Aggregation-induced Emission Luminogens Research Articles

Natural protoberberine alkaloid–montmorillonite nanocomposite powders with AIE features for visualizing high-resolution latent fingerprints

Real-time and in-situ fluorescence visualization technologies have attention to in the forensic analysis of latent fingerprints (LFPs). The fingerprint powders with high performance and biocompatibility are essential for imaging LFPs with high definition and safety. In this work, five quaternary protoberberine alkaloid (QPA) derivatives were analyzed with reorganization energy and four-point calculations to explain the relationship between the substituent effect and luminescent properties and further resolve the luminous behaviors of four QPA-based natural products in solution. Thanks to the restriction of the intramolecular motions mechanism, aggregation-induced emission (AIE) active BBC nanoaggregates could sensitively detect explosive analog, 2,4,6-trinitrophenol, at a nanomolar level (9.8 nM of detection limit). Combined with natural montmorillonite (MMT) mineral powders, three levels of details for fingerprints were successfully imaged with solid-luminous BBC/MMT nanocomposites. The insight into the substituted effect of alkoxy groups on the QPA framework not only provides a new concept to design rotor-free AIE luminogens but also expands natural products and their nanocomposites into LFP and detection applications.

Visible-Light-Mediated Ruthenium-Catalyzed para-Selective Alkylation of Unprotected Anilines

Anilines are important moieties in organic chemistry, pharmaceuticals, and materials science. Although para-selective functionalization of anilides and tertiary anilines is well established, unprotected anilines have posed a challenge. Herein, we report visible-light-mediated Ru(II)-catalyzed para-alkylation of anilines. The distinct Ru(II)–aniline complex enabled the reaction to proceed with extremely high efficiency (2 h) under mild conditions. The good functional group tolerance allowed late-stage functionalization and even aggregation-induced emission luminogen labeling of natural products and drugs. A mechanistic investigation suggests that the Ru(II)–aniline complex is crucial for both triggering the reaction and controlling the para-selectivity.

Promoting the healing of methicillin-resistant Staphylococcus aureus-infected wound by a multi-target antimicrobial AIEgen of 6-Aza-2-thiothymine-decorated gold nanoclusters

The use of conventional antibiotic therapies is in question owing to the emergence of drug-resistant pathogenic bacteria. Therefore, novel, highly efficient antibacterial agents to effectively overcome resistant bacteria are urgently needed. Accordingly, in this work, we described a novel class luminogen of 6-Aza-2-thiothymine-decorated gold nanoclusters (ATT-AuNCs) with aggregation-induced emission property that possessed potent antimicrobial activity against methicillin-resistant Staphylococcus aureus (MRSA). Scanning electron microscopy was performed to investigate the interactions between ATT-AuNCs and MRSA. In addition, ATT-AuNCs exhibited excellent ROS generation efficiency and could effectively ablate MRSA via their internalization to the cells. Finally, tandem mass tag-labeling proteome analysis was carried out to investigate the differential expression proteins in MRSA strains. The results suggested that ATT-AuNCs killed MRSA cells through altering the expression of multiple target proteins involved in DNA replication, aminoacyl-tRNA synthesis, peptidoglycan and arginine biosynthesis metabolism. Parallel reaction monitoring technique was further used for the validation of these proteome results. ATT-AuNCs could also be served as a wound-healing agent and accelerate the healing process. Overall, we proposed ATT-AuNCs could serve as a robust antimicrobial aggregation-induced emission luminogen (AIEgen) that shows the ability to alter the activities of multiple targets for the elimination of drug-resistant bacteria.

Direct self-assembly of AIE-active tetraphenylethene derivative with cucurbit[7]uril as a fluorescence probe for metformin detection

A fast, simple, sensitive and stable “turn-on” fluorescent probe method by the self-assembly of aggregation-induced emission luminogen 1,1,2,2-tetra(biphenyl-4-yl)ethene and cucurbit[7]uril was developed for selective determination of metformin. Simultaneously the host–guest complex can improve the poor water solubility of traditional aggregation-induced emission material. The response mechanism of the supramolecular probe to metformin was studied by UV–visible absorption spectroscopy, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, dynamic light scattering technology, scanning electron microscope. The proposed method showed good sensitivity and accuracy for the detection of metformin. The relative fluorescence intensity was linearly correlated with the concentration of metformin in the range of 5 to 100 µM, with a detection limit of 1.5 µM. In addition, the aggregation-induced emission probe was successfully utilized to determine the metformin concentration in serum samples, and the recovery ranged from 90.80% to 104.0% with satisfactory results. Therefore, the established fluorescence assay provides a promising pathway for metformin analysis in biomedicine.

Discovery of aggregation-induced emission luminogens (AIEgens) from orange peel

In recent years, aggregation-induced emission luminogens (AIEgens) have been widely developed for bio-imaging, theranostics, organic photoelectronics, and chemo/biosensors. While, the existing AIEgens are almost all obtained by organic synthesis, experiencing complicated synthesis routes, high cost, environmentally unfriendly, and poor biocompatibility. Therefore, exploration of AIEgens from natural products is an attractive alternative approach. In this contribution, two natural AIE-active materials, Tangeretin and Nobiletin, were found, which can be extracted from orange peel. Single crystal structure, fluorescence spectra and viscosity analyses verified that restriction of intramolecular rotation was responsible for the AIE phenomenon of Tangeretin and Nobiletin. The theoretical calculation results indicated that the intermolecular charge transfer (ICT) was related with the bathochromic-shift in the solid-state. Moreover, Tangeretin and Nobiletin were biocompatible and could selectively target lysosomes. In short, these natural products provided a new approach for obtaining new kinds of AIEgens, and showing great potential in bioimaging.

Effects of Halogenation on Quinoline-Malononitrile based AIEgens: Photophysical Properties Investigation and Wash-Free Imaging.

Developing halogen-functionalized fluorescent dyes with intriguing photophysical properties, including enhanced photostability, is particularly important for bioimaging. In this work, we synthesized two new halogen-functionalized aggregation-induced emission (AIE)-active molecules, DQMF-OH and DQMCl-OH, based on the quinoline-malononitrile chromophore. The halogen effect on the photophysical characteristics was detailedly studied by absorption and fluorescence spectroscopy, density functional theory calculations, and crystal structures. Compared with non-halogen substituted AIE luminogen (AIEgen) DQM-OH, the halogen substituted DQMF-OH and DQMCl-OH exhibited red-shifted absorptions and emissions in the solution and solid state. In addition, DQMF-OH and DQMCl-OH also possessed enhanced fluorescence toward viscosity changes. These AIEgens served as remarkable imaging tools for cell tracking in a wash-free manner. Furthermore, DQMF-OH and DQMCl-OH showed much more excellent photobleaching resistance than DQM-OH. Our work sheds new light on developing fluorescent halogenated dyes with enhanced photophysical performances for biological applications.

Development of Sulfonamide‐Functionalized Charge‐Reversal AIE Photosensitizers for Precise Photodynamic Therapy in the Acidic Tumor Microenvironment

AbstractTumor‐targeted photodynamic therapy (PDT) is desirable as it can achieve efficient killing of tumor cells with no or less harm to normal cells. Herein, a facile molecular engineering strategy is developed for photosensitizers (PSs) with aggregation induced emission (AIE) characteristics and responsive properties to the acidic tumor microenvironment (TME). By the marriage of pH‐sensitive sulfonamide moieties with AIE PSs, two near‐infrared AIE luminogens called DBP‐SPy and DBP‐SPh are designed and synthesized. Both luminogens can form negatively charged nanoaggregates in the aqueous medium at physiological pH. The DBP‐SPy nanoaggregates undergo surface charge conversion to become positive at pH close to the signature pH of TME, while DBP‐SPh nanoaggregates show no such property. The endowed response to acidic TME enables the enhanced cellular uptake of DBP‐SPy at pH = 6.8. By contrast, its cellular uptake is much sacrificed at pH 7.4. As a result, under white light irradiation, DBP‐SPy nanoaggregates demonstrate a considerable photodynamic therapeutic effect on cancer cells in vitro and excellent tumor growth inhibition in vivo. Hence, this study not only provides an acidic TME‐responsive AIE PS for precise PDT, but also inspires new design strategies for AIE‐based theragnostic systems with targeting characteristics.

Radiolabeled AIE Probes as Dual-modality Imaging Agents for PET/NIR-II Fluorescence-Guided Photothermal Therapy.

Breast cancer has become a huge burden with continued rise of incidence and death rate worldwide. Various methods for diagnosis and therapy of breast cancer have met the challenges of lack of complete information about the tumor location and limited therapy efficacy. Although aggregation-induced emission luminogens (AIEgens) have shown great promise for various cancer treatment applications, they may be incompetent for deep-seated tumor diagnosis due to the limited penetration depth. Herein, we designed and prepared a radiolabeled AIEgen-based organic photothermal agent for bimodal PET/fluorescence imaging-guided breast tumor photothermal therapy. The prepared multifunctional nanoparticles (68 Ga-TPA-TTINC NPs) with NIR-II fluorescence, gamma irradiation and photothermal conversion property could be efficiently taken up by tumor cells and induce reactive oxygen species burst in vitro, further boosting the photothermal treatment of tumor in vivo. More importantly, the nanoprobe could target and clearly visualize 4T1 tumor xenografts through PET and NIR-II fluorescence imaging with high tumor/muscle ratio up to 4.8, which provides a promising tool and solution for breast tumor theranostics.

Interactions of Amino Group Functionalized Tetraphenylvinyl and DNA: A Label-Free “On-Off-On” Fluorescent Aptamer Sensor toward Ampicillin

As a type of aggregation-induced emission (AIE) fluorescent probe, tetraphenylvinyl (TPE) or its derivatives are widely used in chemical imaging, biosensing and medical diagnosis. However, most studies have focused on molecular modification and functionalization of AIE to enhance the fluorescence emission intensity. There are few studies on the interaction between aggregation-induced emission luminogens (AIEgens) and nucleic acids, which was investigated in this paper. Experimental results showed the formation of a complex of AIE/DNA, leading to the quenching of the fluorescence of AIE molecules. Fluorescent test experiments with different temperatures proved that the quenching type was static quenching. The quenching constants, binding constants and thermodynamic parameters demonstrated that electrostatic and hydrophobic interactions promoted the binding process. Then, a label-free "on-off-on" fluorescent aptamer sensor for the detection of ampicillin (AMP) was constructed based on the interaction between the AIE probe and the aptamer of AMP. Linear range of the sensor is 0.2-10 nM with a limit of detection 0.06 nM. This fluorescent sensor was applied to detect AMP in real samples.

AIEgen-Conjugated Phase-Separating Peptides Illuminate Intracellular RNA through Coacervation-Induced Emission.

Intrinsically disordered peptides drive dynamic liquid-liquid phase separation (LLPS) in membraneless organelles and encode cellular functions in response to environmental stimuli. Engineering design on phase-separating peptides (PSPs) holds great promise for bioimaging, vaccine delivery, and disease theranostics. However, recombinant PSPs are devoid of robust luminogen or suitable cell permeability required for intracellular applications. Here, we synthesize a peptide-based RNA sensor by covalently connecting tetraphenylethylene (TPE), an aggregation-induced emission luminogen (AIEgens), to tandem peptide repeats of (RRASL)n (n = 1, 2, 3). Interestingly, the conjugation of TPE luminogen promotes liquid-liquid phase separation of the peptide repeats, and the minimum coacervation concentration (MCC) of TPE-(RRASL)n is decreased by an order of magnitude, compared to that of the untagged, TPE-free counterparts. Moreover, the luminescence of TPE-(RRASL)n is enhanced by up to 700-fold with increasing RNA concentration, which is attributed to the constricted rotation of the TPE moiety as a result of peptide/RNA coacervates within the droplet phase. Besides, at concentrations above MCC, TPE-(RRASL)n can efficiently penetrate through human gallbladder carcinoma cells (SGC-996), translocate into the cell nucleus, and colocalize with intracellular RNA. These observations suggest that AIEgen-conjugated PSPs can be used as droplet-based biosensors for intracellular RNA imaging through a regime of coacervation-induced emission.

Autophagy-Activated Self-reporting Photosensitizer Promoting Cell Mortality in Cancer Starvation Therapy.

Cancer starvation therapy have received continuous attention as an efficient method to fight against wide-spectrum cancer. However, during cancer starvation therapy, the protective autophagy promotes cancer cells survival, compromising the therapeutic effect. Herein, a novel strategy by combination of autophagy-activated fluorescent photosensitizers (PSs) and cancer starvation therapy to realize the controllable and efficient ablation of tumor is conceived. Two dual-emissive self-reporting aggregation-induced emission luminogens (AIEgens), TPAQ and TPAP, with autophagy-activated reactive oxygen species (ROS) generation are prepared to fight against the protective autophagy in cancer starvation therapy. When protective autophagy occurs, a portion of TPAQ and TPAP will translocate from lipid droplets to acidic lysosomes with significant redshift in fluorescence emission and enhanced ROS generation ability. The accumulation of ROS induced by TPAQ-H and TPAP-H causes lysosomal membrane permeabilization (LMP), which further results in cell apoptosis and promotes cell death. In addition, TPAQ and TPAP can enable the real-time self-reporting to cell autophagy and cell death process by observing the change of red-emissive fluorescence signals. Particularly, the efficient ablation of tumor via the combination of cancer starvation therapy and photodynamic therapy (PDT) induced by TPAQ has been successfully confirmed in 3D tumor spheroid chip, suggesting the validation of this strategy.

Natural Coumarin Isomers with Dramatically Different AIE Properties: Mechanism and Application.

Aggregation-induced emission luminogens (AIEgens) are of great importance in optoelectronics and biomedical fields. However, the popular design philosophy by combining rotors with traditional fluorophores limits the imagination and structural diversity of AIEgens. Inspired by the fluorescent roots of the medicinal plant Toddalia asiatica, we discovered two unconventional rotor-free AIEgens, 5-methoxyseselin (5-MOS) and 6-methoxyseselin (6-MOS). Interestingly, a slight structural difference of the coumarin isomers leads to completely contrary fluorescent properties upon aggregation in aqueous media. Further mechanism investigation indicates that 5-MOS forms different extents of aggregates with the assistance of protonic solvents, leading to electron/energy transfer, which is responsible for its unique AIE feature, i.e., reduced emission in aqueous media but enhanced emission in crystal. Meanwhile, for 6-MOS, the conventional restriction of the intramolecular motion (RIM) mechanism is responsible for its AIE feature. More interestingly, the unique water-sensitive fluorescence property of 5-MOS enables its successful application for wash-free mitochondria imaging. This work not only demonstrates an ingenious tactic to seek new AIEgens from natural fluorescent species but also benefits the structure design and application exploration of next-generation AIEgens.

Stretchable and Self-Healing Elastomers with Aggregation-Induced Emission Based on Hydrogen Bonding Cross-Linked Networks

With the fast advancement of flexible and stretchable electronics, the development of organic semiconductors with intrinsic stretchability and self-healing properties is desirable and significant yet remains a substantial challenge. Herein, we propose a simple and effective synthetic strategy to construct intrinsically stretchable and self-healing organic light-emitting elastomers via incorporating aggregation-induced emission (AIE) luminogens into hydrogen-bonding cross-linked networks. Owing to the hydrogen-bonding interactions within the networks, the resulting light-emitting elastomers achieved a stress–strain of about 700% and a self-healing efficiency of over 70% under ambient conditions. More importantly, the resulting elastomers have been examined to be highly adhesive and compatible with the silver nanowire networks, exhibiting smart luminescence behaviors and excellent conductivity. This study sheds light on the design and development of stretchable and self-healing organic light-emitting elastomers with promising optoelectronic characteristics, which would inspire a wide range of fancy applications for flexible and stretchable electronics.

Molecular and Aggregate Synergistic Engineering of Aggregation-Induced Emission Luminogens to Manipulate Optical/Electronic Properties for Efficient and Diversified Functions.

The optical/electronic properties of organic luminescent materials can be regulated by molecular structure modification, which not only requires sophisticated and time-consuming synthesis but also is unable to accurately afford the optical properties of materials in the aggregate state. Herein, a facile strategy of molecular and aggregate synergistic engineering is proposed to manipulate the optical/electronic properties of a luminogen, ACIK, in the solid state for efficient and diversified functions. ACIK is facilely synthesized and exhibits three polymorphic states (ACIK-Y, ACIK-R, and ACIK-N) with a large emission difference of 102 nm from yellow to near-infrared (NIR). Their structure-property relationships were investigated by crystallographic analyses and computational studies. ACIK-Y, with the most twisted structure, exhibits an intriguing color-tuned fluorescence between yellow and NIR in the solid state in response to multiple stimuli. Shuttle-like ACIK-R microcrystals exhibit an optical waveguide property with a low optical loss coefficient of 19 dB mm-1. ACIK dots display bright NIR-I emission, large Stokes shift, and strong NIR-II two-photon absorption. ACIK dots show specific lipid droplets-targeting capability and can be successfully applied for two-photon fluorescence imaging of mouse brain vasculature with deep penetration and high spatial resolution. This study will inspire more insights in developing advanced optical/electronic materials based on a single chromophore for practical applications.

Probing the deep brain: Enhanced multi-photon imaging by aggregation-induced emission luminogens via nanocrystallization

The latest requirement of optical imaging is to visualize vital, thick, and complex biological tissues in real-time and minimum-invasive mode. Among diverse available diagnostic tools, multi-photon imaging (MPI) with long wavelength excitation and exceptional lateral resolution has been a perfect option. However, the existing palette of MPI contrast agents either suffers from sub-optimal imaging performance or non-negligible risk in biosafety, exploration of suitable probes is thus of great significance. To address these concerns, in this work, pure organic nanocrystals (NCs) were developed based on aggregation-induced emission luminogens (AIEgens) (DPTA-BT) with an ultrasound-assisted method. Compared to the amorphous DPTA-BT nanoparticles (NPs), NCs with orderly arranged molecules exhibited highly enhanced nonlinear optical signals, including up to 15.35 folds of two-photon action cross-section (2PACS) and up to 4.11 folds of three-photon action cross-section (3PACS). The combination of MPI and DPTA-BT NCs has contributed to a 1900 μm imaging depth of vasculature after craniotomy and a 765 μm imaging depth through the intact skull. The safe use of DPTA-BT NCs was verified by the in vitro and in vivo biosafety assessment. This work is thus expected to encourage more innovation in the development of organic contrast agents for MPI.

Fabrication of a Large-Area Flexible Scintillating Membrane for High-Resolution X-ray Imaging Using an AIEgen-Functionalized Metal-Organic Framework.

With the growing demand for X-ray imaging, especially for three-dimensional objects with curved surfaces, a large-area flexible X-ray imaging membrane based on scintillating materials becomes the focus of vigorous investigation. Among the developed scintillators, metal-organic frameworks (MOFs) featuring tunable photophysical properties and marked luminescence stability hold great promise for serving as ideal X-ray scintillators. Here, we report a flexible composite scintillating membrane with superior imaging performance. The membrane is achieved by embedding an aggregation-induced emission (AIE) luminogen (AIEgen, H4ETTC)-functionalized MOF scintillator (Y-PCN-94) into a polymer matrix (PDMS). Notably, Y-PCN-94 exhibits a strong AIE effect under both ultraviolet (UV) light and X-ray irradiation, which is also the first time that the AIE effect was observed in the MOF system under an ionizing radiation field. This also gives the material promising radioluminescence properties, such as a low X-ray detection limit (1.6 μGy s-1) and high imaging resolution (>14.3 lp mm-1), which can be mainly attributed to the combination of the AIE effect and strong X-ray stopping power. This work demonstrates that incorporating AIEgens into MOFs or other frameworks can offer an alternative approach for producing high-performance X-ray scintillators.

Tuning Photophysical Properties via Positional Isomerization of the Pyridine Ring in Donor–Acceptor-Structured Aggregation-Induced Emission Luminogens Based on Phenylmethylene Pyridineacetonitrile Derivatives

A series of aggregation-induced emission (AIE)-featured phenylmethylene pyridineacetonitrile derivatives named o-DBCNPy ((Z)-3-(4-(di-p-tolylamino)phenyl)-2-(pyridin-2-yl)acrylonitrile), m-DBCNPy ((Z)-3-(4-(di-p-tolylamino)phenyl)-2-(pyridin-3-yl)acrylonitrile), and p-DBCNPy ((Z)-3-(4-(di-p-tolylamino)phenyl)-2-(pyridin-4-yl)acrylonitrile) have been synthesized by tuning the substitution position of the pyridine ring. The linkage manner of the pyridine ring had influences on the molecular configuration and conjugation, thus leading to different photophysical properties. The absorption and fluorescence emission peak showed a bathochromic shift when the linking position of the pyridine ring changed from the meta to the ortho and para position. Meanwhile, o-DBCNPy exhibited the highest fluorescence quantum yield of 0.81 and the longest fluorescence lifetime of 7.96 ns as a neat film among all three isomers. Moreover, non-doped organic light-emitting diodes (OLEDs) were assembled in which the molecules acted as the light-emitting layer. Due to the relatively prominent emission properties, the electroluminescence (EL) performance of the o-DBCNPy-based OLED was superior to those of the devices based on the other two isomers with an external quantum efficiency (EQE) of 4.31%. The results indicate that delicate molecular modulation of AIE molecules could endow them with improved photophysical properties, making them potential candidates for organic photoelectronic devices.

Neutrophil-like Biomimic AIE Nanoparticles with High-Efficiency Inflammatory Cytokine Targeting Enable Precise Photothermal Therapy and Alleviation of Inflammation.

Although photothermal therapy (PTT) has thrived as a promising treatment for drug-resistant bacterial infections by avoiding the abuse of antibiotics, the remaining challenges that limit the treatment efficiency are the poor targeting properties of infected lesions and low penetration to the cell membrane of Gram-negative bacteria. Herein, we developed a biomimetic neutrophil-like aggregation-induced emission (AIE) nanorobot (CM@AIE NPs) for precise inflammatory site homing and efficient PTT effects. Due to their surface-loaded neutrophil membranes, CM@AIE NPs can mimic the source cell and thus interact with immunomodulatory molecules that would otherwise target endogenous neutrophils. Coupled with the secondary near-infrared region absorption and excellent photothermal properties of AIE luminogens (AIEgens), precise localization, and treatment in inflammatory sites can be achieved, thereby minimizing damage to surrounding normal tissues. Moreover, CM@AIE NP-mediated PTT was stimulated in vivo by a 980 nm laser irradiation, which contributed to the extent of the therapeutic depth and limited the damage to skin tissues. The good biocompatibility and excellent in vitro and in vivo antibacterial effects prove that CM@AIE NPs can provide a strategy for broad-spectrum antibacterial applications.

Free Radical-Mediated Intramolecular Photocyclization of AIEgens Based on 2,3-Diphenylbenzo[b]thiophene S,S-Dioxide

As an important category of photochemical reactions, photocyclization is regarded as an ideal entry point for building intelligent photoresponsive materials. Herein, a series of aggregation-induced emission luminogens (AIEgens) with sensitive photoresponsive behavior are developed based on 2,3-diphenylbenzo[b]thiophene S,S-dioxide (DP-BTO), and the impacts of substituents with different electronic structures are investigated. The comprehensive experimental and computational characterizations reveal that their photoresponsive activity is resulted from triplet diradical-mediated intramolecular photocyclization, followed by dehydrogenation to yield stable polycyclic photoproducts. This photocyclization process is active in solution but suppressed in the solid state, and thus can act as a supplementary nonradiative decay channel for the excited state to contribute to AIE effect. Moreover, the generated triplet diradical intermediates upon light irradiation can effectively inhibit the growth of S. aureus, indicative of their promising application as antibacterial agents. This work provides an in-depth mechanistic description about the photocyclization of DP-BTO derivatives and furnishes a perspective on the correlation of photochemical decay and photophysical property.

Composites of Silk Nanofibrils and Metal–Organic Framework Nanosheets for Fluorescence-Based Sensing and UV Shielding

Silk fibroin, a widely used natural biopolymer, presents remarkable flexibility and biodegradability, making it of great interest as a polymer matrix for functional composite materials. Herein, composites of silk nanofibrils and metal–organic framework (MOF) nanosheets were successfully fabricated by a coincubation and coassembly process. Under heat incubation, silk fibroin self-assembled into one-dimensional nanofibrils, while MOF nanosheets simultaneously covered or wrapped on the silk nanofibrils in a water suspension. Transparent composite membranes were obtained from their water suspensions by the solution casting method. The regenerated silk nanofibrils formed a network structure, and the integrated MOF nanosheets (0.1 to 3.0 wt %) endowed the composites with aggregation-induced emission luminogen (AIEgen)-based fluorescence. The fluorescence intensity of the composites was significantly enhanced owing to the interfacial interactions between silk nanofibrils and MOF nanosheets. The composite membranes also offer excellent UV shielding while maintaining optical transparency in the visible spectrum. This work provides an efficient pathway to fabricate luminescent silk protein-based composites for functional materials such as fluorescence sensing and anticounterfeiting.