Efficient Fluorescence Resonance Energy Transfer Research Articles

An ultrasensitive smartphone-assisted bicolor-ratiometric fluorescence sensing platform based on a “noise purifier” for point-of-care testing of pathogenic bacteria in food

Non-specific binding in fluorescence resonance energy transfer (FRET) remains a challenge in foodborne pathogen detection, resulting in interference of high background signals. Herein, we innovatively reported a dual-mode FRET sensor based on a “noise purifier” for the ultrasensitive quantification of Escherichia coli O157:H7 in food. An efficient FRET system was constructed with polymyxin B-modified nitrogen-sulfur co-doped graphene quantum dots (N, S-GQDs@PMB) as donors and aptamer-modified yellow carbon dots (Y-CDs@Apt) as acceptors. Magnetic multi-walled carbon nanotubes (Fe@MWCNTs) were employed as a “noise purifier” to reduce the interference of the fluorescence background. Under the background purification mode, the sensitivity of the dual-mode signals of the FRET sensor has increased by an order of magnitude. Additionally, smartphone-assisted colorimetric analysis enabled point-of-care detection of E. coli O157:H7 in real samples. The developed sensing platform based on a “noise purifier” provides a promising method for ultrasensitive on-site testing of trace pathogenic bacteria in various foodstuffs.

One-Dimensionally Arranged Quantum-Dot Superstructures Guided by a Supramolecular Polymer Template.

Colloidal quantum dots (QDs) exhibit important photophysical properties, such as long-range energy diffusion, miniband formation, and collective photoluminescence, when aggregated into well-defined superstructures, such as three-dimensional (3D) and two-dimensional (2D) superlattices. However, the construction of one-dimensional (1D) QD superstructures, which have a simpler arrangement, is challenging; therefore, the photophysical properties of 1D-arranged QDs have not been studied previously. Herein, we report a versatile strategy to obtain 1D-arranged QDs using a supramolecular polymer (SP) template. The SP is composed of self-assembling cholesterol derivatives containing two amide groups for hydrogen bonding and a carboxyl group as an adhesion moiety on the QDs. Upon mixing the SP and dispersed QDs in low-polarity solvents, the QDs self-adhered to the SP and self-arranged into 1D superstructures through van der Waals interactions between the surface organic ligands of the QDs, as confirmed by transmission electron microscopy. Furthermore, we revealed efficient photoinduced fluorescence resonance energy transfer between the 1D-arranged QDs by an in-depth analysis of the emission spectra and decay curves.

One‐Dimensionally Arranged Quantum‐Dot Superstructures Guided by a Supramolecular Polymer Template

AbstractColloidal quantum dots (QDs) exhibit important photophysical properties, such as long‐range energy diffusion, miniband formation, and collective photoluminescence, when aggregated into well‐defined superstructures, such as three‐dimensional (3D) and two‐dimensional (2D) superlattices. However, the construction of one‐dimensional (1D) QD superstructures, which have a simpler arrangement, is challenging; therefore, the photophysical properties of 1D‐arranged QDs have not been studied previously. Herein, we report a versatile strategy to obtain 1D‐arranged QDs using a supramolecular polymer (SP) template. The SP is composed of self‐assembling cholesterol derivatives containing two amide groups for hydrogen bonding and a carboxyl group as an adhesion moiety on the QDs. Upon mixing the SP and dispersed QDs in low‐polarity solvents, the QDs self‐adhered to the SP and self‐arranged into 1D superstructures through van der Waals interactions between the surface organic ligands of the QDs, as confirmed by transmission electron microscopy. Furthermore, we revealed efficient photoinduced fluorescence resonance energy transfer between the 1D‐arranged QDs by an in‐depth analysis of the emission spectra and decay curves.

A novel polymer-based probe for fluorescently ratiometric sensing of hydrogen sulfide with multiple applications

Hydrogen sulfide (H2S) as an endogenous signaling molecule, plays an irreplaceable role in many important physiological activities. It is also closely related to sewage treatment, wine quality evaluation, and food spoilage. Herein, we have successfully synthesized a novel polymer-based probe P1 for fluorescently ratiometric sensing of H2S with a high selectivity and sensitivity. By virtue of ring-opening metathesis polymerization (ROMP), P1 was prepared with the disulfide bond linked coumarin-norbornene dyad NB-SS-COU as energy donor, the aggregation-induced emission (AIE) fluorophore anchored norbornene NB-TPE as energy receptor, and the polyethylene glycol (PEG) attached norbornene NB-PEG as a hydrophilic chain. At the 400 nm excitation, P1 displays a bright red emission at 615 nm due to the efficient fluorescence resonance energy transfer (FRET) from energy donor COU to energy acceptor TPE. Upon addition of H2S, it shows strong COU-based blue emission at 473 nm for cleavage of the disulfide bond. We also constructed a smartphone sensing platform to conduct visual quantitative detection of H2S by calculating the B/R (blue/red) emission ratio values. Moreover, P1 can be successfully employed in evaluating the level fluctuations of endogenous and exogenous H2S in living cells, testing water samples/wine samples, and monitoring food freshness.

Efficient FRET process between CsPbBr3 quantum dots and RhB dye molecules by pressure regulation

Fluorescence resonance energy transfer (FRET) based on quantum dots (QDs) and dye molecules have great application potential in biochemical fields. How to achieve an efficient energy transfer process has become an important research topic. Pressure can be used to regulate the energy transfer process, but its regulation on metal halide perovskite systems is rarely reported. Herein, the efficient FRET process between CsPbBr3 QDs and Rhodamine B (RhB) molecules under high pressure is investigated. Upon compression to 1.3 GPa, the FRET rate of the CsPbBr3–RhB composite reaches 0.21 ns−1 and the FRET efficiency is improved from 12.4% to 62.4%, due to enhanced spectral overlap and shortened minimum distance between CsPbBr3 QDs and RhB molecules. This study provides a strategy for achieving efficient FRET research and further promotes the development of applications based on halide perovskite molecular systems.

A nanozipper structured efficient FRET probe for ratiometric detection of ATP based on target-induced cycling amplification

In the realm of disease diagnostics and prognostics, accurate quantification of adenosine triphosphate (ATP) has become crucial, as the intricate interplay between ATP and cellular metabolism is a fundamental factor in the pathogenesis and progression of many pathological conditions. Herein, a ratiometric fluorescence DNA nanozipper is developed, which enables highly sensitive detection of ATP by employing catalytic hairpin assembly. This innovative approach utilizes target-induced conformational changes in the nanozipper structure to tune the distance between the carboxyfluorescein as donor and tetramethylrhodamine as acceptor around the Förster radius, thereby enhancing the efficiency of fluorescence resonance energy transfer (FRET). In the state of nanozipper tension, the rigid and steric hindrance Y-shaped configuration leads to a considerable distance between two fluorophores, resulting in FRET low efficiency. However, the presence of ATP triggers allosteric configuration of the DNA nanozipper, switching the nanozipper to a relaxed state, which results in a visible fluorescent ratiometric signal. The sensing strategy exhibits a linear response to ATP concentrations in the range of 30 − 600 nM and can detect concentrations as low as 9.6 nM. Additionally, this detection method introduces a novel idea for the design of efficient FRET probes and demonstrates promising application potential in biological samples.

Carbon Dot‐Based Fluorescence Resonance Energy Transfer (FRET) Systems for Biomedical, Sensing, and Imaging Applications

AbstractCarbon dots (CDs) emerge as a potential group of photo‐luminescent nano‐materials due to their excellent optical, electrical, and chemical properties, as well as their competence in a wide range of environmental applications. CDs have unique and appealing properties such as excellent stability, low toxicity, water solubility, and derivability. When coupled with CDs, fluorescence resonance energy transfer (FRET) results in the development of highly sensitive ratiometric fluorescence sensor probes with potential applications in bio‐imaging, metal sensing, membrane dynamics, and environmental sensing. In this review, the progress and recent developments in CDs based FRET systems utilized for various environmental applications are conferred. An in‐depth description is provided regarding the numerous donor/acceptor systems which when integrated with CDs generate efficient FRET systems. The review enables researchers to identify and develop specific systems which can be utilized to generate a FRET pair with potential physico–chemical properties that aid the development of the same for various applications.

Ultrasensitive and visual detection of genetically modified crops using two primers-induced cascade exponential amplification assay

The increased global cultivation area of genetically modified (GM) crops has caused severe controversies over potential health and environmental risks worldwide. There is an urgent need to verify even trace amount of a particular GM material in products. Herein, a two primers-induced cascade exponential amplification reaction combined with cationic conjugated polymers (CCPs)-based visual detection method is developed for rapid and ultrasensitive detection of GM crops. This method only uses two primers to specifically recognize the four regions of the target gene, which is easier for primer design and probably more suitable for the detection of shorter targets. By integrating the two exponential amplification reactions, as low as 5 pg genomic DNA from GM maize can be accurately detected, which is more sensitive than the single amplification-based methods. Taking advantage of the efficient fluorescence resonance energy transfer (FRET) between CCPs and the commercial fluorescent dye SYBR Green I (SG), our method can differentiate as low as 0.01 % GM maize from a large amount of non-GM maize, which is the most accurate method so far. By changing the two primers according to target gene, our method can be modified to the detection of any other GM materials, indicating that our method is promising to be applied in other GM materials-related testing and screening system.

Dual-emitting N-doped carbon dots/AuNCs nanohybrids as an efficient ratiometric fluorescent probe and a paper sensor for Pb2+ sensing

Ratiometric fluorescent sensors could effectively eliminate the interference of spontaneous fluorescence or instrument fluctuation to improve the analysis sensitivity and accuracy. In this work, a dual-emission nitrogen-doped carbon dots/AuNCs (NCDs-AuNCs) nanohybrid was fabricated under mild conditions by the hydrothermal method, without additional coupling agents, which is facile and environmentally friendly. The prepared nanohybrid was employed for the sensitive detection of Pb2+. The sensor exhibited dual emission peaks at 460 and 625 nm with efficient fluorescence resonance energy transfer under a single excitation wavelength of 360 nm, in which the red fluorescence of AuNCs was enhanced and the blue fluorescence of NCDs was slightly quenched with the presence of Pb2+. The quantitative analysis of Pb2+ was performed upon the change of both fluorescence intensities. The sensor was successfully used for Pb2+ detection in real water samples with satisfactory spiking recoveries in a range of 91.0%–101.3% and low relatively standard deviations (RSDs < 3%), which exhibited good selectivity and anti-interference ability. In addition, a paper-based sensor was fabricated by immobilizing the nanohybrids on filter paper, which enables the visual semi-quantitative determination of Pb2+ by the naked eye through the color transition from blue to pink. The prepared NCDs-AuNCs nanohybrids showed great application potential in environmental water monitoring in an efficient and green way.

Surfactant regulated aggregation-induced emission of tetraphenylethene-based tetracationic salt for the construction of light harvesting supramolecular system

Fluorescence resonance energy transfer (FRET) is an efficient optical molecular scale that has been widely used in many fields, and aggregation-induced emission (AIE) luminescent materials show great potential in constructing FRET systems. In this paper, an efficient supramolecular polymer of AIE was prepared in aqueous solution based on tetraphenylethene-based tetracationic salt molecule (1) with AIE properties, using the hydrophobic effect and electrostatic interaction with sodium dodecyl sulfonate (AS). Then, based on supramolecular aggregate (1-AS) and Rhodamine B (RB) dye, the efficient FRET system was prepared in aqueous solution with 1-AS as energy donor and RB as energy acceptor. The Stokes shift of the system can reach 208 nm, and the fluorescence intensity of RB aqueous solution with the same concentration increased 11.80 times. Moreover, the energy transfer efficiency and the antenna effect value reached 77.5%, 14.3, respectively. The method based on simple AIE donor to achieve efficient luminescence of dye molecules is of great significance for the realization of efficient light-trapping system of aqueous solution in practical applications.

Engineering highly efficient NIR-II FRET platform for Background-Free homogeneous detection of SARS-CoV-2 neutralizing antibodies in whole blood

Förster or fluorescence resonance energy transfer (FRET) enables to probe biomolecular interactions, thus playing a vital role in bioassays. However, conventional FRET platforms suffer from limited sensitivity due to the low FRET efficiency and poor anti-interference of existing FRET pairs. Here we report a NIR-II (1000–1700 nm) FRET platform with extremely high FRET efficiency and exceptional anti-interference capability. This NIR-II FRET platform is established based on a pair of lanthanides downshifting nanoparticles (DSNPs) by employing Nd3+ doped DSNPs as an energy donor and Yb3+ doped DSNPs as an energy acceptor. The maximum FRET efficiency of this well-engineered NIR-II FRET platform reaches up to 92.2%, which is much higher than most commonly used ones. Owing to the all-NIR advantage (λex = 808 nm, λem = 1064 nm), this highly efficient NIR-II FRET platform exhibits extraordinary anti-interference in whole blood, and thus enabling background-free homogeneous detection of SARS-CoV-2 neutralizing antibodies in clinical whole blood sample with high sensitivity (limit of detection = 0.5 μg/mL) and specificity. This work opens up new opportunities for realizing highly sensitive detection of various biomarkers in biological samples with severe background interference.

Polymeric assembled nanoparticles through kinetic stabilization by confined impingement jets dilution mixer for fluorescence switching imaging

• Rapidly-assembled nanoparticles prepared by flash nanoprecipitation. • Nanoparticles with controllable size and fluorescence intensity. • Fluorescence switching behavior under visible lights. Traditional fluorescence switching molecules achieving the state change between on and off states commonly based on UV irradiation. However, it is worth noting that UV irradiation is harmful to both the cancer cells and the normal cells. To achieve fluorescence switching under visible wavelength and avoid complicate molecular design, a fluorophore of 2,4,5,6-tetrakis(carbazol-9-yl)-1,3-dicyanobenzene (4CzIPN) and a quencher of diarylethene (DAE) were physically incorporated within the biocompatible block copolymer poly(lactic-co-glycolic acid)- b -poly(ethylene glycol) (PLGA- b -PEG) to form 4CzIPN-DAE nanoparticles (NPs) through flash nanoprecipitation (FNP). By using the FNP method, the NPs were prepared within milliseconds in a confined impingement jets dilution (CIJ-D) mixer. Quenching and recovery of fluorescence could achieve in the presence of DAE under 475 nm and 560 nm irradiation. Appropriate structure and fluorescent properties of the nanoparticles can be tuned by external conditions for their efficient fluorescence resonance energy transfer (FRET) in a kinetic stabilization process. This NPs formation process was further optimized by varying the dilution ratio, Reynolds number ( Re ) and polymer concentration to modulate the mixing and particle nucleation and growth process. The size and fluorescence switching properties of the NPs were systematically investigated in solution and in cellular uptake experiments. This work is anticipated to provide a simple and highly effective engineering strategy for the modulation of fluorescence switching nanoparticles and beneficial to its engineering application.

Lateral chain length-dependent thermochromism based on dual emission of non-polycyclic aromatic luminogens

Thermochromism is an optical property wherein color changes dramatically during a phase transition. An effective way to realize thermochromism is to manipulate emission properties depending on supramolecular interactions, and this can be achieved in the bulk state. Herein, we report the lateral chain length-dependent photoluminescence (PL) behavior of non-polycyclic luminogens in the crystalline (Cry) and liquid (Liq) phases. Under UV-irradiation at 365 nm, the emission color of 1, which has shorter tri (ethylene oxide) chains, changed remarkably from sky-blue to blue color upon melting, while that of 2, which has longer poly (ethylene oxide) (PEO) chains, remained blue regardless of the melting transition. Interestingly, dual emission near 400 nm and 515 nm was observed in the Cry phase of 1, whereas emission was observed only near 400 nm in the Cry phase of 2. Upon melting, both compounds emitted near 400 nm. PL and excitation spectra revealed that the emission at 400 nm and 515 nm originated from short- and long-ranged electronically coupled species (SRECS and LRECS), respectively. Notably, efficient fluorescence resonance energy transfer (FRET) from SRECS to LRECS occurred in the Cry phase of 1. Dielectric relaxation spectroscopy analysis indicated that the degree of electronic coupling of aromatic luminogens was closely associated with their rotational dynamics. The rotational motion was fully restricted in the Cry phase of 1, whereas it was activated in the Cry phase of 2. The different rotational dynamics were attributed to the different lengths of the lateral chain, which influenced the degree of electronic coupling in the Cry phase and endowed thermochromism in the non-polycyclic luminogens.

Energy Funneling from Water-Dispersed Perovskites to Chromophores

Cesium lead halide perovskite nanocrystals (PNCs) have enjoyed enormous attention in optoelectronics and photovoltaics. However, instability under polar conditions and limited energy/charge transport due to long-chain capping ligands restrict their large-scale applications. We have engineered a short-chain multidentate bolaamphiphilic ligand (NKE-3), which provides synergistic passivation of the perovskite surface by one multidentate ionic terminal and localizes water molecules by another multidentate ionic terminal, leading to a water-suspended colloidal solution of PNCs. NKE-3 allows efficient long-range dipole-based fluorescence resonance energy transfer (FRET) from perovskites to Rhodamine B isothiocyanate (RITC) in water, with FRET efficiencies ranging from 96% to 98%. We calculated the FRET rate using the acceptor’s rise-time component, as it ensures no contamination from FRET-inactive donors. Moreover, we tuned the emission maxima of PNCs through halide exchange to optimize FRET efficiency. Such energy funneling to a suitable molecular photocatalyst is imperative for PNCs’ potential applications.

Supramolecular alternating copolymers with highly efficient fluorescence resonance energy transfer.

This article reports alternating supramolecular copolymerization of two naphthalene-diimide (NDI)-derived building blocks (NDI-1 and NDI-2) under thermodynamic control. Both monomers contain a central NDI chromophore, attached to a hydrocarbon-chain and a carboxylic-acid group. The NDI core in NDI-2 is symmetrically substituted with two butane-thiol groups, which makes it distinct from NDI-1. In decane, a 1 : 1 mixture of NDI-1 and NDI-2 shows spontaneous gelation and a typical fibrillar network, unlike the behavior of either of the components individually. The solvent-dependent UV/vis spectrum of the mixed sample in decane shows bathochromically shifted sharp absorption bands and a sharp emission band (holds a mirror-image relationship) with a significantly small Stokes shift compared to those in CHCl3, indicating J-aggregation. In contrast, the aggregated spectra of the individual monomers show broad structureless features, suggesting ill-defined aggregates. Cooling curves derived from the temperature-dependent UV/vis spectroscopy studies revealed early nucleation and a signature of well-defined cooperative polymerization for the mixed sample, unlike either of the individual components. Molecular dynamics simulations predicted the greatest dimer formation tendency for the NDI-1 + NDI-2 (1 : 1), followed by pure NDI-1 and NDI-2. Theoretical studies further revealed a partial positive charge in the NDI ring of NDI-1 when compared to NDI-2, promoting the alternating stacking propensity, which is also favored by the steric factor as NDI-2 is core-substituted with alkyl thiols. Such theoretical predictions fully corroborate with the experimental results showing 1 : 1 stoichiometry (from Job's plot) of the two monomers, indicating alternate stacking sequences in the H-bonded (syn-syn catemer type) supramolecular copolymer. Such alternating supramolecular copolymers showed highly efficient (>93%) fluorescence resonance energy transfer (FRET).

Synthesis, TD-DFT, and optical properties study of a chromeno-quinoline (acceptor) and mirror-less laser action enabled by energy transfer from a conjugated-polymer (Donor)

Structurally interesting chromeno-quinolines were constructed via the cyclization reaction of O-propargylated naphthaldehyde and substituted anilines in good yields. We explored compound methyl-chromenoquinoline (MCQ) in detail for its optical properties using Time-dependent density-functional theory (TD-DFT) and experimental studies. The conjugated-polymer (CP) Poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(2,5-p-xylene)] or [(ADS145UV or PFOPX)] was studied as donor. The TD-DFT implied that MCQ is a fluorescent compound with well-defined highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) structure at −5.327 eV and −1.836 eV, respectively, with an energy gap of 3.49 eV in toluene captivity. The TD-DFT-based model and experimental study showed an energy gap of 3.326 eV and 3.351 eV, respectively, and the deviation was 0.025 eV. The experimental studies of MCQ showed solvent-dependent fluorescence peak shifted from 445 ± 2 nm to 538 ± 2 nm for dielectric constant ranging from 0.01 (hexane) to 10.2 (water). Despite the good optical properties, MCQ produced a weak laser-induced fluorescence (LIF) and not produce amplified spontaneous emission (ASE) to any pump energy of 3rd harmonic from Nd:YAG laser (5 ns, 355 nm). When PFOPX of concentration 500 nM (500 μL) was added to MCQ of 506 mM (3.5 mL) concentration, the LIF suddenly improved tenfold due to efficient Fluorescence resonance energy transfer (FRET) process. At the optimal concentration of PFOPX (670 nM) in MCQ solution, the spectrum changed dramatically. The spectrum has five peaks with a LIF in the background, where peaks around 393.5 nm and 417.3 nm attribute to the oligomer; 438.7 nm attributed to a combined fluorescence of PFOPX and MCQ; 466.4 nm, and 493.1 nm corresponding to MCQ. Analysis shows that the peaks at 440 nm (partly) and 493 nm were ASE from MCQ.

Construction of FRET-based metallacycles with efficient photosensitization efficiency and photocatalytic activity

The fabrication of highly effective photosensitizers has received considerable attention because of their attractive functions and applications in the fields of photodynamic therapy, photosynthesis, photocatalysis, etc. Thus, it is highly desirable to develop a new approach to enhance photosensitization efficiency. Herein, through coordination-driven self-assembly, a series of metallacycles with efficient fluorescence resonance energy transfer (FRET) were effectively constructed, which displayed higher photosensitization efficiency and photocatalytic activity than their model metallacycles without FRET due to broadband absorption and singlet energy transfer from the energy acceptor to the energy donor. Moreover, iodization of fluorophores induced a significant enhancement of the photosensitization efficiency and photocatalytic activity of the metallacycles. This research provides an efficient strategy for improving photosensitization efficiency and a promising platform for the preparation of effective photosensitizers and photocatalysts.

Highly efficient fluorescence resonance energy transfer in co-encapsulated BODIPY nanoparticles

Fluorescence resonance energy transfer (FRET) is a powerful tool used in a wide range of applications due to its high sensitivity and many other advantages. Co-encapsulation of a donor and an acceptor in nanoparticles is a useful strategy to bring the donor-acceptor pair in proximity for FRET. A highly efficient FRET system based on BODIPY-BODIPY (BODIPY: boron-dipyrromethene) donor-acceptor pair in nanoparticles was synthesized. Nanoparticles were formed by co-encapsulating a green emitting BODIPY derivative (FRET donor, lmax = 501 nm) and a red emitting BODIPY derivative (FRET acceptor, lmax = 601 nm) in an amphiphilic polymer using the precipitation method. Fluorescence measurements of encapsulated BODIPY in water following 501 nm excitation caused a 3.6 fold enhancement of the acceptor BODIPY emission at 601 nm indicating efficient energy transfer between the green emitting donor BODIPY and the red emitting BODIPY acceptor with a 100 nm Stokes shift. The calculated FRET efficiency was 96.5%. Encapsulated BODIPY derivatives were highly stable under our experimental conditions.

Development of a Single Quantum Dot-Mediated FRET Nanosensor for Sensitive Detection of Single-Nucleotide Polymorphism in Cancer Cells.

Single-nucleotide polymorphisms (SNPs) are important hallmarks of human diseases. Herein, we develop a single quantum dot (QD)-mediated fluorescence resonance energy transfer (FRET) nanosensor with the integration of multiple primer generation rolling circle amplification (MPG-RCA) for sensitive detection of SNPs in cancer cells. This assay involves only a linear padlock probe for MPG-RCA. The presence of a mutant target facilitates the circularization of linear padlock probes to initiate RCA, producing three short single-stranded DNAs (ssDNAs) with the assistance of nicking endonuclease. The resulting ssDNAs can function as primers to induce cyclic MPG-RCA, resulting in the exponential amplification and generation of large numbers of linker probes. The linker probes can subsequently hybridize with the Cy5-labeled reporter probes and the biotinylated capture probes to obtain the sandwich hybrids. The assembly of these sandwich hybrids on the 605 nm-emission quantum dot (605QD) generates the 605QD-oligonucleotide-Cy5 nanostructures, resulting in efficient FRET from the 605QD to Cy5. This nanosensor is free from both the complicated probe design and the exogenous primers and has distinct advantages of high amplification efficiency, zero background signal, good specificity, and high sensitivity. It can detect SNPs with a large dynamic range of 8 orders of magnitude and a detection limit of 5.41 × 10-20 M. Moreover, this nanosensor can accurately distinguish as low as 0.001% mutation level from the mixtures, which cannot be achieved by previously reported methods. Furthermore, it can discriminate cancer cells from normal cells and even quantify SNP at the single-cell level.

Graphene quantum dot-decorated luminescent porous silicon dressing for theranostics of diabetic wounds

Diabetic wound healing is highly desirable but remains a great challenge owing to the continuous damage of excess reactive oxygen species (ROS) and degradation of therapeutic peptide drugs by over-expressed matrix metalloproteinase (MMP). Herein, we developed a stimuli-responsive smart dressing for theranostics of diabetic wounds using graphene quantum dots-decorated luminescent porous silicon (GQDs@PSi), which was further loaded with peptide and embedded in chitosan (CS) film. The confinement of GQDs in nanochannels of PSi endowed GQDs@PSi with efficient fluorescence resonance energy transfer (FRET) effect, leading to initial red fluorescence of PSi with complete quench of GQD's blue fluorescence. Furthermore, the decoration of GQDs on PSi surface significantly enhanced the loading capacity for peptide drugs including epidermal growth factor (EGF) and insulin (Ins) which can promote diabetic wounds healing. The peptides coloaded in GQDs@PSi exhibited sustained release behavior and could be protected in presence of MMP owing to size exclusion of PSi's nanochannels. As H2O2-triggered oxidation of PSi lead to weakened FRET effect and degradation of PSi, GQDs@PSi demonstrated H2O2-responsive ratiometric fluorescence change (from red PSi to blue GQDs) and drug release behavior. In combination with CS's degradation in the acidic and oxidation microenvironment, the smart dressing also showed stimuli-responsive drug release toward slightly acid and highly oxidative conditions in diabetic wounds. In vitro and in vivo results demonstrated the smart dressing enhanced the proliferation and migration of cells as well as significantly healed diabetic wounds. Real-time indicating of the exacerbation or healing of diabetic wounds was also realized using the rate of fluorescent discoloration of the dressing. Statement of significanceIn this work, a dual luminescent nanomaterial was created by hosting graphene quantum dots (GQDs) in the nanochannel of porous silicon (PSi), which was further applied for theranostics of diabetic wound. The synergistic effect of the host-guest nanohybrid is significant. The GQDs can significantly improve the capacity for peptide drug loading and form a stimuli-response visual ratiometric sensor with luminescent PSi, which can also protect and sustain release of peptide drugs for effective diabetic wounds treatment. After embedded in a chitosan film, the smart dressing displayed H2O2-responsive visual ratiometric fluorescence change and drug release behavior. In vitro and in vivo results demonstrated the smart dressing enhanced the proliferation and migration of cells as well as significantly healed diabetic wounds.