Facile one-step fabrication of Cu-doped carbon dots as a dual-selective biosensor for detection of pyrophosphate ions and measurement of pH.

High-performance determination of pyrophosphate ions (PPi) and pH is an important goal in biological systems. In this work, Cu-doped carbon dots (Cu-CDs) were synthesized rapidly and simply via a one-pot hydrothermal method. The as-obtained Cu-CDs, with an average size of 2.55 nm, exhibit an excitation-independent fluorescence emission and possess desirable functional groups of carboxyl and amine, which can be served as fluorescence nanoprobes for detection of PPi based on surface passivation. Under the optimal condition, the linear range for detection of PPi was 0.05-20 µM, and the corresponding limit of detection (LOD) was 0.013 µM, indicative of a promising assay for the PPi. Moreover, the fluorescent intensity of the Cu-CDs is linear against pH value from 6 to 8.7 in buffer solution, suggesting the feasibility as a pH sensor. The synthesized Cu-CDs coated fluorescent paper indeed can monitor pH in urine with satisfaction by naked eyes through ultraviolet irradiation. The successful detection of PPi and the visual detection of pH value suggest a highly promising application of Cu-CDs in the field of biosensing.

Nitrogen and copper-doped carbon quantum dots with intrinsic peroxidase-like activity for double-signal detection of phenol.

Herein, a simple and facile one-step hydrothermal carbonization synthesis procedure for the fabrication of N, Cu-doped carbon quantum dots (N, Cu-CQDs) as a peroxidase-mimicking enzyme was reported. The peroxidase-like performance of N, Cu-CQDs was assessed based on the oxidative coupling reaction of phenol with 4-aminoantipyrine (4-AAP) in the presence of hydrogen peroxide (H2O2). The N, Cu-CQDs/4-AAP/H2O2 system was applied to sensing phenol based on double signals of absorption spectra (or colorimetric visualization) as well as fluorescence spectra. The obtained limits of detection (LODs) were as low as 0.12 µM and 0.02 µM, respectively. Moreover, the proposed method was successfully applied to the determination of phenol in sewage with satisfactory recovery. Our results demonstrate that the N, Cu-CQDs/4-AAP/H2O2/phenol sensing system has a great potential prospect for applications in environmental chemistry and biotechnology.

Yellow emission carbon dots for highly selective and sensitive OFF-ON sensing of ferric and pyrophosphate ions in living cells.

A simple "OFF-ON" fluorescent system was proposed for selective and sensitive detection of ferric ion (Fe3+) and pyrophosphate (PPi) in living cells. The method was constructed based on the bright yellow emission of carbon dots (y-CDs), which were prepared using o-phenylenediamine (OPD) as the precursor via a facile hydrothermal treatment. The as-obtained y-CDs, with an average size of 2.6 nm, exhibited an excitation-independent emission peak at 574 nm. The fluorescence of y-CDs can be remarkably quenched by Fe3+ with high selectivity and sensitivity. Interestingly, the quenched fluorescence can be recovered regularly upon addition of PPi, showing a promising detection for PPi. The linear ranges for Fe3+ and PPi detections were 0.05-80 and 0.5-120 µM, respectively, and the corresponding limit of detections (LODs) were 22.1 and 73.9 nM. As we proved the y-CDs have negligible cytotoxicity and excellent biocompatibility, further application to the fluorescence imaging of intracellular Fe3+ and PPi were conducted, suggesting the prepared y-CDs can be used to monitor Fe3+ and PPi variation in living cells. Overall, our developed y-CDs-based OFF-ON switch fluorescent probe has the advantages of simplicity, agility, high sensitivity and selectivity, which provides a promising platform for environmental and biology applications, and paves a new avenue for monitoring the hydrolysis process of adenosine triphosphate disodium salt (ATP) by detection of PPi in organisms.

Fabrication of highly active phosphatase-like fluorescent cerium-doped carbon dots for in situ monitoring the hydrolysis of phosphate diesters.

Ce-Doped carbon dots (CeCDs) were fabricated via a one-step hydrothermal carbonization using Ce(NO3)3·6H2O and EDTA·2H2O as precursors, and various experimental techniques were employed to characterize the morphology, structure and composition of the as-obtained CeCDs. Using the disodium salt of bis(4-nitrophenyl)phosphate (BNPP) as a DNA model substrate, mimetic phosphatase activity toward phosphate ester hydrolysis cleavage was investigated. It was found that similar to the catalytic character of the natural enzyme, CeCDs as a hydrolase mimic can exhibit a good catalytic activity for promoting BNPP hydrolysis, in which metal Ce(iii) acts as a center for binding and activation of the metal-bound hydroxide complex as well as a source of nucleophilic metal hydroxides. Additionally, based on the Inner Filter Effect (IFE), fluorescence spectra can be used to monitor the hydrolysis of BNPP using CeCDs, which mimic phosphatase. Thus, the unique properties of the CeCD mimetic phosphatases as well as the IFE sensing strategy would provide an ideal platform to monitor the catalytic phosphate ester hydrolysis processes. Finally, to validate the availability of the established catalytic systems, the CeCDs were further applied for degradation of organophosphorus pesticide chlorpyrifos. The degradation efficiency was estimated to be a satisfactory value of 74.50%, exhibiting a potential application prospect for treatment of the pollutants in the soil and water.

Preparation of palladium/carbon dot composites as efficient peroxidase mimics for H2O2 and glucose assay.

In this study, palladium/carbon dot composites (Pd-CDs) were fabricated via a facial hydrothermal route using ethanediamine and palladium chloride dihydrate as precursors. The obtained Pd-CDs showed an excellent intrinsic peroxidase-like activity, which could catalyze the oxidization of 3,3'5,5'-tetramethylbenzidine with the assistance of hydrogen peroxide (H2O2) and thus resulted in color change, accompanied by an absorption peak which appeared at 652 nm. Such response is H2O2 concentration-dependent and allows for the assay of H2O2 in the range of 0.1 to 30 µM with a limit of detection of 0.03 µM. Simultaneously, by combination of enzymatic oxidation of glucose with glucose oxidase and Pd-CD catalytic reaction, a colorimetric sensing platform was also constructed for glucose detection with high selectivity and sensitivity (limit of detection as low as 0.2 µM). Additionally, the proposed method exhibited capability for determination of glucose in real samples (fruit juice) with satisfactory recovery (98.5-103%), indicating potential application prospects in biochemical analysis.

Manganese(II)-doped carbon dots as effective oxidase mimics for sensitive colorimetric determination of ascorbic acid.

A colorimetric assay is presented for the determination of ascorbic acid (AA). Manganese(II) doped carbon dots (Mn-CDs) were prepared by a convenient hydrothermal route and are shown to possess oxidase-like catalytic ability. They catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by dissolved oxygen to form a blue colored product (oxTMB). AA can reduce blue oxTMB to colorless TMB. The fading of the blue color (measured at 652 nm) can be applied for quantifying AA in the 50 to 2500 nM concentration range and with a 9 nM detection limit. The method was successfully used for the quantitation of AA in real samples. Graphical abstract Schematic representation of a colorimetric assay platform for the sensitive detection of ascorbic acid (AA) in view of inhibitory effect of AA on the 3,3',5,5'-tetramethylbenzidine (TMB) oxidation, benefitting from excellent oxidase-like catalytic activity of manganese(II) doped carbon dots (Mn-CDs).

Facile fabrication of fluorescent Fe-doped carbon quantum dots for dopamine sensing and bioimaging application.

In this paper, we have presented a novel strategy to fabricate Fe-doped carbon quantum dots (Fe-CQDs) for dopamine sensing applications. The Fe-CQDs are obtained by one step hydrothermal carbonization, using ethylenediamine tetraacetic acid salts and ferric nitrate as the carbon and iron source, which simultaneously incorporates Fe (dopamine-bonding site) and luminescent carbon quantum dots (fluorophores). The added dopamine containing catechol groups might form complexes with Fe ions (doped in CQDs) due to coordination. Subsequently, dopamine was oxidized to generate dopamine-quinone (a known potent electron acceptor) species by ambient O2. Thus, the coordination induced dopamine in proximity to the CQDs, which provided favourable electron acceptors in close proximity to the CQDs and produced high quenching efficiencies. Such fluorescence responses can be used for well quantifying dopamine in the range of 0.01-50 µM with a detection limit of 5 nM (S/N = 3). The proposed sensing system has been successfully used for the assay of dopamine in human urine samples. Preliminary cell image study indicates that the obtained Fe-CQDs possess high photostability and low cytotoxicity, which make them promising for biological applications.

High-throughput and rapid fluorescent visualization sensor of urinary citrate by CdTe quantum dots.

In this paper, we have presented a novel CdTe quantum dots (QDs) based fluorescent sensor for visual and turn-on sensing of citrate in human urine samples. The europium ion (Eu(3+)) can lead to the fluorescence quenching of thioglycollic acid (TGA) modified CdTe QDs due to photoinduced electron transfer accompanied by the change of emission color from yellow to orange. Next, addition of citrate breaks the preformed assembly because citrate can replace the CdTe QDs, based on the fact that the Eu(3+) ion displays higher affinity with citrate than the CdTe QDs. Thus the photoinduced electron transfer is switched off, and the fluorescence emission of CdTe QDs is rapidly (within 5min) recovered, simultaneously, the orange emission color restores to yellow. Such proposed strategy may conveniently discriminate the patient of renal stone from normal person by naked eyes. In addition to visualization detection, the fluorescence responses can be used for well quantifying citrate in the range of 0.67-133µM. So, the present, simple, low-cost and visualized citrate fluorescence sensor has great potential in the applications for earlier screening in clinical detection.

Fluorescent graphene quantum dot nanoprobes for the sensitive and selective detection of mercury ions.

Graphene quantum dots were prepared by ultrasonic route and served as a highly selective water-soluble probe for sensing of Hg(2+). The fluorescence emission spectrum of graphene quantum dots was at about 430nm. In the presence of Hg(2+), the fluorescence of the quantum dots significantly quenched. And the fluorescence intensity gradually decreased with the increasing concentration of Hg(2+). The change of fluorescence intensity is directly proportional to the concentration of Hg(2+). Under optimum conditions, the linear range for the detection of Hg(2+) was 8.0×10(-7) to 9×10(-6)M with a detection limit of 1.0×10(-7)M. In addition, the preliminary mechanism of fluorescence quenching was discussed in the paper. The constructed sensor with high sensitivity and selectivity, simple, rapid properties makes it valuable for further application.

Label-free fluorescence polarization detection of pyrophosphate based on 0D/1D fast transformation of CdTe nanostructures.

A novel and label-free fluorescence polarization (FP) method for the determination of pyrophosphate (PPi) is developed based on the change in FP signals during fast reversible transformation between CdTe zero-dimensional (0D) nanocrystals (NCs) and one-dimensional (1D) nanorods (NRs) induced by addition of PPi. Under optimum conditions, the FP ratio was linearly proportional to the logarithm of the concentration of PPi between 2.0 × 10(-5) and 1.0 × 10(-9) M with a detection limit of 8.0 × 10(-10) M. The developed method, with high signal selectivity and stability, was successfully applied to the detection of PPi in human urine samples.

Eu(III)-induced room-temperature fast transformation of CdTe nanocrystals into nanorods.

A fast and mild synthesis method of highly crystalline CdTe nanorods (NRs) was developed by adding europium nitrate hexahydrate to an aqueous solution of CdTe nanocrystals (NCs) at room temperature within 30 min. It was suggested that strong coordination strength of Eu(III) decreases zeta potential, thereby accelerates aggregation of NCs, and favors the transformation process from NCs to NRs. The oriented attachment of aggregated particles was suggested as a major path for the formation of highly crystalline NRs under experimental conditions. The proposed extremely fast room-temperature methodology opens up novel pathways for the synthesis of one-dimensional (1D) semiconductor nanostructures with high crystallinity, which would become potential candidates for many practical applications such as photovoltaics, circuit design and fabrication of functional architectures.

Upconversion and downconversion fluorescent graphene quantum dots: ultrasonic preparation and photocatalysis.

A facile ultrasonic route for the fabrication of graphene quantum dots (GQDs) with upconverted emission is presented. The as-prepared GQDs exhibit an excitation-independent downconversion and upconversion photoluminescent (PL) behavior, and the complex photocatalysts (rutile TiO(2)/GQD and anatase TiO(2)/GQD systems) were designed to harness the visible spectrum of sunlight. It is interesting that the photocatalytic rate of the rutile TiO(2)/GQD complex system is ca. 9 times larger than that of the anatase TiO(2)/GQD complex under visible light (λ > 420 nm) irradiation in the degradation of methylene blue.

Determination of nucleic acids with a near infrared cyanine dye using resonance light scattering technique.

A new method for the determination of nucleic acids has been developed based on the enhancement effect of resonance light scattering (RLS) with a cationic near infrared (NIR) cyanine dye. Under the optimal conditions, the enhanced RLS intensity at 823 nm is proportional to the concentration of nucleic acids in the range of 0-400 ng mL-1 for both calf thymus DNA (CT DNA) and fish sperm DNA (FS DNA), 0-600 ng mL-1 for snake ovum RNA (SO RNA). The detection limits are 3.5 ng mL-1, 3.4 ng mL-1 and 2.9 ng mL-1 for CT DNA, FS DNA and SO RNA, respectively. Owing to performing in near infrared region, this method not only has high sensitivity endowed by RLS technique but also avoids possible spectral interference from background. It has been applied to the determination of nucleic acids in synthetic and real samples and satisfactory results were obtained.

High selective determination iron(II) by its enhancement effect on the fluorescence of pyrene-tetramethylpiperidinyl (TEMPO) as a spin fluorescence probe.

A novel fluorescence method determination for iron(II) with a high selectivity and sensitivity has been proposed, based on the enhancement of fluorescence signals resulting from specific redox reaction between synthesized spin fluorescence probe pyrene-tetramethylpiperidinyl (TEMPO) and iron(II). Under the experimental conditions, fluorescent probe displayed a rapid and linear response for iron(II) over the concentration range from 2.4 x 10(-7) to 3.6 x 10(-6) mol/L. The limit of detection was 4.0 x 10(-8) mol/L. The relative standard deviation of six replicate measurements was 1.90% for 3.0 x 10(-7) mol/L iron(II). Because of the specific redox reaction between developed spin fluorescence probe and iron(II), there are few interference by other ions, especially in the presence of relative high concentration iron(III). The method has been successfully applied for iron(II) determinations in two different kinds of real samples. Results determined by the proposed method agree favorably with those determined UV-vis spectrometry method with 1,10-phenanthroline.

Determination of nucleic acids based on shifting the association equilibrium between tetracarboxy aluminum phthalocyanine and poly-lysine.

A new method based on near-infrared (near-IR) fluorescence recovery was presented for the determination of nucleic acids. This method employed a two-reagent system composed of anionic tetracarboxy aluminum phthalocyanine (AlC4Pc) and polycationic poly-lysine. The fluorescence of AlC4Pc, with the maximum excitation and emission wavelengths at 620 and 701 nm, respectively, was quenched by poly-lysine with a proper concentration, but recovered by adding nucleic acids. Under optimal conditions, the recovered fluorescence was in proportional to the concentration of nucleic acids. The linear ranges of the calibration curves were 5-200 ng mL(-1) for both calf thymus DNA (ctDNA) and fish sperm DNA (fsDNA) with the detection limit of 2.6 ng mL(-1) for ctDNA and 2.1 ng mL(-1) for fsDNA. The relative standard deviation (n = 6) was 1.9 and 1.3% for 50 ng mL(-1) ctDNA and fsDNA, respectively. The proposed method was applied to the determination of nucleic acids in synthetic samples with satisfactory results.

Preparation and application of cysteine-capped ZnS nanoparticles as fluorescence probe in the determination of nucleic acids.

Cysteine-capped ZnS nanometer-sized fluorescent particles were produced by a colloidal aqueous synthesis. The functionalized nanoparticles are water-soluble and suitable for biological application. A synchronous fluorescence method has been developed for the rapid determination of DNA with functionalized nano-ZnS as a fluorescence probe, based on the synchronous fluorescence enhancement of cysteine-capped nano-ZnS in the presence of DNA. When Deltalambda =190 nm, maximum synchronous fluorescence is produced at 267 nm at pH 5.12. Under optimum conditions, the synchronous fluorescence intensity is proportional to the concentration of nucleic acids in the range 0.1-1.2 microg ml(-1) for calf thymus DNA, 0.1-0.6 microg ml(-1) for fish sperm DNA. The corresponding detection limit is 32.9 ng ml(-1) for calf thymus DNA and 24.6 ng ml(-1) for fish sperm DNA. This method is simple, inexpensive, rapid and sensitive. The recovery and relative standard deviation are satisfactory.

Fluorescence enhancement method for measuring anionic surfactants with a hydrophobic cyanine dye.

A novel fluorimetric method based on use of a hydrophobic cationic cyanine dye has been developed for determination of the anionic surfactant sodium dodecylbenzenesulfonate (DBS). The method is based on the enhancement effect of DBS on the fluorescence of the hydrophobic cyanine dye 2-[-4'-chloro-7'-(1"-ethyl-3",3"-dimethylindolin-2"-ylidene)-3',5'-(propane-1"',3"'-diyl)-1',3',5'-heptatrien-1'-yl]-1-ethyl-3,3-dimethyl-3 H-indolium iodide. Under the optimum conditions the extent of fluorescence enhancement is proportional to the concentration of DBS in the range 0.05-5.0 mg L(-1); the detection limit is 0.014 mg L(-1). The relative standard deviation for 0.35 mg L(-1) DBS was 1.1% (n=10). The proposed method, which avoided use of toxic solvents and tedious solvent-extraction, and was applied to the determination of DBS in natural water with recoveries between 99.9 and 107%. Preliminary research shows that the fluorescence enhancement is due to the formation of a dye aggregate facilitated by DBS.

Determination of nucleic acids with tetra-(N-hexadecylpyridiniumyl) porphyrin sensitized by cetyltrimethylammonium bromide (CTMAB) using a Rayleigh light-scattering technique.

Using a common spectrofluorometer to measure the intensity of Rayleigh light-scattering (RLS), a method for determination of nucleic acids has been developed. At pH 10.24 and ionic strength 0.01 mol l-1 (NaCl), the Rayleigh light-scattering of the tetra-(N-hexadecylpyridiniumyl) porphyrin (TC16PyP) is greatly enhanced by nucleic acids in the presence of cetyltrimethylammonium bromide (CTMAB), with the scattering peak located at 311.8 nm. The enhanced RLS intensity is in proportion to the concentration of calf thymus DNA (ctDNA) in the range 0.2-6.0 microg ml-1 and to that of fish sperm DNA (fsDNA) in the range 0.05-3.0microg ml-1. The limits of detection are 0.016 microg ml-1 for calf thymus DNA and 0.023 microg ml-1 for fish sperm DNA when the concentration of TPP was chosen 2.0 x 10(-6) mol l-1. Four synthetic samples were determined satisfactorily.

Fluorescence enhancement method for the determination of nucleic acids using cationic cyanine as a fluorescence probe.

A fluorescence enhancement method with a cationic cyanine as a probe was developed for the determination of nucleic acids. Under the experimental conditions, the fluorescence enhancement of cyanine (lambda(ex)/lambda(em)= 524/591.5 nm) was observed in the presence of DNA. The calibration graphs were linear over the range of 0.01-15 microg mL(-1) for both calf thymus DNA (CT DNA) and fish sperm DNA (FS DNA). The limits of detection were 0.005 and 0.007 microg mL(-1) for CT DNA and FS DNA, respectively. The method was applied to the determination of DNA in synthetic and real samples and satisfactory results were obtained. A possible fluorescence enhancement mechanism was also studied.

Near-infrared fluorimetric determination of nucleic acids by shifting the ion-association equilibrium between tetracarboxy aluminum phthalocyanine and tetra-N-hexadecylpyridiniumyl porphyrin.

A new method was developed for determination of micro amounts of nucleic acids based on near-infrared (near-IR) fluorescence recovery, employing a two-reagent system which is composed of an anionic tetracarboxy aluminum phthalocyanine (AlC(4)Pc) and a cationic tetra-N-hexadecylpyridiniumyl porphyrin (TC(16)PyP). The fluorescence of the AlC(4)Pc, with the maximum emission wavelength at 701nm, could be quenched by TC(16)PyP at its proper concentration, but recovered by adding nucleic acids. Under optimal conditions, the recovered fluorescence is proportional to the concentration of nucleic acids. The calibration graphs are linear over the range of 1-200ngmL(-1) for fish sperm DNA (FS DNA) and 2-400ngmL(-1) for calf thymus DNA (CT DNA). The corresponding detection limits are 0.59ngmL(-1) for FS DNA and 0.82ngmL(-1) for CT DNA, respectively. Four synthetic and three real nucleic acid samples were determined with satisfactory results.