Chemiluminescence Resonance Energy Transfer Process Research Articles

Organic Semiconductor Nanosheets for Sulfite Detecting Based on Activation of Sulfite and a Synergetic Chemiluminescence Resonance Energy Transfer Process in a Mild System of Fe2+-SO32.

Sulfur dioxide (SO2) as one kind of air pollution not only causes extreme environmental pollution but also negatively affects human health. Chemiluminescence (CL) methods applied for sulfite analysis with high selectivity based on activating sulfite with oxidants are always implemented in acid media with a high background rise. In this work, we proposed to develop a mild CL system of Fe2+-SO32- to detect sulfite under neutral conditions and provide in situ CL spectral data for deeply studying the CL mechanism of Fe2+-SO32-. Herein, we first synthesized one type of water-soluble supramolecular nanosheets, APDI NSs, which had a strong oxidation potential (+2.9 V) due to a π-conjugated system for activation of sulfite to enhance the generation of SO3̇- and other active radicals, and strong a CL signal from the APDI NSs-Fe2+-SO32- system was generated. By studying the CL mechanism under acidic and neutral conditions, a new CL reaction pathway (path-1) and a key intermediate, S2O42-, from the reaction of Fe2+ and SO32- were found. The CL signal was emitted by SO2* after oxidation of S2O42- by strong oxidants like SO4•- and further amplified by APDI NSs through the CL resonance energy transfer (CRET) process. Based on the APDI NSs-Fe2+-SO32- system under neutral conditions, a CL method for detecting SO32- was established. The detection limit was 2.7 × 10-8 M (S/N = 3), and the recovery rates in spiked water samples were in the range of 87%-101%. This study strengthens the understanding of the CL reaction process of the Fe2+-SO32- system and provides a mild sulfite sensing platform for environmental samples.

Chemiluminescence resonance energy transfer-based multistage nucleic acid amplification circuits for MiRNA detection with low background.

Chemiluminescence resonance energy transfer (CRET)-based assays have shown great potential in biosensing due to their negligible background autofluorescence, yet are still limited by their low sensitivity and short half-life luminescence. Herein, a multistage CRET-based DNA circuit was constructed with amplified luminescence signals for accurate miRNA detection and fixed reactive oxygen species (ROS) signals for cell imaging. The DNA circuit is designed through an ingenious programmable catalytic hairpin assembly (CHA), hybridization chain reaction (HCR), and the use of DNAzyme to realize target-triggered precise regulation of distance between the donor and acceptor for CRET-mediated excitation of photosensitizers. In detail, the analyte catalyzes the hybridization of CHA reactants, which leads to the assembly of multiple HCR-mediated DNAzyme nanowires. Subsequently, DNAzymes catalyze the oxidation of luminol by H2O2, and the adjacent photosensitizer chlorin e6 (Ce6) anchored on the DNA nanostructure is stimulated by the CRET process, resulting in the amplified long-wavelength luminescence and the generation of single oxygen signals through further energy transfer to oxygen. The biomarker miRNA can be detected with great sensitivity by integrating the recognition module into a universal platform. Furthermore, the DNA circuit enables CRET-mediated intracellular miRNA imaging, by detecting singlet oxygen signals through a ROS probe. The significant amplification effect is attributed to the robust multiple recognition of the target and the guaranteed transduction of the CRET signal through programmable engineering of DNA nanostructures. The CRET-based DNA circuit achieves amplified long-wavelength luminescence for accurate miRNA detection with low background and ROS-mediated signal fixation for cell imaging, making it a promising candidate for early diagnosis and theranostics.

A simple and stable chemiluminescence resonance energy transfer system based on Ce(IV)-MOFs for detection of sulfite

Chemiluminescence (CL) is an effective way for designing sulfite (SO32-) sensors. However, the practical application of these sensors was hampered so far due to the poor selectivity or stability of the probes (e.g., KMnO4 and Ce4+). In this work, the Ce(IV)-MOF was fabricated through a simple and time-saving hydrothermal synthetic method. The special structure of Ce(IV)-MOF endowed it with high selectivity and stability in the CL reaction. Based on chemiluminescence resonance energy transfer (CRET) from the luminescent intermediate of the CL system to dyes (Nile blue, and rhodamine B), a simple, stable and sensitive CL sensing platform for SO32- was successfully established. The proposed CL sensing platform with the outstanding CL efficiency hold great potential for detecting SO32- in complex samples. This study not only broadened the application of MOF in CL field, but also provided a new clue for the design of stable CL system and CRET process.

Self-Illuminating Photodynamic Therapy with Enhanced Therapeutic Effect by Optimization of the Chemiluminescence Resonance Energy Transfer Step to the Photosensitizer.

The major obstacles to the wider application of photodynamic therapy (PDT) are drawbacks of the current photosensitizers and the tissue penetration limit of the common outer light source. In the present study, the chemiluminescence (CL) from the luminol-H2O2-horseradish peroxidase reaction was explored as a potential inner light source for the intracellular activation of carbon dots (CDs)-based PDT system. To fully use the light and enhance the overall PDT yield, the nanocarrier of CDs, the light of CL, and the PDT agent chlorin e6 (Ce6) were carefully selected and designed to form an efficient and united system. Bright-yellow-emissive CDs (y-CDs) were synthesized through purposeful regulation of the absorption and emission spectra to enhance the overlapping areas in the chemiluminescence resonance energy transfer (CRET) and fluorescence resonance energy transfer (FRET) processes. Our results reflected CL-induced y-CDs-Ce6 system (10 μM) successfully generated reactive oxygen species (ROS, 35.93%), killed ∼90% SMMC-7721 cells in vitro, and significantly delayed tumor growth in vivo. On the basis of immunohistochemical observations of proliferating cell nuclear antigen (PCNA) and platelet/endothelial cell adhesion molecule-1 (PECAM-1 or CD31) results, we concluded that the CL-induced y-CDs-Ce6 system had excellent performance in cancer therapy. The enhanced therapeutic effect was ascribed to two pathways: a direct CRET process and another process of CRET with subsequent y-CD-mediated FRET (CRET-to-FRET).

Target-Catalyzed DNA Four-Way Junctions for CRET Imaging of MicroRNA, Concatenated Logic Operations, and Self-Assembly of DNA Nanohydrogels for Targeted Drug Delivery.

Here we report a target-catalyzed DNA four-way junction (DNA-4WJ) on the basis of toehold-mediated DNA strand displacement reaction (TM-SDR), which is readily applied in enzyme-free amplified chemiluminescence resonance energy transfer (CRET) imaging of microRNA. In this system, the introduction of target microRNA-let-7a (miR-let-7a) activates a cascade of assembly steps with four DNA hairpins, followed by a disassembly step in which the target microRNA is displaced and released from DNA-4WJ to catalyze the self-assembly of additional branched junctions. As a result, G-quadruplex subunit sequences and fluorophore fluorescein amidite (FAM) are encoded in DNA-4WJ in a close proximity, stimulating a CRET process in the presence of hemin/K(+) to form horseradish peroxidase (HRP)-mimicking DNAzyme that catalyzes the generation of luminol/H2O2 chemiluminescence (CL), which further transfers to FAM. The background signal is easily reduced using magnetic graphene oxide (MGO) to remove unreacted species through magnetic separation, which makes a great contribution to improve the detection sensitivity and achieves a detection limit as low as 6.9 fM microRNA-let-7a (miR-let-7a). In addition, four-input concatenated logic circuits with an automatic reset function have been successfully constructed relying on the architecture of the proposed DNA-4WJ. More importantly, DNA nanohydrogels are self-assembled using DNA-4WJs as building units after centrifugation, which are driven by liquid crystallization and dense packaging of building units. Moreover, the DNA nanohydrogels are readily functionalized by incorporating with aptamers, bioimaging agents, and drug loading sites, which thus are served as efficient nanocarriers for targeted drug delivery and cancer therapy with high loading capacity and excellent biocompatibility.

Orderly arranged fluorescence dyes as a highly efficient chemiluminescence resonance energy transfer probe for peroxynitrite.

Chemiluminescence (CL) probes for reactive oxygen species (ROS) are commonly based on a redox reaction between a CL reagent and ROS, leading to poor selectivity toward a specific ROS. The energy-matching rules in the chemiluminescence resonance energy transfer (CRET) process between a specific ROS donor and a suitable fluorescence dye acceptor is a promising method for the selective detection of ROS. Nevertheless, higher concentrations of fluorescence dyes can lead to the intractable aggregation-caused quenching effect, decreasing the CRET efficiency. In this report, we fabricated an orderly arranged structure of calcein-sodium dodecyl sulfate (SDS) molecules to improve the CRET efficiency between ONOOH* donor and calcein acceptor. Such orderly arranged calcein-SDS composites can distinguish peroxynitrite (ONOO(-)) from a variety of other ROS owing to the energy matching in the CRET process between ONOOH* donor and calcein acceptor. Under the optimal experimental conditions, ONOO(-) could be assayed in the range of 1.0-20.0 μM, and the detection limit for ONOO(-) [signal-to-noise ratio (S/N) = 3] was 0.3 μM. The proposed strategy has been successfully applied in both detecting ONOO(-) in cancer mouse plasma samples and monitoring the generation of ONOO(-) from 3-morpholinosydnonimine (SIN-1). Recoveries from cancer mouse plasma samples were in the range of 96-105%. The success of this work provides a unique opportunity to develop a CL tool to monitor ONOO(-) with high selectivity in a specific manner. Improvement of selectivity and sensitivity of CL probes holds great promise as a strategy for developing a wide range of probes for various ROS by tuning the types of fluorescence dyes.

Label free and homogeneous histone sensing based on chemiluminescence resonance energy transfer between lucigenin and gold nanoparticles

AbstractIn this paper, a label free and homogeneous protocol without recognition elements such as antibody or DNA based on nonenzymatic chemiluminescence resonance energy transfer between lucigenin and gold nanoparticles (AuNPs) is developed for the detection of histone. This chemiluminescence resonance energy transfer process originated from a chemiluminescent donor–acceptor pair in which the chemiluminescence system of the lucigenin–H2O2 as a donor and AuNPs as an acceptor owing to the overlapping of the chemiluminescence spectrum of the lucigenin–H2O2 system and the absorption spectrum of AuNPs, leading to a significant decrease in chemiluminescence signal from the lucigenin–H2O2 system. However, the presence of histone resulted in the aggregation of AuNPs via the electrostatic interaction between negatively charged AuNPs and positively charged histone, which inhibited the chemiluminescence resonance energy transfer process. Thus the chemiluminescence signal of the lucigenin–H2O2 system was restored. This could be used for the detection of histone with a linear range of 30–500ng/mL, and a detection limit of 25ng/mL. This sensitivity increased about 4 orders of magnitude over that of the reported fluorometric method. The proposed strategy for the detection of histone is simple, facile, reliable, and opens a new avenue for the determination of histone.

Sensing and Biosensing with Semiconductor Quantum Dots

AbstractDue to an internal error, the following article was added after the original publication of the special issue on Nanochemistry (11‐12/2012).Semiconductor quantum dots (QDs) exhibit unique photophysical properties, turning these nanomaterials into ideal components for the development of optical or optoelectronic sensors and biosensors. Various methods and mechanisms of using QDs for sensing have been implemented, including the probing of recognition events by the luminescence of the QDs, their application in fluorescence resonance energy transfer (FRET), electron transfer (ET), chemiluminescence resonance energy transfer (CRET), and photoelectrochemical generation of photocurrents. These different mechanisms are exemplified by discussing the QD‐based sensing of low‐molecular‐weight substrates, chiroselective sensing of amino acids, probing of the catalytic activities of enzymes (casein kinase, tyrosinase, NAD+‐dependent enzymes), and analysis of DNA and of aptamer‐substrate complexes. Specifically, the amplified QD‐based sensing of DNA using exonuclease III as target regeneration biocatalyst and the multiplexed detection of DNAs using differently sized QDs are discussed. Also, the implementation of the CRET process for the multiplexed analysis of DNA using differently sized QDs is addressed. Finally, the use of semiconductor QDs for the photoelectrochemical detection of DNA, aptamer‐substrate complexes and enzyme activities are discussed. Specifically, the use of QDs for photoelectrochemical sensors, using the CRET process as internal excitation light source, is described. The future applications of the various QD‐based sensors as analytical devices and as nanotools that probe intracellular processes are discussed.

Following Glucose Oxidase Activity by Chemiluminescence and Chemiluminescence Resonance Energy Transfer (CRET) Processes Involving Enzyme-DNAzyme Conjugates

A hybrid consisting of glucose oxidase-functionalized with hemin/G-quadruplex units is used for the chemiluminescence detection of glucose. The glucose oxidase-mediated oxidation of glucose yields gluconic acid and H2O2. The latter in the presence of luminol acts as substrate for the hemin/G-quadruplex-catalyzed generation of chemiluminescence. The glucose oxidase/hemin G-quadruplex hybrid was immobilized on CdSe/ZnS quantum dots (QDs). The light generated by the hybrid, in the presence of glucose, activated a chemiluminescence resonance energy transfer process to the QDs, resulting in the luminescence of the QDs. The intensities of the luminescence of the QDs at different concentrations of glucose provided an optical means to detect glucose.

Chemiluminescence and Chemiluminescence Resonance Energy Transfer (CRET) Aptamer Sensors Using Catalytic Hemin/G-Quadruplexes

The incorporation of hemin into the thrombin/G-quadruplex aptamer assembly or into the ATP/G-quadruplex nanostructure yields active DNAzymes that catalyze the generation of chemiluminescence. These catalytic processes enable the detection of thrombin and ATP with detection limits corresponding to 200 pM and 10 μM, respectively. The conjugation of the antithrombin or anti-ATP aptamers to CdSe/ZnS semiconductor quantum dots (QDs) allowed the detection of thrombin or ATP through the luminescence of the QDs that is powered by a chemiluminescence resonance energy-transfer (CRET) process stimulated by the hemin/G-quadruplex/thrombin complex or the hemin/G-quadruplex/ATP nanostructure, in the presence of luminol/H(2)O(2). The advantages of applying the CRET process for the detection of thrombin or ATP, by the resulting hemin/G-quadruplex DNAzyme structures, are reflected by low background signals and the possibility to develop multiplexed aptasensor assays using different sized QDs.

Design of Molecular Beacons as Signaling Probes for Adenosine Triphosphate Detection in Cancer Cells Based on Chemiluminescence Resonance Energy Transfer

In the present study, binary and triplex DNA molecular beacons, as signaling probes based on a luminol-H(2)O(2)-horseradish peroxidase (HRP)-fluorescein chemiluminescence resonance energy transfer (CRET) system and structure-switching aptamers for highly sensitive detection of small molecules, are developed using adenosine triphosphate (ATP) as a model analyte to demonstrate the generality of the strategy. This CRET process occurs from donor luminol to acceptor fluorescein, which is oxidized by H(2)O(2) and catalyzed by HRP. DNA aptamer for ATP is first attached on the surface of magnetic nanoparticles (MNPs). The cDNA linker has an extension that hybridizes with two other DNAs (LumAuNP-DNA and F-DNA) or three other DNAs (HRP-DNA, LumAuNP-DNA, and F-DNA) to fabricate CRET-BMBP-MNP or CRET-TMBP-MNP conjugates that provide the CRET signals. Thus, in the absence of ATP, when the MNPs are removed from the solution, they also take with them the linker DNA and the CRET signal probes, and no CRET signal can be detected. However, when ATP is introduced, a competition for the ATP aptamer between ATP and the cDNA linker occurs. As a result, CRET-BMBP and CRET-TMBP are forced to dissociate from the MNP surface based on the structure switching of the aptamer. The CRET signals are proportional to the concentration of ATP. In order to accelerate the rate of the aptamer structure-switching process, an invader DNA is introduced into the proposed strategy. The present CRET system provides a low detection limit of 1.1 x 10(-7) and 3.2 x 10(-7) M for ATP detection by BMBP and TMBP, respectively, which also exhibits a good selectivity for ATP detection. Sample assays of ATP in K562 leukemia cells and 4T1 breast cancer cells confirm the reliability and practicality of the protocol, which reveal a good prospect of this platform for biological sample analysis.