of soft salts based on cyclometalated platinum complexes.

A series of nine new soft salts based on two platinum(II) complexes, namely ([Pt(C^N)(CN)2]-[Pt(C^N)(en)]+) (en = ethane-1,2-diamine), has been developed and synthesized. Their photophysical properties in both solution and the solid state were described. All soft salt complexes exhibit phosphorescence emission with PLQY in the solid state up to 0.36. Most of these materials displayed aggregation-induced emission (AIE) or aggregation-induced emission enhancement (AIEE) in water/DMSO solutions as the water ratio increased. Structure-property relationships were analyzed in relation to emission properties. The presence of the free nitrogen atoms in soft salt complexes with a C^N pyrimidine-based ligand allowed for reversible sensitivity to acidic vapors, resulting in the quenching of phosphorescence emission. Additionally, for selected soft salts, we described reversible vapochromism behaviour, making these new materials interesting for multi-detection purposes in anti-counterfeiting applications.

Enhanced fluorescent detection of oxaliplatin via BSA@copper nanoclusters: a targeted approach for cancer drug monitoring.

A new fluorescence sensing approach has been proposed for the precise determination of the anti-cancer drug oxaliplatin (Oxal-Pt). This method entails synthesizing blue-emitting copper nanoclusters (CuNCs) functionalized with bovine serum albumin (BSA) as the stabilizing agent. Upon excitation at 360 nm, the resultant probe exhibits emission at 460 nm. Notably, the fluorescence response of BSA@CuNCs substantially increases upon incubation with Oxal-Pt due to multiple binding interactions between the drug and the fluorescent probe. These interactions involve hydrogen bonding, hydrophobic interaction, and the high affinity between the SH groups (cysteine residues of BSA) and platinum (in Oxal-Pt). Consequently, this interaction induces aggregation-induced emission enhancement (AIEE) of BSA@CuNCs. The probe demonstrates a broad response range from 0.08 to 140.0 μM, along with a low detection limit of 20.0 nM, determined based on a signal-to-noise ratio of 3. Furthermore, the probe effectively detects Oxal-Pt in injections, human serum, and urine samples, yielding acceptable results. This study represents a significant advancement in the development of a straightforward and efficient sensor for monitoring platinum-containing anti-cancer drugs during chemotherapy.

CinNapht AIE(E)gens for selective imaging of lipid droplets.

This article describes the synthesis and photophysical properties of Aggregation-Induced Emission (enhancement) luminogens derivated from CinNaphts dyes. These fluorophores can be obtained in good yields in a single SNAr step of a fluorinated CinNapht derivative by incorporating hindered aromatic amines. They exhibit AIE(E) behavior associated with solid-state fluorescence covering an emission range from 563 to 722 nm. One carbazole derivative demonstrates a remarkable efficiency in imaging lipid droplets in living cells through an original photophysical mechanism.

Detecting carcinoembryonic antigen based on the aggregation-induced emission enhancement effect.

In this study, a novel label-free fluorescent aptasensor with an aggregation-induced emission enhancement effect was developed and applied for the detection of carcinoembryonic antigen (CEA). The sensor has a simple detection mechanism, easy operation, high sensitivity (with low limit of detection of 1 pg mL-1), good selectivity, and wide linear range (0.003-10 ng mL-1). In addition, it can be directly applied for the determination of CEA in human serum.

Solvatochromism of new tetraphenylethene luminogens: integration of aggregation-induced emission and conjugation-induced rigidity for emitting strongly in both solid and solution state.

In this study, we synthesized and characterized four tetraphenylethene (TPE) analogs, investigated their photophysical properties, and conducted quantum chemical calculations. Some molecules exhibited aggregation-induced emission enhancement behavior and showed efficient emission in both solid and solution states. Solvatochromism was observed in particular derivatives, with solvent polarity influencing either a bathochromic or hypsochromic shift, indicating the occurrence of photoinduced intramolecular charge transfer (ICT) processes. Quantum chemical calculations confirmed that variations in molecular packing and rigidity among the TPE analogs contributed to their diverse behavior. The study showcases aggregation in luminophores without significant impact on the excited state and highlights how minor alterations in terminal substituents can lead to unconventional behavior. These findings have implications for the development of luminescent materials. Furthermore, the synthesized compounds exhibited biocompatibility, suggesting their potential for cell imaging applications.

Adjustable luminescence copper nanoclusters nanoswitch based on competitive coordination of samarium ions for cascade detection of adenosine triphosphate and acid phosphatase activity.

Benefit from the strong coordination property, lanthanide metal ions have been used as competitive reagents to modulate the fluorescence changes of the system. However, lanthanide metal ions as inducers for aggregation-induced emission enhancement in nanosystems is rare. Herein, we report a "turn on-off-on" fluorescent switch for cascade detection of acid phosphatase (ACP) and adenosine triphosphate (ATP) based on the competitive coordination of samarium ions (Sm3+). Novel copper nanoclusters (CuNCs) with long wavelength emission (614nm) stabilized by glutathione (GSH) and glycylglycine (Gly-Gly) have been confirmed to have AIE property. With the continuous aggregation of GSH/Gly-Gly CuNCs under the induction of Sm3+, the fluorescence of the system increased to achieve the "turn-on" process. The coordinated behaviour between Sm3+ and GSH/Gly-Gly CuNCs is discussed. Due to the strong metal coordination ability of ATP, the Sm3+ coordinated with the GSH/Gly-Gly CuNCs is competed out, resulting in the fluorescence "turn-off" process of the system. As the substrate of enzymatic hydrolysis of ACP, with the continuous hydrolysis of ATP by ACP, Sm3+ coordinates with GSH/Gly-Gly CuNCs again, which leads to the AIE effect and realize the fluorescence "turn-on" process of the system. This strategy results inATP linear range of 0.508 ~ 120.0μM with a detection limit of 0.508μM (S/N = 3) and ACP linear range of 0.011 ~ 30.0 U·L-1 with a detection limit of 0.011 U·L-1 (S/N = 3). Application tobiologic samples wassuccessful.

Combination of gold nanoclusters and silicon quantum dots for ratiometric fluorometry: One system, two mechanisms

A ratiometric fluorometry based on silicon quantum dots (SiQDs) and gold nanoclusters (AuNCs) is constructed for detecting activity of butyrylcholinesterase (BChE) in human serum. By using thiobutyrylcholine iodide (BTCh) as the substrate of BChE-catalyzed hydrolysis reaction, variation of fluorescence emission from AuNCs is employed as an indicator of BChE activity since one of the hydrolysis products, thiocholine (TCh), would influence the aggregation state of AuNCs and consequently led to the change of fluorescence quantum efficiency of AuNCs. It is interesting that there are two mechanisms working for the fluorescence emission of aggregated AuNCs: aggregation-induced emission enhancement (AIEE) and aggregation-caused quenching (ACQ) with the presence of TCh at very low and higher concentration levels, respectively. Although both of these mechanisms can be utilized for sensing BChE, their opposite influence on the fluorescence emission of aggregated AuNCs should be worthy of attention, especially in the process of developing fluorescence methods for detecting trace targets by using AuNCs. In order to eliminate the fluctuation of fluorophotometer, SiQDs is chosen as the fluorophore to develop by ratiometric fluorescence methods in this work. Additionally, obvious aggregation of AuNCs induces significant decrease of inner filter effect (IFE) on the fluorescence emitted from SiQDs, while mild aggregation of AuNCs demonstrates little IFE. The linear ranges for detecting activity of BChE are 0.004 – 0.05 U/L and 0.5 – 20 U/L by ratiometric fluorometry based on the AIEE and ACQ, respectively. The very different responses originated from AIEE and ACQ of AuNCs would respectively make their own contributions to the determination of BChE activities at very low or high levels, which facilitate the developments of enhanced or quenched fluorescence methods. However, the detection of BChE activities at medium levels might suffer from the combination of AIEE and ACQ with ambiguous fractions. Therefore, it must be careful during the processes of developing and applying fluorescence methods based on the AIEE and ACQ of AuNCs, as well as the process of evaluating their analytical performance.

A rapid and specific fluorescent probe based on aggregation-induced emission enhancement for mercury ion detection in living systems

Mercury is a harmful heavy metal that seriously threatens the environment and organisms. In this study, we combined the aggregation-induced emission mechanism and the advantages of peptides to design a novel tetraphenylene (TPE)-based peptide fluorescent probe, TPE-Cys-Pro-Gly-His (TPE-CPGH), in which the sulfhydryl group of Cys in the peptide chain and the imidazolium nitrogen provided by His were used to mimic the Hg2+ binding site of metalloproteins. The β-fold formed by Pro-Gly was used to promote the spatial coordination of the probe with Hg2+ and the formation of the coordination complex aggregates, these changes led to the “turn on” response to Hg2+. The detection of Hg2+ by TPE-CPGH not only showed high specificity and sensitivity (LOD=46.2 nM), but also had the advantages of fast response and applicability for detection over a wide pH range. Additionally, TPE-CPGH effectively detected Hg2+ in environmental samples, living cells and organisms due to its low cytotoxicity, high water solubility and cell membrane permeability. More interestingly, TPE-CPGH was also mitigated Hg2+ exposure-induced oxidative stress toxicity in vitro and in vivo.

A very rare fluorescent chemosensor of zinc(II) exhibiting AIEE, ESIPT and TICT: Spectroscopic, crystallographic and theoretical exploration

The basic systems in this study are HL (1; 1:2 condensation product of 2,6-diformyl-4-ethylphenol and o-anisidine) and its ZnII and CdII complexes of composition [ZnII(LH)Cl2]·CH3OH (2) and [CdII(LH)Cl2] (3), all of which are synthesized and characterized by CHN elemental analyses, single crystal X-ray crystallography, powder X-ray diffraction (PXRD) and fourier transform infrared (FT-IR) spectrum. It has been established from the following experimental and theoretical studies that 1 is a fluorescent turn on sensor of ZnII ion and it exhibits all of excited state intramolecular proton transfer (ESIPT), photoinduced electron transfer (PET), twisted intramolecular charge transfer (TICT) and aggregation induced enhanced emission (AIEE): (i) Detailed absorption and emission (steady state / time resolved) studies in various single solvents, in solvent mixtures, with pH variation, with various single metal ions, with mixtures of metal ions, on varying temperature and on varying viscosity; (ii) dynamic light scattering (DLS) and scanning electron microscopy (SEM) in solvent mixtures; (iii) density functional theory (DFT) and time dependent density functional theory (TD-DFT) calculations in ground and excites states of 1–3. It is shown that 1 can be efficaciously applied in inkless writing with the “write − erase − write” facility. The mechanisms/reasons of the observed properties have been addressed. The difference in fluorescence of ZnII and CdII complexes, unusual case of crystal structures of probe and complexes with ZnII and CdII, unusual features in the structures of 2 and 3 as well as a structure–property correlation have been discussed.

Impact of alkyl chains, electron donor substituents and acidic group on aggregation-induced emission of carboxylic acid functionalized quinoxalines

We report an optical study of quinoxaline-based luminogens derived from 2,3-bis(aryl)-quinoxaline-6-carboxylic acid (1a, 1b, and 2) in solution and solid state. These compounds were fluorescent in solid films and in solutions with emission bands ranging from blue to green (445–517 nm). They showed a positive solvatochromism in the PL spectra, indicative of intramolecular charge transfer (ICT) in the excited state. 1a, 1b, and 2 exhibited Aggregation-Induced Enhanced Emission (AIEE) characteristics with a drastic change in properties by increasing alkyl chains and donor alkoxy groups. Their carboxylate potassium salts had a blueshift emission compared to the acid carboxylic form and a significant quenching in PL intensity in protic polar solvents. The salt of 1a presented an Aggregation-Induced Emission (AIE) profile, its weak fluorescence in water had an expressive enhancement by adding THF. Theoretical calculations were also carried out considering implicit solvent effects. The optimized structures of compounds and their simulated UV–vis absorption spectra showed no significant differences in water and acetonitrile. These results are in good agreement with the solvatochromism experiments. The calculated HOMO-LUMO energy gaps were 3.47 eV in both solvents, and the energy levels for HOMO and LUMO are slightly lower in water.

A novel chromophore reaction-based pyrrolopyrrole aza-BODIPY fluorescent probe for H2S detection and its application in food spoilage.

In this work, we developed an aggregation-induced emission enhancement (AIEE) active and NIR emissive pyrrolopyrrole aza-BODIPY (PPAB) polymer (P1) for H2S detection for the first time. P1 showed obvious colorimetric change from green to yellow-green and ratiometric fluorescence "turn on" phenomenon with 167nm blue-shift (from dark red to bright green). The sensing mechanism revealed a novel chromophore reaction between imine in PPAB core and H2S was involved, leading to less conjugated product. It exhibited distinct advantages of good selectivity, high sensitivity, and low detection limit of 0.66μM. The potential applicability of P1 for H2S detection in the real samples (tap water, lake water and milk) was demonstrated. In addition, the solid sensor prepared by loading P1 on the PMMA film was successfully realized the visual detection of gaseous H2S gas produced from egg spoilage. Therefore, this work provides a promising approach based on novel sensing mechanism for monitoring H2S in complicated biological systems and practical food samples.

Exploring the dual sensing properties of an anthraldehyde based Schiff base for the successive determination of picric acid using AIEEF and copper using colorimetric methods

A novel and lucid Schiff base, designated as AHN, exhibiting multiple analytical responses comprising AIEE (Aggregation Induced Emission Enhancement) and colorimetric activity towards distinct analytes has been designed and synthesized. The probe, AHN, effectively leverages AIEE activity to selectively detect picric acid (PA) on behalf of fluorescence switch-off response amidst other nitro chemicals. Additionally, it offers remarkable colorimetric selectivity to bivalent copper ions (Cu2+) via a distinct colour change from colourless to yellow. The multi-response characteristics of AHN propel its practicality for naked-eye detection of these analytes. The addition of PA to the aggregate of AHN in DMSO with a 90% water fraction induces a quenching in the fluorescence intensity of the AHN aggregate and the limit of detection of PA was found to be 24.5 × 10−7 M with a quenching constant value of 6.21 × 107 M−1. Stern Volmer plots and lifetime measurements, clearly indicate that both static and dynamic processes were involved in the quenching mechanism. It is also evident that ground-state complexation between electron-rich fluorescent aggregates of AHN and electron-deficient PA takes place through π-π interactions and intramolecular hydrogen bonding interactions. Further, AHN in DMSO exhibits a selective colorimetric response to bivalent copper among various metal ions with a detection limit of 3.16 µM which is substantially below the permitted limit recommended by WHO in drinking water. The mechanism of colorimetric response is the complexation of AHN with Cu2+ in the 2:1 stoichiometry, as confirmed by Job’s plot method. Consequently, the versatility of probe AHN in detecting PA and Cu2+ through distinct mechanisms fosters its significance in the field of sensing and opens promising avenues for practical sensing applications.

Fluorescence enhancement induced by supramolecular J-aggregation of pyrene dye containing a flexible rotation group

A pyrene dye bearing a flexibly rotated hydrophobic group (3,4,5-tri(dodecyloxy)benzoyl-) was synthesized and fully characterized. In cooling processes for the dye monomer in CHCl3/CH3OH, the monomer was transformed into the J-aggregates which were characterized to possess a typically nanowired shape. A thermodynamic hysteresis of the molar fraction of the aggregates was observed explicitly between the cooling and heating processes. A pronounced self-absorption was involved in the aggregate solutions of the dye at high concentrations. Clearly, the J-aggregation conferred a few intriguing attributes such as a red-shift of maximum absorption peak, a higher quantum yield of absolute fluorescence and a shorter fluorescence lifetime than the monomer. Collectively, these attributes brought about a phenomenon of aggregation-induced emission enhancement (AIEE). In addition, the HOMO and LUMO energies were calculated by DFT for both the monomeric and aggregated states. Furthermore, the stacking parameters in the J-aggregates were evaluated according to the molecular exciton theory. It can be concluded that the J-aggregation enhanced substantially the emission of the dye. Undoubtedly, the strategy for the development of the AIEE molecules containing a flexible rotation group via J-aggregation as revealed in this work will be very useful in the future design of new organic light-emitting dyes.