Highly fluorescent N, F co-doped carbon dots with tunable light emission for multicolor bio-labeling and antibacterial applications.

Carbon dots (CDs) have emerged as potential biomaterials for bioimaging and antimicrobial applications. However, the lack of tunable long-wavelength emission performance and imprecise antibacterial mechanism limit their practical application. Thus, developing versatile CDs that combine outstanding optical performance and excellent antibacterial activity is of great practical significance. Herein, we prepared a novel nitrogen and fluorine co-doped CDs (N, F-CDs) from o-phenylenediamine and 2,3,5,6-tetrafluoroterephthalic acid, which exhibit high fluorescence quantum yield of 52.2%, large Stokes shift of 112 nm, as well tunable multicolor emission light from blue to red region. Thanks to the high biocompatibility and excellent photostability, the N, F-CDs were successfully implemented to multicolor biolabeling of mammalian cells, protozoan cells and plant cells. Moreover, the negatively charged N, F-CDs hold inherent efficient antibacterial activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). By thoroughly studying the underlying antibacterial mechanisms at the molecular level through real-time quantitative PCR assay, we found the expression of related genes was notably down-regulated, further demonstrated that N, F-CDs against two bacterial strains had distinct target pathways. Our work provides a new reference for developing highly fluorescent multicolor CDs, and may facilitate the design and application of CDs-based nanomaterials in biological environment.

Cell membrane coated smart two-dimensional supraparticle for in vivo homotypic cancer targeting and enhanced combinational theranostics.

Development of intelligent and multifunctional nanoparticle for the diagnosis and treatment of cancer has drawn great attention recently. In this work, we design a smart two-dimensional (2D) supraparticle for tumor targeted magnetic resonance imaging (MRI)/photothermal imaging (PTI) and chemo/photothermal therapy (PTT). Methods: The nanoparticle consists of a manganese dioxide (MnO2) nanosheet coated gold nanorod (GNR) core (loading with chemotherapeutics doxorubicin (DOX)), and cancer cell membrane shell (denoted as CM-DOX-GMNPs). Decoration of cell membrane endows the nanoparticle with greatly improved colloidal stability and homotypic cancer cell targeting ability. Once the nanoparticles enter tumor cells, MnO2 nanosheets can be etched to Mn2+ by glutathione (GSH) and acidic hydrogen peroxide (H2O2) in the cytosol, leading to the release of DOX. Meanwhile, stimuli dependent releasing of Mn2+ can act as MRI contrast agent for tumor diagnosis. Illumination with near-infrared (NIR) light, photothermal conversion effect of GNRs can be activated for synergistic cancer therapy. Results:In vivo results illustrate that the CM-DOX-GMNPs display tumor specific MRI/PTI ability and excellent inhibition effect on tumor growth. Conclusion: This bioinspired nanoparticle presents an effective and intelligent approach for tumor imaging and therapy, affording valuable guidance for the rational design of robust theranostics nanoplatform.

Digital counting of single semiconducting polymer nanoparticles for the detection of alkaline phosphatase.

Alkaline phosphatase (ALP) as a necessary hydrolase in phosphate metabolism is closely related to various diseases. Ultrasensitive detection of ALP with a convenient and sensitive method is of fundamental importance. In this work, a fluorescence resonance energy transfer (FRET)-based single-particle enumeration (SPE) method is proposed for the quantitative analysis of ALP. This strategy is based on the effective fluorescence suppression by a polydopamine (PDA) shell on the surface of semiconducting polymer nanoparticles (SPNs). PDA with broadband absorption in the UV-vis region can serve as an excellent quencher for SPNs. However, ascorbic acid (AA), the product of the hydrolysis of 2-phosphate-l-ascorbic acid trisodium salt (AAP) in the presence of ALP, can effectively inhibit the self-polymerization of dopamine (DA) to form a PDA layer. Therefore, ALP can be accurately quantified by counting the concentration-related fluorescent particles in the fluorescence image. A linear range from 0.031 to 12.4 µU mL-1 and a limit-of-detection (LOD) of 0.01 µU mL-1 for ALP determination are achieved. The spiked recoveries for ALP determination in a human serum sample are between 90% and 108% with RSD less than 3.1%. In summary, this convenient and sensitive approach proposed here provides promising prospects for ALP detection in a complex biological matrix.

Ratiometric fluorescence nanoprobe for monitoring of intracellular temperature and tyrosine based on a dual emissive carbon dots/gold nanohybrid.

A novel dual-emission nitrogen doped carbon dots/gold nanohybrid (NCDs-Au) was designed for specific and sensitive ratiometric detection of intracellular temperature and tyrosine. In this probe, a reductive NCDs was successfully prepared with the use of natural biomass Dendrobium officinale as precursor. The new prepared NCDs acted as both reducers and stabilizers to synthesize a novel NCDs-Au nanohybrid by a facile one-step procedure along with a quantum yield of 14.3%. The prepared nanoprobe showed characteristic fluorescence emissions of NCDs and Au NCs with single-wavelength excitation. Notably, the nanoprobe shows an interesting wavelength-dependent dual response to temperature (448 nm) and tyrosine (660 nm), enabling the two targets to be detected proportionally. As an effective temperature sensor, the nanoprobe exhibited good temperature-dependent fluorescence with a sensational linear response from 5 to 75 °C. In addition, the sensor has a linear response toward tyrosine in the range of 0.5-175 µM with a detection limit of 0.19 µM. Moreover, the fluorescent nanoprobe was successfully applied to ratiometricly monitor the variation of temperature or tyrosine level in cells because of the low cytotoxicity, chemical stability and excellent fluorescence properties. These results suggested that the nanoprobe here has provided the possibility for rapidly biosensing with the acceptable selectivity and sensitivity.

Enzyme activity-modulated etching of gold nanobipyramids@MnO2 nanoparticles for ALP assay using surface-enhanced Raman spectroscopy.

The detection of enzyme activity can provide valuable insights into clinical diagnosis. Herein, we synthesize gold nanobipyramids@MnO2 nanoparticles (AMNS) as the surface-enhanced Raman spectroscopy (SERS) substrate for the first time and design a "turn-on" SERS strategy for the detection of enzyme activity without the need for a complicated SERS nanotag preparation process. In the presence of alkaline phosphatase (ALP), 2-phosphate-l-ascorbic acid trisodium salt (AAP) can be hydrolyzed to ascorbic acid (AA), which can etch the shell of AMNS by reducing MnO2 to Mn2+. The cracked MnO2 shell-caused electromagnetic field enhancement from AMNS can give rise to a significant increase in the Raman intensity of the adsorbed molecules (i.e., crystal violet, CV) on the surfaces of nanobipyramids. Thus, the ALP activity can be accurately quantified based on the MnO2 shell thickness dependent Raman signal output from CV. A linear dynamic range from 0.4 to 20 mU mL-1 with a detection limit of 0.04 mU mL-1 is achieved, which is more sensitive than other spectroscopic methods for ALP detection. Because of its advantages of sensitivity, convenience and versatility, this approach provides a new perspective to disease-related biomolecular detection in the future.

Applications of hydrothermal synthesis of Escherichia coli derived carbon dots in in vitro and in vivo imaging and p-nitrophenol detection.

Carbon dots (CDs) have broad prospective applications in various fields, and expanding the applications of fluorescent CDs, especially for CDs derived from bacteria, is a major research goal. In this study, novel CDs derived from Escherichia coli BW25113 (WT) were successfully synthesized via a one-step hydrothermal method. Unlike previously developed CDs-E. coli, CDs-WT can be used for microbial imaging of both live and dead cells. We demonstrated the biocompatibility, excellent penetrability, and nontoxic characteristics of CDs-WT for use as fluorescent probes for bioimaging both in vitro and in vivo. Importantly, we provide the first demonstration of CDs-WT distribution in various organs of mice, including the ability to cross the blood-brain barrier and the potential for rapid excretion through the intestines. Additionally, CDs-WT can be instantly utilized as a fluorescent probe for the highly selective and rapid detection of p-nitrophenol (p-NP) by the inner filter effect, with a limit of detection for p-NP of 11 nM, the lowest value reported to date. Hence, our results demonstrate the feasibility of p-NP detection and extend the bio-imaging applications of CDs prepared from bacteria.

Bacteria-derived fluorescent carbon dots for highly selective detection of p-nitrophenol and bioimaging.

p-Nitrophenol (p-NP) pollutants are widely present in soil and aquatic environments and can seriously impair the health of living beings. Hence, a rapid, sensitive, and selective method for p-NP detection is urgently needed. Herein, for the first time, we successfully synthesized fluorescent carbon dots (CDs) from Bacillus cereus (BC) via a one-step hydrothermal process. The obtained CDs-BC can be applied as a rapid, highly selective, and sensitive sensor for p-NP detection. The fluorescence quenching efficiency of the CD-BC sensor exhibited excellent linear responses with p-NP concentrations at both 0.3-6.5 µM and 6.5-30 µM, with a detection limit of 0.11 µM. The mechanism of p-NP detection is based on the inner filter effect (IFE). Preliminary bacteria, cell, and animal studies showed that the as-prepared CDs-BC possess high photostability, excellent biocompatibility, low or no biotoxicity, and multicolor fluorescence emission properties; furthermore, they can be rapidly excreted from the body of mice, which suggests their potential for applications in the biomedical field.

A ratiometric fluorescence and light scattering sensing platform based on Cu-doped carbon dots for tryptophan and Fe(III).

A new Cu-doped carbon dots (Cu-CDs) were synthesized rapidly and simply via one-step thermolysis of Na2[Cu(EDTA)] and ascorbic acid (AA) at 250°C for 2h with a high quantum yield of 9.8%. The Cu-CDs exhibits two signals of fluorescence at 396nm and second-order scattering (SOS) at 617nm under a single excitation wavelength of 308nm, and can be obviously enhanced by tryptophan (Trp) or Fe(III) leading to the ratiometric fluorescence and SOS response with a good linear wider range of 0.5-250µM and 0.1-50µM, respectively. This sensing system exhibits good selectivity and sensitivity toward Trp and Fe(III) over other analytes with a low detection limit of 275nM and 46nM, respectively. Furthermore, the proposed sensing system displays a prospective application for quantitative assay of Trp and Fe(III) in practical sample.

Fabrication of CDs/CdS-TiO2 ternary nano-composites for photocatalytic degradation of benzene and toluene under visible light irradiation.

An efficient cadmium sulfide quantum-dots (CdS QDs) and carbon dots (CDs) modified TiO2 photocatalyst (CdS/CDs-TiO2) was successfully fabricated. The as-prepared ternary nano-composites simultaneously improved the photo-corrosion of CdS and amplified its photocatalytic activity. The introduction of CdS QDs and CDs could enhance more absorbance of light, prevent the undesirable electron/hole recombination, and promote charge separation, which was important for the continuous formation of OH and O2- radicals. When the optimal mass ratio of CdS QDs to CDs was 3:1, above 90% degradation efficiencies were achieved for benzene within 1h and toluene in 2h, while that of pure TiO2 (P25), CdS QDs-TiO2, CDs-TiO2 nano-composites was around 15%. Owing to the symmetric structure and conjugation of methyl with benzene ring, the degradation of toluene was more difficult than benzene to carry on. The new fabricated nano-composites showed good prospective application of cleaning up refractory pollutants and the resource utilization.

Determination of norfloxacin or ciprofloxacin by carbon dots fluorescence enhancement using magnetic nanoparticles as adsorbent.

The authors describe a method for the determination of norfloxacin (NOR) or ciprofloxacin (CIP). It is making use of a combination of fluorescence enhancement and magnetic solid-phase extraction (MSPE). Sulfur-doped carbon dots (S-CDs) are used as a fluorescent probe. They were prepared by a one-pot method using poly(4-styrenesulfonic acid-co-maleic acid) (PSMA) as a source for carbon and sulfur. NOR or CIP act as sensitizers of fluorescence (with excitation/emission maxima at 324/412 nm), probably due to strong hydrogen bond interaction and charge transfer with the S-CDs. The S-CDs were characterized by using TEM, XRD, XPS, FT-IR, UV-Vis and fluorescence spectroscopies. Response is linear in the 0.02-1.25 µM NOR concentration range, and the detection limit is 4.6 nM. The respective data for CIP are 0.02-1.0 µM and 6.7 nM. The average recoveries of NOR and CIP residues from spiked bovine raw milk are 96.2%~105.2% and 92.3%~102.5%. Graphical abstract Sulfur doped carbon dots (S-CDs) were synthesized by a hydrothermal method using poly(4-styrenesulfonic acid-co-maleic acid) (PSMA). Norfloxacin (NOR) or ciprofloxacin (CIP) was extracted by magnetic nanoparticles (MNPs), they were detected by carbon dots fluorescence enhancement.

Hydrothermal Synthesis of Nitrogen-Doped Carbon Quantum Dots as Fluorescent Probes for the Detection of Dopamine.

Nitrogen-doped carbon quantum dots (N-CQDs) were synthesized though a facile, economical and straightforward hydrothermal method by using polyacrylamide as both carbon and nitrogen sources. The as-prepared N-CQDs offered high quantum yield of 23.1%, exhibited good water solubility and fluorescence properties. Moreover, the N-CQDs can be used as effective probes for sensitive and selective detection of dopamine. Fluorescence of N-CQDs was effectively quenched after the addition of dopamine owing to dopamine would be transformed into dopamine-quinone under alkaline conditions. A good linear relationship between fluorescence quenching and the concentration of dopamine in the range 0.1-200 µM was obtained with a low detection limit of 0.05 µM. The proposed method showed high selectivity for dopamine in the presence of potential interfering species. Moreover, this method was successfully applied to the determination of DA in urine sample with satisfactory recoveries.

Nitrogen-doped carbon quantum dots as a fluorescence probe combined with magnetic solid-phase extraction purification for analysis of folic acid in human serum.

A novel and sensitive method based on nitrogen-doped carbon quantum dots as a fluorescence probe coupled with magnetic solid-phase extraction (MSPE) purification for analysis of folic acid (FA) in human serum samples has been established for the first time. In the developed system, magnetic nanoparticles coated with hexanoic acid (Fe3O4@C6) were synthesized by a one-step chemical co-precipitation method with good magnetic properties and dispersibility for sample purification, and it is better to be separated from the sample. High fluorescence nitrogen-doped carbon quantum dots (N-CQDs), simply prepared using a one-step hydrothermal method with nitrilotriacetic acid, could be selectively quenched by FA. Based on this phenomenon, a fluorescence assay was proposed for specific determination of FA. Various operational experiment parameters have been studied and optimized in detail. Under the optimum experimental conditions, the detection limit of the proposed method for FA was evaluated to be 0.5 nM (S/N = 3), while the relative standard deviation (RSD) was 1.2% (n = 6). Finally, the proposed method was applied for determination of trace levels of FA from human serum samples and quantitative recoveries were achieved within the range of 95.7-103.5%. All of the results showed that the proposed method had significant application in further research. Graphical abstract Schematic of synthesis of N-CQDs and schematic of suggested mode for analysis of folic acid (FA).

Highly fluorescent carbon quantum dots as nanoprobes for sensitive and selective determination of mercury (II) in surface waters.

A novel carbon quantum dots (CQDs) was successfully prepared through one-step green hydrothermal method using polyacrylamide as carbon source. The prepared CQDs were characterized using TEM, XRD, XPS, FT-IR, UV-Vis, and fluorescence spectroscopy. The CQDs was demonstrated as nanoprobes for mercury ion detection, moreover, it demonstrated excitation-dependent and superior stability in acidic and alkaline media. Besides, the probe exhibited a good linearity range (0.25-50µM) and a low detection limit (13.48nM). These attractive properties indicated that this novel CQDs can adapt to a variety of complex pH environment, which had extensive prospect and promising application for detection of mercury ions in complex water samples.