Quenching study of Cu2S-MPA/NGODs composites in electrochemiluminescence detection by modulating resonance energy transfer and adsorption process.

This study explores the principles of resonance energy transfer and adsorption modulation using composites of Cu2S-MPA/NGODs. These composites can efficiently control the quenching process of electrochemiluminescence (ECL). Mercaptopropionic acid (MPA) was added during the synthesis of Cu2S-MPA to enhance its attachment to nitrogen-doped graphene quantum dots (NGODs). The UV absorption peaks of NGODs coincided with the emission peaks of luminol ECL, enabling resonance energy transfer and enhancing the quenching capability of Cu2S-MPA. Meanwhile, there is another quenching strategy. When the readily reducible Cu+ ions underwent partial reduction to Cu when they were bound to NGODs. This weakened the electrocatalytic effect on reactive oxygen species (ROS) and had a detrimental impact on electron transfer. Under optimal conditions, the immunosensor ECL intensity decreased linearly with the logarithm of carcinoembryonic antigen (CEA) concentration in the range of 0.00001-40 ng/mL, with a detection limit of 0.269 fg/mL. The sensor was effectively utilized for the identification of CEA in actual serum samples.

Improved resolution of 3-mercaptopropionate dioxygenase active site provided by ENDOR spectroscopy offers insight into catalytic mechanism.

3-mercaptopropionate (3MPA) dioxygenase (MDO) is a mononuclear nonheme iron enzyme that catalyzes the O2-dependent oxidation of thiol-bearing substrates to yield the corresponding sulfinic acid. MDO is a member of the cysteine dioxygenase family of small molecule thiol dioxygenases and thus shares a conserved sequence of active site residues (Serine-155, Histidine-157, and Tyrosine-159), collectively referred to as the SHY-motif. It has been demonstrated that these amino acids directly interact with the mononuclear Fe-site, influencing steady-state catalysis, catalytic efficiency, O2-binding, and substrate coordination. However, the underlying mechanism by which this is accomplished is poorly understood. Here, pulsed electron paramagnetic resonance spectroscopy [1H Mims electron nuclear double resonance spectroscopy] is applied to validate density functional theory computational models for the MDO Fe-site simultaneously coordinated by substrate and nitric oxide (NO), (3MPA/NO)-MDO. The enhanced resolution provided by electron nuclear double resonance spectroscopy allows for direct observation of Fe-bound substrate conformations and H-bond donation from Tyr159 to the Fe-bound NO ligand. Further inclusion of SHY-motif residues within the validated model reveals a distinct channel restricting movement of the Fe-bound NO-ligand. It has been argued that the iron-nitrosyl emulates the structure of potential Fe(III)-superoxide intermediates within the MDO catalytic cycle. While the merit of this assumption remains unconfirmed, the model reported here offers a framework to evaluate oxygen binding at the substrate-bound Fe-site and possible reaction mechanisms. It also underscores the significance of hydrogen bonding interactions within the enzymatic active site.

Thiol-Ene Click Cross-linking of Starch Oleate Films for Enhanced Properties.

Biobased films were synthesized from starch oleate (DS = 2.2) cross-linked with polyethylene glycol with Mn = 2000 and 1000 g · mol-1, and ethylene glycol, all of which were esterified with either lipoic acid (LA) or 3-mercaptopropionic acid (MPA). Cross-linking was achieved through a UV-initiated thiol-ene click, and confirmed by Fourier transform infrared spectroscopy and rheometry. The films exhibit higher degradation temperatures, and an increased degree of crystallinity as cross-linker length increased. The introduction of MPA-based cross-linkers resulted in hydrophilic films, while the contact angle was barely affected by the addition of LA-based cross-linkers. A reduction in maximum strength upon introducing the cross-linkers was observed, while an increase in elongation was observed for most of the LA-based cross-linkers. Our results demonstrate the potential for tuning the mechanical and thermal properties of starch-based films through the cross-linker choice, with some formulations exhibiting increased flexibility that may be well suited for packaging applications.

Fine tuning of CdxZn1-xS for photo-depolymerization of alkaline lignin into vanillin.

Lignin is abundant and contains a large number of aromatic groups. Herein, CdxZn1-xS photocatalyst with tunable band gap energy was successfully synthesized by using 3-mercaptopropionic acid as a structure tuning additive. CdxZn1-xS can depolymerize alkaline lignin to vanillin by the photocatalytic process. Each gram of alkaline lignin can produce 46.5 mg of vanillin. 2-Phenoxy-1-phenylethanol (PP-ol) and other model compounds were used to understand the depolymerizing process of lignin. Fine tuned CdxZn1-xS can effectively cleave the Cß-O-4 bond existed in PP-ol under simulated sunlight. The highest conversion of PP-ol was 89.5% with phenol and acetophenone yields of 66.2% and 33.5%, respectively. The mechanism studies confirm that the Cα-H in PP-ol and lignin is firstly dehydrogenated to form Cα radical intermediates, and then the photogenerated electrons break the adjacent Cß-O bond. This research provides a new strategy to prepare valuable chemicals by virtue of renewable biomass and simulated sunlight.

Structure of 3-mercaptopropionic acid dioxygenase with a substrate analog reveals bidentate substrate binding at the iron center.

Thiol dioxygenases are a subset of nonheme iron oxygenases that catalyze the formation of sulfinic acids from sulfhydryl-containing substrates and dioxygen. Among this class, cysteine dioxygenases (CDOs) and 3-mercaptopropionic acid dioxygenases (3MDOs) are the best characterized, and the mode of substrate binding for CDOs is well understood. However, the manner in which 3-mercaptopropionic acid (3MPA) coordinates to the nonheme iron site in 3MDO remains a matter of debate. A model for bidentate 3MPA coordination at the 3MDO Fe-site has been proposed on the basis of computational docking, whereas steady-state kinetics and EPR spectroscopic measurements suggest a thiolate-only coordination of the substrate. To address this gap in knowledge, we determined the structure of Azobacter vinelandii 3MDO (Av3MDO) in complex with the substrate analog and competitive inhibitor, 3-hydroxypropionic acid (3HPA). The structure together with DFT computational modeling demonstrates that 3HPA and 3MPA associate with iron as chelate complexes with the substrate-carboxylate group forming an additional interaction with Arg168 and the thiol bound at the same position as in CDO. A chloride ligand was bound to iron in the coordination site assigned as the O2-binding site. Supporting HYSCORE spectroscopic experiments were performed on the (3MPA/NO)-bound Av3MDO iron nitrosyl (S = 3/2) site. In combination with spectroscopic simulations and optimized DFT models, this work provides an experimentally verified model of the Av3MDO enzyme-substrate complex, effectively resolving a debate in the literature regarding the preferred substrate-binding denticity. These results elegantly explain the observed 3MDO substrate specificity, but leave unanswered questions regarding the mechanism of substrate-gated reactivity with dioxygen.

An injectable hydrogel with pH-sensitive and self-healing properties based on 4armPEGDA and N-carboxyethyl chitosan for local treatment of hepatocellular carcinoma.

Injectable hydrogels with pH-sensitive and self-healing properties have great application potential in the field of anti-cancer drug carriers. In this work, an injectable hydrogel is prepared using 4armPEG-benzaldehyde (4armPEGDA) and N-carboxyethyl chitosan (CEC) as a new drug carrier. The gelation time, equilibrium swelling rate, degradation time, and dynamic modulus of the injectable hydrogels can be adjusted by merely changing the concentration of 4armPEGDA. The volume of the hydrogel shrinks at pH 5.6 and expands at pH 7.4, which helps to control the release of anti-cancer drug. At pH 5.6, the hydrogels show a fast and substantial Dox release effect, which is five times higher than that at pH 7.4. In vitro cumulative drug release of all the hydrogels reached equilibrium on about the fourth day, and the hydrogel is completely degraded within five days, which contributes to the Dox-loaded hydrogel to further release the remaining Dox. Moreover, the Dox-loaded hydrogel shows a strong inhibitory effect on the growth of human hepatocellular carcinoma cells (HepG2). Finally, the anti-tumor model experiment in vivo demonstrated that the Dox-loaded hydrogel can significantly inhibit tumor growth within five days. Therefore, such injectable hydrogels are excellent carriers for the potential treatment of hepatocellular carcinoma.

DNA Electrochemical Biosensor Based on Iron Oxide/Nanocellulose Crystalline Composite Modified Screen-Printed Carbon Electrode for Detection of Mycobacterium tuberculosis.

Death from tuberculosis has resulted in an increased need for early detection to prevent a tuberculosis (TB) epidemic, especially in closed and crowded populations. Herein, a sensitive electrochemical DNA biosensor based on functionalized iron oxide with mercaptopropionic acid (MPA-Fe3O4) nanoparticle and nanocellulose crystalline functionalized cetyl trimethyl ammonium bromide (NCC/CTAB) has been fabricated for the detection of Mycobacterium tuberculosis (MTB). In this study, a simple drop cast method was applied to deposit solution of MPA-Fe3O4/NCC/CTAB onto the surface of the screen-printed carbon electrode (SPCE). Then, a specific sequence of MTB DNA probe was immobilized onto a modified SPCE surface by using the 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) coupling mechanism. For better signal amplification and electrochemical response, ruthenium bipyridyl Ru(bpy)32+ was assigned as labels of hybridization followed by the characteristic test using differential pulse voltammetry (DPV). The results of this biosensor enable the detection of target DNA until a concentration as low as 7.96 × 10-13 M with a wide detection range from 1.0 × 10-6 to 1.0 × 10-12 M. In addition, the developed biosensor has shown a differentiation between positive and negative MTB samples in real sampel analysis.

MPA-CdTe quantum dots as "on-off-on" sensitive fluorescence probe to detect ascorbic acid via redox reaction.

Mercaptopropionic acid (MPA) capped CdTe quantum dots (MPA-CdTe QDs) were synthesized in aqueous medium by hydrothermal method, which modified by Fe3+ could be used as a fluorescent probe to detect ascorbic acid (AA). MPA-CdTe QDs fluorescence probe could be used as successive sensor for metal ions and AA with "on-off-on" process. The fluorescence of QDs was quenched after adding Fe3+ to MPA-CdTe QDs. Then, the fluorescence of the Fe3+@MPA-CdTe QDs can be sensitively turned on by AA to give an "on-off-on" fluorescence response according to the oxidation-reduction between Fe3+ and AA. There was a linear relationship between fluorescence intensity quenching value and the concentration of Fe3+ in the range of 2-10 µM since Fe3+ sensitively reacted with CdTe QDs. The linear detection range for AA was 0.1-1 µM with a limit of detection of 6.6 nM. The principle is proved by fluorescence emission spectroscopy, nuclear magnetic resonance spectroscopy. The proposed method is successfully used to detect the AA in human plasma sample.

Sensitive and selective nitrite assay based on fluorescent gold nanoclusters and Fe2+/Fe3+ redox reaction.

In recent years, gold nanoclusters (AuNCs) have received considerable attention as optical transducers in chemo/biosensors. Herein, a facile and efficient assay for NO2- has been successfully developed based on the fluorescence quenching of AuNCs co-modified by bovine serum albumin and 3-mercaptopropionic acid (BSA/MPA-AuNCs). In the presence of NO2- under acidic conditions, Fe2+ can be readily oxidized and transformed to Fe3+, which can significantly suppress the fluorescence of BSA/MPA-AuNCs via non-radiative electron-transfer mechanism. The linear range and detection limit for this system were found to be 5-30 µM (r = 0.9975) and 0.7 µM, respectively. Other common anions and cations showed only very minor interference with the NO2- detection. Furthermore, the effectiveness of the proposed sensing strategy was validated by the demonstration of good performance in the determination of the amount of NO2- in ham samples, rendering it a powerful tool for the assessment of food security and water quality.

Sulfur doped graphene quantum dots as a potential sensitive fluorescent probe for the detection of quercetin.

In this work, a novel, selective and sensitive fluorescent probe (sulfur doped graphene quantum dots, SGQDs) was designed for real-time detection of quercetin in red wine samples. SGQDs were synthesized by pyrolyzing citric acid (CA) and 3-Mercaptopropionic acid (MPA) and characterized through advanced techniques. It was observed that fluorescence intensity of SGQDs could be substantially quenched by the addition of quercetin through inner filter effect (IFE) mechanism. Additionally, a visual color change (colorless to light yellow) was also noticed after addition of quercetin into a solution of SGQDs. The change in SGQDs fluorescence intensity with varying quercetin content revealed good linearity in the 0-50.0 µM range with regression coefficient of 0.9943 and a lowest detection limit of 0.006 µg/mL. To authenticate the real-time application of SGQDs as a potential fluorescent probe, red wine samples having different quercetin concentrations were used for quantitative analysis, after the optimization of several analytical parameters.

Synthesis of water-soluble Ni(II) complexes and their role in photo-induced electron transfer with MPA-CdTe quantum dots.

Photocatalytic water splitting using solar energy for hydrogen production offers a promising alternative form of storable and clean energy for the future. To design an artificial photosynthesis system that is cost-effective and scalable, earth abundant elements must be used to develop each of the components of the assembly. To develop artificial photosynthetic systems, we need to couple a catalyst for proton reduction to a photosensitizer and understand the mechanism of photo-induced electron transfer from the photosensitizer to the catalyst that serves as the fundamental step for photocatalysis. Therefore, our work is focused on the study of light driven electron transfer kinetics from the quantum dot systems made with inorganic chalcogenides in the presence of Ni-based reduction catalysts. Herein, we report the synthesis and characterization of four Ni(II) complexes of tetradentate ligands with amine and pyridine functionalities (N2/Py2) and their interactions with CdTe quantum dots stabilized by 3-mercaptopropionic acid. The lifetime of the quantum dots was investigated in the presence of the Ni complexes and absorbance, emission and electrochemical measurements were performed to gain a deeper understanding of the photo-induced electron transfer process.

Pore Confinement-Enhanced Electrochemiluminescence on SnO2 Nanocrystal Xerogel with NO3- As Co-Reactant and Its Application in Facile and Sensitive Bioanalysis.

Herein, 10-fold electrochemiluminescence (ECL) enhancement from a porous SnO2 nanocrystal (SnO2 NC) xerogel (vs discrete SnO2 NCs) was first observed with NO3- as a novel coreactant. This new booster phenomenon caused by pore characteristic was defined as "pore confinement-induced ECL enhancement", which originated from two possible reasons: First, the SnO2 NC xerogel with hierarchically porous structure could not only localize massive luminophore near the electrode surface, more importantly, but could accelerate the electrochemical and chemiluminescence reaction efficiency because the pore channels of xerogel could promote the mass transport and electron transfer in the confined spaces. Second, the NO3- could be in situ reduced easily to the active nitrogen species by means of the pore confinement effect, which could be served as a new coreactant for nanocrystal-based ECL amplification with the excellent stability and good biocompatibility. As a proof of concept, a facile and sensitive sensing platform for SO32- detection has been successfully constructed upon effectively quenching of SO32- toward the SnO2 NC xerogel/NO3- ECL system. The key feature about this work presented a grand avenue to achieve the strong ECL signal, especially from weak emitters, which gave a fresh impetus to the construction of new-generation of surface-confined ECL platform with potential applications in ECL imaging and sensing.

Selective Reactivity of Myrcene for Vat Photopolymerization 3D Printing and Postfabrication Surface Modification.

Biosourced materials are gaining interest industrially, but there are still limitations on the library of available materials suitable for advanced manufacturing, especially using photopolymerization-based processing techniques. Terpenes, such as myrcene, are naturally produced materials possessing structural features, specifically alkenes, that avail themselves for such techniques. Free-radical and anionic polymerization techniques were used to explore molecular architecture, such as branching, as well as molecular weight and dispersity on physical properties prior to the production of 3D printing photopolymer resins. The polymyrcene resins were printed into dogbones and mold templates for soft materials. Model reactions with monofunctional thiols were used to demonstrate the potential for postpolymerization and fabrication functionalization, accompanying a physical demonstration where the surface hydrophobicity of polymyrcene could be tuned from superhydrophobic when using an alkyl chain monothiol (greater than 100° water contact angle) to a hydrophilic surface displaying a water contact angle of less than 45° compared with that of the unmodified surface (∼60°). Tunable bulk and surface properties are a unique feature for 3D printing materials and demonstrate the potential of polymyrcene and other biosourced photopolymers to a wide range of research applications.

Tuning optical properties and optical rotation of 3-mercaptopropionic acid capped organic-inorganic hybrid perovskites.

The emission wavelength of organic-inorganic hybrid perovskite quantum dots (QDs) can be tuned by controlling reaction time relevant to the halide exchange. It is because halide exchange with different time would lead to different molar ratio of halides in perovskite QDs such as Cl and Br. Here, to research the ligand's effect on the halide exchange, this work synthesized 3-mercaptopropionic acid (MPA)-capped CH3 NH3 PbBrx Cl3-x QDs. It was found that SH- of MPA appeared to inhibit the halide exchange during the reation. Moreover, although the MPA-capped CH3 NH3 PbBrx Cl3-x QDs did not contain the chiral centre, they exhibit the optical rotation. This may provide a method for chirality manipulation of perovskite.

Colorimetric determination of As(III) based on 3-mercaptopropionic acid assisted active site and interlayer channel dual-masking of Fe-Co-layered double hydroxides with oxidase-like activity.

A colorimetric method is described for the determination of As(III). It is based on the use of 3-mercaptopropionic acid (3-MPA) assisted active site and interlayer channel dual-masking of oxidase-like Fe-Co-layered double hydroxides (Fe-Co-LDH). The Fe-Co-LDH acts as an oxidase-mimicking nanozyme with high activity. It catalyzes the oxidation of colorless 3,3'5,5'-tetramethylbenzidine (TMB) to form a blue product (oxTMB) with an absorption maximum at 652 nm. It is found that As(III) firmly anchors onto the Fe* sites of the 3-MPA-modified Fe-Co-LDH via forming a stable Fe─As(III)─3-MPA─As(III)─Fe structure. This results in masking the active sites and interlayer channels of the Fe-Co-LDH nanozyme. As a result, the presence of As(III) as well as 3-MPA specifically inhibit the LDH-catalyzed chromogenic reaction. Based on the above principle, a colorimetric assay was designed for the determination of As(III). It provided linear response in the 0.10~8.33 µM As(III) concentration range and a detection limit as low as 35 nM. The assay was applied to the quantitation of As(III), even in the presence of potential interferents including As(V), Hg(II) and Pb(II), in environmental and drinking water samples. Graphical abstractSchematic illustration of the As(III) sensing mechanism based on 3-mercaptopropionic acid (3-MPA) assisted active site and interlayer channel dual-masking of Fe-Co-layered double hydroxides (Fe-Co-LDH) with oxidase-like activity. 3-MPA with sulfhydryl and carboxyl groups can assist As(III) to firmly anchor onto the Fe* sites inside the interlayer channels of the Fe-Co-LDH via forming a Fe─As(III)─3-MPA─As(III)─Fe structure, thus selectively resulting in a significant suppression of the chromogenic reaction.

Flower-like curcumin-loaded folic acid-conjugated ZnO-MPA- ßcyclodextrin nanostructures enhanced anticancer activity and cellular uptake of curcumin in breast cancer cells.

Non-spherical structures are beneficial to advance drug delivery effectiveness compared with common spherical ones, due to increased drug loading capability, improved bonding to a vascular wall, enhanced cellular uptake efficacy and prolonged circulation times. In this study, flower-like Zinc oxide-ßcyclodextrin (ßCD) nanostructures functionalized by 3-mercaptopropionic acid (MPA) as a non-spherical delivery system was successfully synthesized for aqueous delivery of curcumin (CUR) to enhance its targeting, bioavailability, and release profile. Terminal carboxyl functional groups were used for the conjugation of folic acid (FA) with the aim of active targeting to folate overexpressing breast cancer cells. The in vitro experimental study and mathematical modeling of CUR release revealed a sustained release with Fickian diffusion as the major release mechanism. MTT, colony formation and Annexin-V FITC/PI assays showed the superior anticancer effect of the system compared to free CUR against breast cancer cell line MDA-MB-231 by promoting the apoptotic respond with no cytotoxic effect on HEK293 normal cells. The efficacy of targeting strategy with FA moieties was demonstrated using the augmented cellular uptake of the FA-conjugated system on overexpressed folate receptor alpha (FRα) cells (MDA-MB-468 breast cancer cell line). Furthermore, loading of CUR to the delivery systems significantly lowered the MIC values (2.5 to 5-fold) against S. aureus and E. coli the infections of which are serious problems in cancer patients. According to the results of this study, the system can serve as a promising non-spherical delivery vehicle for enhancing bioavailability and targeting of hydrophobic anticancer agents in the future.

Ratiometric Upconversion Luminescence Nanoprobe with Near-Infrared Ag2S Nanodots as the Energy Acceptor for Sensing and Imaging of pH in Vivo.

A luminescence resonance energy transfer (LRET) system was successfully developed using near-infrared (NIR) Ag2S nanodots (NDs) as the energy acceptors and upconversion nanoparticles (UCNPs) as the energy donors. The system possessing the properties of NIR excitation (980 nm) and NIR emission (795 nm) was used for the ratiometric detection and bioimaging of pH in tumor cells and zebrafish. Glutathione and mercaptopropionic acid (MPA) co-modified Ag2S NDs (GM-Ag2S NDs) were prepared by ligand exchange with an excellent pH-responsive property over a pH range of 4.0 to 9.0. The NIR GM-Ag2S NDs were covalently grafted with silica coated UCNPs, and an efficient LRET platform was developed via modulation of the thickness of the silica coating. Due to the LRET process between UCNPs and GM-Ag2S NDs, a ratiometric luminescence nanoprobe with the properties of NIR excitation-NIR emission was constructed for pH biosensing and bioimaging. On the basis of high contrast bioimaging, the nanoplatform can distinguish between tumor and normal tissue in the zebrafish model.

Substrate Specificity in Thiol Dioxygenases.

Thiol dioxygenases make up a class of ferrous iron-dependent enzymes that oxidize thiols to their corresponding sulfinates. X-ray diffraction structures of cysteine-bound cysteine dioxygenase show how cysteine is coordinated via its thiolate and amine to the iron and oriented correctly for O atom transfer. There are currently no structures with 3-mercaptopropionic acid or mercaptosuccinic acid bound to their respective enzymes, 3-mercaptopropionate dioxygenase or mercaptosuccinate dioxygenase. Sequence alignments and comparisons of known structures have led us to postulate key structural features that define substrate specificity. Here, we compare the rates and reactivities of variants of Rattus norvegicus cysteine dioxygenase and 3-mercaptopropionate dioxygenases from Pseudomonas aureginosa and Ralstonia eutropha (JMP134) and show how binary variants of three structural features correlate with substrate specificity and reactivity. They are (1) the presence or absence of a cis-peptide bond between residues Ser158 and Pro159, (2) an Arg or Gln at position 60, and (3) a Cys or Arg at position 164 (all RnCDO numbering). Different permutations of these features allow sulfination of l-cysteine, 3-mercaptopropionic acid, and ( R)-mercaptosuccinic acid to be promoted or impeded.

CdTe quantum dots coated with a molecularly imprinted polymer for fluorometric determination of norfloxacin in seawater.

A fluorescent nanoprobe consisting of CdTe quantum dots (QDs) and coated with molecularly imprinted layers was prepared and successfully applied to the determination of norfloxacin (NOR) in seawater and wastewater samples. The 3-mercaptopropionic acid capped QDs were prepared and then covered with a protective silica shell. A molecularly imprinted layer was finally synthesized around the silanized QDs using 3-aminopropyltriethoxysilane as functional monomer and norfloxacin as the template. Compared with the non-imprinted polymer, the fluorescence of the nanoprobe with imprinted polymer (measured at excitation/emission wavelengths of 300/596 nm) is strongly reduced in the presence of NOR, and the imprinting factor is 8.8. Under the optimal experimental conditions, the detection limit of the nanoprobe is 0.18 µM, and response is linear between 0.5 - 28 µM of NOR. The relative standard deviation of the detection of NOR is <7.2%. In order to evaluate the practicality of the probe, wastewater and seawater samples spiked with norfloxacin were analyzed by this method, and recoveries ranged from 96.2 - 106.0%. Graphical abstract Schematic presentation and fluorescence spectrum of fluorescent nanoprobe with selectivity for norfloxacin (NOR). CdTe quantum dots (QDs) are used as fluorescent carriers, 3-aminopropyltriethoxysilane (APTES) as template molecules, tetraethyl orthosilicate (TEOS) as crosslinking agent, and aqueous ammonia as initiator.

An electrochemiluminescent aptasensor for amplified detection of exosomes from breast tumor cells (MCF-7 cells) based on G-quadruplex/hemin DNAzymes.

Exosomes are non-invasive biomarkers for cancer diagnosis. Herein, we describe an electrochemiluminescent (ECL) aptasensor for the detection of exosomes from breast tumor cells. Mercaptopropionic acid (MPA)-modified Eu3+-doped CdS nanocrystals (MPA-CdS:Eu NCs) and H2O2 were used as ECL emitters and coreactant, respectively. The exosomes are recognized and captured by the CD63 aptamer, and then form a G-quadruplex/hemin DNAzyme, which efficiently catalyzes the decomposition of H2O2, resulting in the decreased ECL signal of MPA-CdS:Eu NCs. The exosomes from breast tumor cells (MCF-7 cells) can be detected in the range of 3.4 × 105 to 1.7 × 108 particles per mL. The limit of detection (LOD) was estimated to be 7.41 × 104 particles per mL at a signal-to-noise ratio of 3. The aptasensor has been successfully used to detect exosomes in the serum.