Red-Emissive Carbon Dots for "Switch-On" Dual Function Sensing Platform Rapid Detection of Ferric Ions and l-Cysteine in Living Cells.
ABSTRACT: Ferric ions (Fe3+ ions) and l-cysteine (( l-Cys) in the human body have always played an irreplaceable role in biological processes, and overload or deficiency of Fe3+ ions and l-Cys in the biological system leads to various diseases. In this work, N,S-co-doped red-emitting carbon dots (R-CDs) were synthesized by a facile hydrothermal method. Because the doping of N and S gives a unique functional group distribution on the surface of R-CDs, it can be complexed with Fe3+ ions to construct an energy transfer quenching system. However, the presence of l-Cys competitively binds to Fe3+ ions, thus resulting in the photoluminescence recovery of R-CDs. Therefore, a "switch-on" dual function sensing platform has successfully been developed based on R-CDs for rapid identification and quantification of Fe3+ ions and l-Cys. The linear detection range of Fe3+ ions is 0-30 ?M (limit of detection (LOD): 0.27 ?M) and that of l-Cys is 0-24 ?M (LOD: 0.14 ?M). The sensor platform was used to detect Fe3+ ions and l-Cys in human serum samples with satisfactory results. Compared with traditional detection methods, this method is more time-saving and efficient and can be completed in 3 min. It is worth mentioning that the R-CDs not only has high optical stability but also has negligible cytotoxicity and has been successfully applied to in vitro/vivo imaging, indicating that R-CDs have excellent tissue penetration and biomarker potential. More interestingly, the switch-on fluorescence behavior for stepwise detection of Fe3+ ions and l-Cys can also be observed in cell imaging, which provides the possibility of visual detection of the probe to be applied in vivo.
Project description:Carbon dots (CDs) demonstrate very poor fluorescence quantum yield (QY). In this study, with the help of a hydrothermal method, we combined CDs with nitrogen and phosphorus elements belonging to the VA group (in the periodic table) to form heteroatom co-doped CDs, i.e., nitrogen and phosphorus co-doped carbon dots (NPCDs). These displayed a significant improvement in the QY (up to 84%), which was as much as four times than that of CDs synthesized by the same method. The as-prepared NPCDs could be used as an "off-on" fluorescence detector for the rapid and effective sensing of ferric ions (Fe3+) and catecholamine neurotransmitters (CNs) such as dopamine (DA), adrenaline (AD), and noradrenaline (NAD). The fluorescence of NPCDs was "turned off" and the emission wavelength was slightly red-shifted upon increasing the Fe3+ concentration. However, when CNs were incorporated, the fluorescence of NPCDs was recovered in a short response time; this indicated that CN concentration could be monitored, relying on enhancing the fluorescence signal of NPCDs. As a result, NPCDs are considered as a potential fluorescent bi-sensor for Fe3+ and CN detection. Particularly, in this research, we selected DA as the representative neurotransmitter of the CN group along with Fe3+ to study the sensing system based on NPCDs. The results exhibited good linear ranges with a limit of detection (LOD) of 0.2 and 0.1 µM for Fe3+ and DA, respectively.
Project description:In the present work, we reported the luminescence of a green-emitting carbon dots (CDs) synthesized via solid state reaction method using diammonium hydrogen citrate and urea as a starting materials. The obtained green-emitting CDs shows strong absorption in the 350-450 nm region and gives intense green emission (λmax = 537 nm) with quantum yield as high as 46.4% under 420 nm excitation. The obtained green-emitting CDs also demonstrates high photo-stability, which is evidenced by the fact that its emission intensity almost has no change under irradiation by a 365 nm UV lamp for 2 hours. Moreover, the obtained green-emitting CDs shows high sensitivity and selectivity for the detection of Fe3+, and their emission intensity response towards Fe3+ ions is highly linear (R2 = 0.995) over the concentration range from 25 to 300 µM, which could provide an effective platform for detection of Fe3+. Mostly important, we further demonstrate that such photoluminescent green-emitting CDs exhibits low toxicity and are biocompatible for use with in cellular imaging. Combining with low cytotoxicity, good water solubility and excellent luminescence properties, green-emitting CDs could be used as a biocompatible fluorescent ink in future applications.
Project description:Dual functional fluorescence nanosensors have many potential applications in biology and medicine. Monitoring temperature with higher precision at localized small length scales or in a nanocavity is a necessity in various applications. As well as the detection of biologically interesting metal ions using low-cost and sensitive approach is of great importance in bioanalysis. In this paper, we describe the preparation of dual-function highly fluorescent B, N-co-doped carbon nanodots (CDs) that work as chemical and thermal sensors. The CDs emit blue fluorescence peaked at 450?nm and exhibit up to 70% photoluminescence quantum yield with showing excitation-independent fluorescence. We also show that water-soluble CDs display temperature-dependent fluorescence and can serve as highly sensitive and reliable nanothermometers with a thermo-sensitivity 1.8% °C-1, and wide range thermo-sensing between 0-90?°C with excellent recovery. Moreover, the fluorescence emission of CDs are selectively quenched after the addition of Fe2+ and Fe3+ ions while show no quenching with adding other common metal cations and anions. The fluorescence emission shows a good linear correlation with concentration of Fe2+ and Fe3+ (R2?=?0.9908 for Fe2+ and R2?=?0.9892 for Fe3+) with a detection limit of of 80.0?±?0.5?nM for Fe2+ and 110.0?±?0.5?nM for Fe3+. Considering the high quantum yield and selectivity, CDs are exploited to design a nanoprobe towards iron detection in a biological sample. The fluorimetric assay is used to detect Fe2+ in iron capsules and total iron in serum samples successfully.
Project description:A facile one-step hydrothermal synthesis approach was proposed to prepare nitrogen and chlorine co-doped carbon dots (CDs) using l-ornithine hydrochloride as the sole precursor. The configuration and component of CDs were characterized by transmission electron microscopy and X-ray photoelectron and Fourier transform infrared spectroscopies. The obtained CDs (Orn-CDs) with a mean diameter of 2.1 nm were well monodispersed in aqueous solutions. The as-prepared CDs exhibited a bright blue fluorescence with a high yield of 60%, good photostability and low cytotoxicity. The emission of Orn-CDs could be selectively and effectively suppressed by Fe3+. Thus, a quantitative assay of Fe3+ was realized by this nanoprobe with a detection limit of 95.6 nmol l-1 in the range of 0.3-50 µmol l-1. Furthermore, ascorbic acid could recover the fluorescence of Orn-CDs suppressed by Fe3+, owing to the transformation of Fe3+ to Fe2+ by ascorbic acid. The limit of detection for ascorbic acid was 137 nmol l-1 in the range of 0.5-10 µmol l-1. In addition, the established method was successfully applied for Fe3+ and ascorbic acid sensing in human serum and urine specimens and for imaging of Fe3+ in living cells. Orn-CD-based sensing platform showed its potential to be used for biomedicine-related study because it is cost-effective, easily scalable and can be used without additional functionalization and sample pre-treatment.
Project description:Poly(ethylene glycol) passivated graphene quantum dots (PEG-GQDs) were synthesized based on a green and effective strategy of the hydrothermal treatment of cane molasses. The prepared PEG-GQDs, with an average size of 2.5 nm, exhibit a brighter blue fluorescence and a higher quantum yield (QY) (up to approximately 21.32%) than the QY of GQDs without surface passivation (QY = 10.44%). The PEG-GQDs can be used to detect and quantify paramagnetic transition-metal ions including Fe3+, Cu2+, Co2+, Ni2+, Pb2+, and Mn2+. In the case of ethylenediaminetetraacetic acid (EDTA) solution as a masking agent, Fe3+ ions can be well selectively determined in a transition-metal ion mixture, following the lowest limit of detection (LOD) of 5.77 ?M. The quenching mechanism of Fe3+ on PEG-GQDs belongs to dynamic quenching. Furthermore, Fe3+ in human serum can be successfully detected by the PEG-GQDs, indicating that the green prepared PEG-GQDs can be applied as a promising candidate for the selective detection of Fe3+ in clinics.
Project description:We report the responsive fluorescence chemosensory phenomena of a carbazole-functionalized crosslinked polymer (PCaT) with pendent terpyridine (tpy) groups as receptors of metal ions. The polymer was synthesized using Heck polymerization between 3,6-dibromide groups in a carbazole-based polymer (PC2Br) and divinyl tpy monomer. The effects of the polymeric structure on the optical and chemosensory properties of the PCaT were compared with those of a carbazole-tpy alternating conjugated polymer (PCT). Photoluminescence titrations demonstrated that the PCaT and PCT had the high sensing ability toward Fe3+ ions, with Stern⁻Volmer constants of 8.10 × 10⁴ and 6.68 × 10⁴ M-1, respectively. The limit of detection (LOD) toward Fe3+ of the PCaT and PCT was estimated to be 1.31 × 10-6 and 1.81 × 10-6 M, respectively, and the superior LOD of the PCaT was ascribed to its lowly crosslinked structure. The fluorescence of the solutions of these polymers that were quenched by Fe3+ ions recovered when trace CN- anions were added because of the high stability constant of the CN-⁻Fe3+ complex. Micellar aggregates with a mean diameter of approximately 239.5 nm were formed by dissolving the PCaT in tetrahydrofuran (THF) solution. Our results suggest that the PCaT is a promising material for chemosensory applications.
Project description:Citric acid capped CdS quantum dots (CA-CdS QDs), a new assembled fluorescent probe for copper ions (Cu<sup>2+</sup>), was synthesized successfully by a simple hydrothermal method. In this work, the fluorescence sensor for the detection of heavy and transition metal (HTM) ions has been extensively studied in aqueous solution. The results of the present study indicate that the obtained CA-CdS QDs could detect Cu<sup>2+</sup> with high sensitivity and selectivity. It found that the existence of Cu<sup>2+</sup> has a significant fluorescence quenching with a large red shifted (from greenish-yellow to yellowish-orange), but not in the presence of 17 other HTM ions. As a result, Cu?S, the energy level below the CdS conduction band, could be formed at the surface of the CA-CdS QDs and leads to the quenching of fluorescence of CA-CdS QDs. Under optimal conditions, the copper ions detection range using the synthesized fluorescence sensor was 1.0 × 10<sup>?8</sup> M to 5.0 × 10<sup>?5</sup> M and the limit of detection (LOD) is 9.2 × 10<sup>?9</sup> M. Besides, the as-synthesized CA-CdS QDs sensor exhibited good selectivity toward Cu<sup>2+</sup> relative to other common metal ions. Thus, the CA-CdS QDs has potential applications for detecting Cu<sup>2+</sup> in real water samples.
Project description:A novel sensing system has been designed for the detection of cupric ions. It is based on the quenched fluorescence signal of carbon dots (CDs), which were carbonized from poly(vinylpyrrolidone) (PVP) and L-Cysteine (CYS). Cupric ions interact with the nitrogen and sulfur atoms on surface of the CDs to form an absorbed complex; this results in strong quenching of the fluorescence of the CDs via a fast metal-to-ligand binding affinity. The synthesized water-soluble CDs also exhibited a quantum yield of 7.6%, with favorable photoluminescent properties and good photostability. The fluorescence intensity of the CDs was very stable in high ionic strength (up to 1.0 M NaCl) and over a wide range of pH levels (2.0-12.0). This facile method can therefore develop a sensor that offers reliable, fast, and selective detection of cupric ions with a detection limit down to 0.15 ?M and a linear range from 0.5 to 7.0 ?M (<i>R</i><sup>2</sup> = 0.980). The CDs were used for cell imaging, observed that they were low toxicity to Tramp C1 cells and exhibited blue and green and red fluorescence under a fluorescence microscope. In summary, the CDs exhibited excellent fluorescence properties, and could be applied to the selective and sensitive detection of cupric ion and multicolor cell imaging.
Project description:A photoelectrochemical (PEC) sensor with excellent sensitivity and detection toward copper (II) ions (Cu2+) was developed using a cadmium sulphide-reduced graphene oxide (CdS-rGO) nanocomposite on an indium tin oxide (ITO) surface, with triethanolamine (TEA) used as the sacrificial electron donor. The CdS nanoparticles were initially synthesized via the aerosol-assisted chemical vapor deposition (AACVD) method using cadmium acetate and thiourea as the precursors to Cd2+ and S2-, respectively. Graphene oxide (GO) was then dip-coated onto the CdS electrode and sintered under an argon gas flow (50 mL/min) for the reduction process. The nanostructured CdS was adhered securely to the ITO by a continuous network of rGO that also acted as an avenue to intensify the transfer of electrons from the conduction band of CdS. The photoelectrochemical results indicated that the ITO/CdS-rGO photoelectrode could facilitate broad UV-visible light absorption, which would lead to a higher and steady-state photocurrent response in the presence of TEA in 0.1 M KCl. The photocurrent decreased with an increase in the concentration of Cu2+ ions. The photoelectrode response for Cu2+ ion detection had a linear range of 0.5-120 ?M, with a limit of detection (LoD) of 16 nM. The proposed PEC sensor displayed ultra-sensitivity and good selectivity toward Cu2+ ion detection.
Project description:We developed a microreactor with porous copper fibers for synthesizing nitrogen-doped carbon dots (N-CDs) with a high stability and photoluminescence (PL) quantum yield (QY). By optimizing synthesis conditions, including the reaction temperature, flow rate, ethylenediamine dosage, and porosity of copper fibers, the N-CDs with a high PL QY of 73% were achieved. The PL QY of N-CDs was two times higher with copper fibers than without. The interrelations between the copper fibers with different porosities and the N-CDs were investigated using X-ray photoelectron spectroscopy (XPS) and Fourier Transform infrared spectroscopy (FTIR). The results demonstrate that the elemental contents and surface functional groups of N-CDs are significantly influenced by the porosity of copper fibers. The N-CDs can be used to effectively and selectively detect Hg<sup>2+</sup> ions with a good linear response in the 0~50 ?M Hg<sup>2+</sup> ions concentration range, and the lowest limit of detection (LOD) is 2.54 nM, suggesting that the N-CDs have great potential for applications in the fields of environmental and hazard detection. Further studies reveal that the different <i>d</i> orbital energy levels of Hg<sup>2+</sup> compared to those of other metal ions can affect the efficiency of electron transfer and thereby result in their different response in fluorescence quenching towards N-CDs.