Resonance Energy Transfer System Research Articles

Development of fluorescent FRET probe for determination of glucose based on β-cyclodextrin modified ZnS-quantum dots and natural pigment 3-hydroxyflavone

An environmental friendly fluorescence resonance energy transfer probe for determination of glucose has been developed. The natural pigment, 3-hydroxyflavone, can enter the hydrophobic cavity of beta-cyclodextrin functionalized ZnS quantum dots, forming a fluorescence resonance energy transfer system with beta-cyclodextrin modified ZnS quantum dots as energy donor and 3-hydroxyflavone as energy acceptors. Glucose can be oxidized with assistance of the glucose oxidase to quantitatively produce hydrogen peroxide, which could rapidly quench the fluorescence intensity of the 3-hydroxyflavone in the probe by catalysis of horseradish peroxidase. The probe was successfully applied to determination of glucose in human serum and urine samples, and the results indicated that the average spiking recoveries of glucose ranged from 102 to 113%, with relative standard deviations below 15%. The developed approach were simple and possessed high sensitivity and selective for glucose, and this work provides a new clue for developing fluorescent probe.

Selective Determination of Trinitrotoluene Based on Energy Transfer between Carbon Dots and Gold Nanoparticles.

A fluorescence resonance energy transfer (FRET) system between carbon dots (C-dots) and amine-capped gold nanoparticles (AuNPs) was developed for the selective determination of 2,4,6-trinitrotoluene (TNT). C-dots have an intrinsic florescence emission depending on their exciting wavelength. In the presence of AuNPs, C-dots adsorb on the Au surfaces, and NPs treat as energy acceptor, which can receive light emitted by C-dots, leading to decrease the fluorescence intensity of C-dots. Furthermore, it is observed that nitroaromatic compounds, especially TNT, could restore this fluorescence due to selective interaction with AuNPs via amine groups, and so releasing the C-dots. Based on this effect, a sensitive and selective fluorescence turn-on probe was designed for the determination of TNT. Some important factors including AuNPs and C-dot concentrations and media pH, which would affect the efficiency of the probe, were optimized. Under the optimum experimental conditions, good linear relationships in the range of 7 - 250 nmol L(-1) TNT with the detection limit of 2.2 nmol L(-1) were obtained. The proposed method was satisfactorily applied to the determination of TNT in the environmental water samples. Compared with previous reports, the developed method has relatively high sensitivity, short analysis time, low cost and ease of operation.

Intraparticle FRET of Mn(ii)-doped carbon dots and its application in discrimination of volatile organic compounds.

To achieve an energy transfer system in emissive nanoparticles, a conventional strategy is to graft an exterior fluorophore onto the surface of the host. In this paper, we report for the first time an intraparticle Förster resonance energy transfer (IPFRET) system formed intrinsically in Mn(ii)-doped carbon dots (MCDs). In virtue of the small particle size of MCDs and the modified band structure, intraparticle energy transfer from a fluorophore-like donor component to a metal-related acceptor component takes place. The IPFRET of MCDs was found to be sensitive to the chemical environment (e.g., polarity) via the effects of external influences on the metal-to-ligand charge transfer (MLCT). Surface enhanced Raman spectroscopy was employed to verify the MLCT-related metal-coordination conformation, and proved capable of collecting bonding information of metal-doped species of carbon dots. Benefitting from the sensitivity of the IPFRET signal, MCDs exhibited high potential in sensing applications.

A boron difluoride dye showing the aggregation-induced emission feature and high sensitivity to intra- and extra-cellular pH changes.

A novel AIE-active boron difluoride fluorescent probe P3T was designed and synthesized. P3T exhibited high sensitivity to intra- and extra-cellular pH changes. Furthermore, a Förster resonance energy transfer (FRET) system was constructed, where P3T acted as a donor fluorophore and DOX as the acceptor.

A pillar[5]arene-based [2]rotaxane lights up mitochondria.

Subcellular organelle-specific reagents for simultaneous targeting, imaging and treatment are highly desirable for cancer therapy. However, it remains a challenge to fabricate a single molecular platform containing a targeting group, imaging and therapeutic agents through traditional synthesis. Due to their superior sensitivity and photostability, fluorescent probes with aggregation-induced emission (AIE) characteristics have attracted more and more attention in studying the process of translocation, drug release, and excretion of nanomedicines in vitro or in vivo. We construct a pillar[5]arene-based [2]rotaxane (R1) by employing tetraphenylethene (TPE) and triphenylphosphonium (TPP) moieties as stoppers; the TPE unit retains the aggregation-induced emission (AIE) attribute and the TPP group is used as a mitochondria-targeting agent. R1 exhibits enhanced AIE, high specificity to mitochondria, and superior photostability. By introducing doxorubicin (DOX) into R1, prodrug R2 is constructed as a dual-fluorescence-quenched Förster resonance energy transfer (FRET) system, in which the TPE-based axle acts as a donor fluorophore and the DOX unit acts as the acceptor. Upon hydrolysis of R2 in endo/lysosomes, the fluorescences of the carrier and the drug recover. R1 is further utilized as a drug delivery platform to conjugate other anticancer drugs containing amine groups through imine formation to prepare prodrugs. The anticancer drugs are released from these prodrugs in the cells upon hydrolysis of the pH-responsive imine bonds.

Dual Stimulus-responsive Fluorescence Behavior and Mechanism of P(NIPAM-co-RhBHA)-NP

In the present study, based on spectral overlap between 1,8-naphthalimide and N-acrylyl-N'-rhodamine B acylhy- drazine thiourea (RhBHA), reversible on-off ring reaction of RhBHA at various pH values, and thermosensitive property of poly(N-isopropyl acrylamide) (PNIPAM), a novel linear polymer P(NIPAM-co-RhBHA)-NP was prepared via a series of chemical reactions. Firstly, 4-(2-aminoethyl)amino-N-aminopropane-1,8-naphthalimide (NP-NH2) and RhBHA were prepared respectively, and they were used as the donor and acceptor to construct a fluorescence resonance energy transfer (FRET) system. Secondly, incorporating RhBHA into PNIPAM by reversible addition-fragmentation chain transfer polymerization (RAFT), P(NIPAM-co-RhBHA) was synthesized. Finally, P(NIPAM-co-RhBHA)-NP was fabricated by amide condensation between NP-NH2 and the as-prepared P(NIPAM-co-RhBHA). The structure of P(NIPAM-co-RhBHA)-NP was characterized via 1 H NMR, FTIR, UV-vis and GPC. The fluorescence responsive behavior of the polymer to environmental temperature and pH value was investigated by photoluminescence (PL) in buffer solutions, and the mechanism was discussed in detail. The results indicate that, in an acidic solution, energy can be transferred from NP-NH2 moieties to RhBHA moieties via FRET mechanism, either pH values or environmental temperatures play important roles to affect the fluorescence emission of P(NIPAM-co-RhBHA)-NP. Keywords 1,8-naphthalimide; N-acrylyl-N'-rhodamine B acylhydrazine thiourea; poly(N-isopropyl acrylamide); fluores- cence resonance energy transfer; stimulus-responsive polymer

Applications of Hairpin DNA-Functionalized Gold Nanoparticles for Imaging mRNA in Living Cells.

Molecular imaging agents are useful for imaging molecular processes in living systems in order to elucidate the function of molecular mediators in health and disease. Here, we demonstrate a technique for the synthesis, characterization, and application of hairpin DNA-functionalized gold nanoparticles (hAuNPs) as fluorescent hybridization probes for imaging mRNA expression and spatiotemporal dynamics in living cells. These imaging probes feature gold colloids linked to fluorophores via engineered oligonucleotides to resemble a molecular beacon in which the gold colloid serves as the fluorescence quencher in a fluorescence resonance energy transfer system. Target-specific hybridization of the hairpin oligonucleotide enables fluorescence de-quenching and subsequent emission with high signal to noise ratios. hAuNPs exhibit high specificity without adverse toxicity or the need for transfection reagents. Furthermore, tunability of hAuNP emission profiles by selection of spectrally distinct fluorophores enables multiplexed mRNA imaging applications. Therefore, hAuNPs are promising tools for imaging gene expression in living cells. As a representative application of this technology, we discuss the design and applications of hAuNP targeted against distinct matrix metalloproteinase enzymes for the multiplexed detection of mRNA expression in live breast cancer cells using flow cytometry and fluorescence microscopy.

A chemiluminescence resonance energy transfer system composed of cobalt(II), luminol, hydrogen peroxide and CdTe quantum dots for highly sensitive determination of hydroquinone

This article describes a nonenzymatic chemiluminescence resonance energy transfer (CRET) system for highly sensitive determination of hydroquinone. It was found that the Co(II)-catalyzed luminescence of luminol in pH 11.5 solution is transferred to CdTe quantum dots (QDs) via a CRET mechanism. Hydroquinone is oxidized by H2O2 to benzoquinone which quenches the fluorescence of the QDs. The enhancement is attributed to the adsorption of Co(II) on the surface of the negatively charged QDs. The CRET system was applied in an assay for hydroquinone that has a detection limit of 0.17 nmol L−1. The detection limit was lower by factors between 100 and 250,000 than earlier reported methods. The assay was successfully applied to the quantitation of hydroquinone in (spiked) water samples, with recoveries ranging from 95 % to 106 %, and relative standard deviations between 0.5 % and 2.4 %.

Multi step FRET among three laser dyes Pyrene, Acriflavine and Rhodamine B

Fluorescence Resonance Energy Transfer (FRET) system using three dyes has been demonstrated. It has been observed that multi step energy transfer occurred from Pyrene to Rhodamine B via Acriflavine. Here Acriflavine acts as an antenna to receive energy from Pyrene and transfer the same to Rhodamine B. This multi step FRET system is advantageous compared to the conventional FRET as this can be used to study molecular level interaction beyond conventional FRET distance (1–10nm) as well as studying multi-branched macromolecules. The introduction of clay enhances the FRET efficiencies among the dye pair, which is an advantage to make the multi step system more useful. Similar approach can be used for increasing FRET efficiencies by using other dyes.

Magnetic Separation-Assistant Fluorescence Resonance Energy Transfer Inhibition for Highly Sensitive Probing of Nucleolin.

For the widely used "off-on" fluorescence (or phosphorescence) resonance energy transfer (FRET or PRET) system, the separation of donors and acceptors species was vital for enhancing the sensitivity. To date, separation of free donors from FRET/PRET inhibition systems was somewhat not convenient, whereas separation of the target-induced far-between acceptors has hardly been reported yet. We presented here a novel magnetic separation-assistant fluorescence resonance energy transfer (MS-FRET) inhibition strategy for highly sensitive detection of nucleolin using Cy5.5-AS1411 as the donor and Fe3O4-polypyrrole core-shell (Fe3O4@PPY) nanoparticles as the NIR quenching acceptor. Due to hydrophobic interaction and π-π stacking of AS1411 and PPY, Cy5.5-AS1411 was bound onto the surface of Fe3O4@PPY, resulting in 90% of fluorescence quenching of Cy5.5-AS1411. Owing to the much stronger specific interaction of AS1411 and nucleolin, the presence of nucleolin could take Cy5.5-AS1411 apart from Fe3O4@PPY and restore the fluorescence of Cy5.5-AS1411. The superparamagnetism of Fe3O4@PPY enabled all separations and fluorescence measurements complete in the same quartz cell, and thus allowed the convenient but accurate comparison of the sensitivity and fluorescence recovery in the cases of separation or nonseparation. Compared to nonseparation FRET inhibition, the separation of free Cy5.5-AS1411 from Cy5.5-AS1411-Fe3O4@PPY solution (the first magnetic separation, MS-1) had as high as 25-fold enhancement of the sensitivity, whereas further separation of the nucleolin-inducing far-between Fe3O4@PPY from the FRET inhibition solution (the second magnetic separation, MS-2) could further enhance the sensitivity to 35-fold. Finally, the MS-FRET inhibition assay displayed the linear range of 0.625-27.5 μg L(-1) (8.1-359 pM) and detection limit of 0.04 μg L(-1) (0.05 pM) of nucleolin. The fluorescence intensity recovery (the percentage ratio of the final restoring fluorescence intensity to the quenched fluorescence intensity of Cy5.5-AS1411 solution by 0.09 g L(-1) Fe3O4@PPY) was enhanced from 36% (for nonseparation) to 56% (for two magnetic separations). This is the first accurate evaluation for the effect of separating donor/acceptor species on the FRET inhibition assay.

Au@NaYF4:Tb3+ core@shell nanostructures: Synthesis and construction of luminescence resonance energy transfer

Luminescence resonance energy transfer (LRET) system can be constructed using NaYF4:Tb3+ luminescence nanocrystals and gold nanoparticles (AuNPs) served as energy donor and acceptor, respectively. The AuNPs modified by cetyltrimethylammonium bromide (CTAB) were synthesized first and NaYF4:Tb3+ shells encapsulated Au cores via a hydrothermal method. The synthesized materials were well characterized by X-ray diffraction (XRD), Fourier-transform infrared spectra (FT-IR), Transmission electron microscopy (TEM), X-ray photoelectron spectrum (XPS), UV–vis absorption spectra (UV–vis) and photoluminescence (PL) measurement. The results indicate that the synthesized Au@NaYF4:Tb3+ core–shell nanoparticles have spherical morphology with a size of 80–90nm and the shell layers of NaYF4:Tb3+ nanocrystals have pure cubic structure. The luminescence properties of Au@NaYF4:Tb3+ core–shell nanoparticles are same as those of NaYF4:Tb3+ particles. The LRET process was realized using the core–shell nanoarchitectures due to the absorption spectrum of AuNPs matches well with the major emission peaks of Tb3+ ions. The LRET experiments have successfully verified the energy transfer between NaYF4:Tb3+ nanocrystals and AuNPs. Additionally, the emission intensities of Tb3+ ions and the content of AuNPs exhibited a fair linear correlation.

Efficient fluorescence energy transfer system between fluorescein isothiocyanate and CdTe quantum dots for the detection of silver ions.

We report a fluorescence resonance energy transfer (FRET) system in which the fluorescent donor is fluorescein isothiocyanate (FITC) dye and the fluorescent acceptor is CdTe quantum dot (QDs). Based on FRET quenching theory, we designed a method to detect the concentration of silver ions (Ag(+)). The results revealed a good linear trend over Ag(+) concentrations in the range 0.01-8.96 nmol/L, a range that was larger than with other methods; the quenching coefficient is 0.442. The FRET mechanism and physical mechanisms responsible for dynamic quenching are also discussed.

Fluorescent carbon dots for sensitive determination and intracellular imaging of zinc(II) ion

We describe the preparation of carbon dots (CDs) from glucose that possess high stability, a quantum yield of 0.32, and low toxicity (according to an MTT assay). They were used, in combination with the fluorogenic zinc(II) probe quercetin to establish a fluorescence resonance energy transfer (FRET) system for the determination of Zn(II). The CDs are acting as the donor, and the quercetin-Zn(II) complex as the acceptor. This is possible because of the strong overlap between the fluorescence spectrum of CDs and the absorption spectrum of the complex. The method enables Zn(II) to be determined in the 2 to 100 μM concentration range, with a 2 μM detection limit. The method was applied to image the distribution of Zn(II) ions in HeLa cells.

Thioflavin T as an Efficient G-Quadruplex Inducer for the Highly Sensitive Detection of Thrombin Using a New Föster Resonance Energy Transfer System.

We report a new Föster resonance energy transfer (FRET) system that uses a special dye, thioflavin T (ThT), as an energy acceptor and a water-soluble conjugated polymer (CP) with high fluorescence as an energy donor. A simple, label-free, and sensitive strategy for the detection of thrombin in buffer and in diluted serum was designed based on this new system using ThT as an efficient inducer of the G-quadruplex. The difference between the blank and the positive samples was amplified due to distinctive FRET signals because thrombin has little effect on the intercalation of ThT into the G-quadruplex. In the absence of the target, ThT induces the aptamer to form a G-quadruplex and intercalates into it with strong fluorescence. The electrostatic attractions between the negatively charged G-quadruplex and positively charged CP allow a short donor-acceptor distance, resulting in a high FRET signal. However, in the presence of the target, the aptamer forms a G-quadruplex-thrombin complex first, followed by the intercalation of ThT into the G-quadruplex. A long distance exists between the donor and acceptor due to the strong steric hindrance from the large-sized thrombin, which leads to a low FRET signal. Compared with previously reported strategies based on the FRET between the CP and dye, our strategy is label-free, and the sensitivity was improved by an order of magnitude. Our strategy also shows the advantages of being simple, rapid (about 50 min), sensitive, label-free, and low-cost in comparison to strategies based on the FRET between quantum dots and dyes.

A novel electrochemiluminescence resonance energy transfer system for ultrasensitive detection of prostate-specific antigen

A novel electrochemiluminescence resonance energy transfer (ECL-RET) system from Eu3 +-doped CdS nanocrystals (CdS:Eu NCs) to Ru(bpy)32 +-doped silica nanoparticle (RuSi) was designed for ultrasensitive detection of prostate-specific antigen (PSA). The platform consists of a CdS:Eu NCs film on glassy carbon electrode (GCE) as ECL emitter and a sandwich-type immunocomplex formed by the primary antibody, PSA and RuSi-tagged second antibody. This system showed a maximum of 4.83-fold enhancement of ECL intensity at 620 nm due to the efficient ECL-RET and high Ru(bpy)32 + quantum yields. By the signal amplification of RuSi and the specific antibody–antigen interactions, this ECL-RET system could sensitively respond down to 1.0 fg mL− 1 PSA.

Gold Nanoclusters@Ru(bpy)₃²⁺-Layered Double Hydroxide Ultrathin Film as a Cathodic Electrochemiluminescence Resonance Energy Transfer Probe.

Herein, it is the first report that a cathodic electrochemiluminescence (ECL) resonance energy transfer (ERET) system is fabricated by layer-by-layer (LBL) electrostatic assembly of CoAl layered double hydroxide (LDH) nanosheets with a mixture of blue BSA-gold nanoclusters (AuNCs) and Ru(bpy)3(2+) (denoted as AuNCs@Ru) on an Au electrode. The possible ECL mechanism indicates that the appearance of CoAl-LDH nanosheets generates a long-range stacking order of the AuNCs@Ru on an Au electrode, facilitating the occurrence of the ERET between BSA-AuNC donors and Ru(bpy)3(2+) acceptors on the as-prepared AuNCs@Ru-LDH ultrathin films (UTFs). Furthermore, it is observed that the cathodic ECL intensity can be quenched efficiently in the presence of 6-mercaptopurine (6-MP) in a linear range of 2.5-100 nM with a detection limit of 1.0 nM. On the basis of these interesting phenomena, a facile cathodic ECL sensor has successfully distinguished 6-MP from other thiol-containing compounds (e.g., cysteine and glutathione) in human serum and urine samples. The proposed sensing scheme opens a way for employing the layered UTFs as a platform for the cathodic ECL of Ru(bpy)3(2+).

Electrochemiluminescence Resonance Energy Transfer System: Mechanism and Application in Ratiometric Aptasensor for Lead Ion.

In this paper, a novel electrochemiluminescence resonance energy transfer (ECL-RET) system from O2/S2O8(2-) to a kind of amino-terminated perylene derivative (PTC-NH2) was demonstrated for the first time, which was then applied to construct a ratiometric aptasensor for lead ion (Pb(2+)) detection. First, gold-nanoparticles-functionalized fullerene nanocomposites (AuNPs@nano-C60) were coated on a glassy carbon electrode (GCE), and then thiol-modified assistant probes (APs) were attached on AuNPs@nano-C60/GCE. Then the resultant electrode was hybridized with capture probes (the aptamer of the Pb(2+), abbreviated as CPs) to generate DNA duplexes, which could induce PTC-NH2 to be intercalated into the dsDNA grooves by the electrostatic adsorption. Herein, ECL dual peaks at -0.7 V (vs Ag/AgCl) and -2.0 V (vs Ag/AgCl) were obtained when the prepared aptasensor was detected in air-saturated S2O8(2-) solution, which could be attributed to the emission of excited dimmers (π-excimers) ((1)(NH2-PTC)2*) and (1)(O2)2*, respectively. In the presence of Pb(2+), the dsDNA was unwound, and Pb(2+) G-quadruplex structure was generated because of the highly specific affinity between Pb(2+) and CPs, which made the PTC-NH2 release from the electrode surface. As a result, the ECL signal at -0.7 V was decreased, and the ECL signal around -2.0 V was increased. By measuring the ratio of ECL intensities at two excitation potentials, the developed aptasensor exhibited the linear response range from 1.0 × 10(-12) M to 1.0 × 10(-7) M with a detection limit of 3.5 × 10(-13) M (S/N = 3) for Pb(2+), which could offer an alternative analytical method with excellent properties of high selectivity, accuracy, and sensitivity.

Fluorescent CdS Quantum Dots: Synthesis, Characterization, Mechanism and Interaction with Gold Nanoparticles.

CdS quantum dot (QD) is a typical kind of II-IV nanoparticles, which plays an important role in the common type of core-shell QDs. It is of great practical significance to synthesize the water-soluble CdS QDs used in multicolor biomarkers and prepare core-shell QDs. In our case, we came up with a novel green method to manufacture CdS QDs with high quality, different size, and adopted UV-vis absorption, fluorescence, FTIR, XPS, HRTEM, SAED and STEM-EDX to discuss their growth mechanism. We successfully constructed fluorescence resonance energy transfer (FRET) system between CdS QDs and gold nanoparticles (AuNPs), then comprehensively and systematically studied the interaction between them.

Carbon dots-silver nanoparticles fluorescence resonance energy transfer system as a novel turn-on fluorescent probe for selective determination of cysteine

Abstract In this paper, we investigated the interaction of carbon dots (C-dots) prepared from orange juice with silver nanoparticles (AgNPs) using fluorescence spectroscopy. It was found that AgNPs efficiently quench the fluorescence of C-dots as a result of fluorescence resonance energy transfer (FRET). Thus, a novel FRET system between C-dots (as the donor) and AgNPs (as the acceptor) was introduced. Moreover, it was found that cysteine even at nanomolar levels could recover the fluorescence of C-dots due to the competitive adsorption of this compound onto AgNPs. This was exploited to design a simple and selective method for the determination of cysteine in the concentration range from 6.0 to 300 nM, with a detection limit of 4.0 nM. Cysteine was determined by this method in human plasma and urine samples with satisfactory results.

An enhanced chemiluminescence resonance energy transfer system based on target recycling G-guadruplexes/hemin DNAzyme catalysis and its application in ultrasensitive detection of DNA

An enhanced chemiluminescence resonance energy transfer (CRET) system based on target recycling G-guadruplexes/hemin DNAzyme catalysis was developed for ultrasensitive detection of DNA. CRET system consists of luminol as chemiluminescent donor, and fluorescein isothiocyanate (FITC) as acceptor. The sensitive detection was achieved by using the system consisted of G-riched DNA, blocker DNA, and the Nb.BbvCI biocatalyst. Upon addition of target DNA to the system, target DNA hybridizes with the quasi-circular DNA structure, and forms a DNA duplex. The formation of DNA duplex triggers selective enzymatic cleavage of quasi-circular DNA by Nb.BbvCI, resulting in the release of target DNA and two G-riched DNAzyme segments. Released target DNA then hybridizes with another quasi-circular DNA structure to initiate the cleavage of the quasi-circular DNA structure. Eventually, each target DNA can go through many cycles, resulting in the digestion of many quasi-circular DNA structures, generating many G-riched DNAzyme segments. G-riched DNAzyme segment products assemble with hemin to form stable hemin/G-quadruplexes that exhibit peroxidase-like activity which can catalyze the oxidation of luminol by H2O2 to produce CL signals. In the presence of FITC, CL of luminol can excite FITC molecules, and thus produced CRET between the luminol and FITC. This unique analysis strategy gives a detection limit down to 80fM, which is at least four orders of magnitude lower than that of unamplified DNA detection methods.