发绿色荧光碳点的制备并用于Pb2+的灵敏检测和细胞成像

碳点作为一种新型的荧光纳米材料,与传统的半导体量子点相比具有优异的生物相容性、低毒性、易修饰等优点,使其在生物医学领域具有广泛的应用前景。本文以L-半胱氨酸和蔗糖为原料,在0.1 mol·L^-1的NaOH溶液中成功的制备出发绿色荧光的碳点(G-CDs),最佳发射波长是515 nm,经表征得出其表面主要还有氨基、羟基和羧基等基团,荧光量子产率高达33.4%,其荧光可被Pb^2+特异性猝灭,最终应用于Pb^2+的灵敏检测,检出限为0.025μmol·L^-1。经MTT法测定G-CDs对人肝癌细胞(SMMC-7721)为低毒性,最后应用到细胞荧光成像中,通过细胞成像技术成功检测细胞中Pb^2+的存在。     

Ionic liquids as precursors for highly luminescent,surface-different nitrogen-doped carbon dots used for label-free detection of Cu/Fe and cell imaging

Carbon nanodots (C-Dots) have attracted much attention in recent years due to their low cost, ready scalability, excellent chemical stability, biocompatibility and multicolor luminescence. Here, we report a facile strategy for producing highly luminescent, surface-different nitrogen-doped carbon dots (C-Dots) by using different ionic liquids (ILs). Intriguingly, the surface-different C-Dots show different selectivity for Cu²⁺ and Fe³⁺. To the best of our knowledge, this is the first example which shows that ILs are excellent precursors for producing luminescent nanomaterial used for detection of different metal ions. The resultant nitrogen-doped C-Dots are highly photoluminescent and can be used for multicolor bioimaging. Most notable, by taking different ILs as precursors, we obtain surface-different C-Dots, which can be directly used for selective detection of Cu²⁺ and Fe³⁺ without any modification. These C-Dots based sensors exhibit high sensitivity and selectivity and the sensing process can be easily accomplished with one-step rapid operation. More importantly, compared with other method using QDs, organic dyes and organic solvent, this strategy is much more eco-friendly. This work may offer a new approach for developing low cost and sensitive C-Dots-based sensors for biological and environmental applications.     

Ratiometric fluorescence detection of mercuric ion based on the nanohybrid of fluorescence carbon dots and quantum dots

A novel nanohybrid ratiometric fluorescence probe comprised of carbon dots (C-dots) and hydrophilic CdSe@ZnS quantum dots (QDs) has been developed by simply mixing the blue-emission C-dots with red-emission carboxylmethyldithiocarbamate modified CdSe@ZnS QDs (GDTC-QDs). The nanohybrid ratiometric fluorescence probe exhibits dual emissions at 436 nm and 629 nm under a single excitation wavelength. Due to the strong chelating ability of GDTC on the surface of QDs to mercuric ion (Hg²⁺), the fluorescence of the GDTC-QDs in the nanohybrid system could be selectively quenched in the presence of Hg²⁺ while the fluorescence of the C-dots remained constant, resulting in an obviously distinguishable fluorescence color evolution (from red to blue) of the nanohybrid system. The detection limit of this method was found to be as low as 0.1 μM. Furthermore, the recovery result for Hg²⁺ in real samples including tap water and lake water by this method was satisfying, suggesting its potential application for Hg²⁺ sensing.     

Field-portable ratiometric fluorescence imaging of dual-color label-free carbon dots for uranyl ions detection with cellphone-based optical platform

Under the public spotlight, uranyl (UO₂²⁺) ions has attracted considerable attention for the extreme radioactive and chemical toxicity to ourselves and our environment. Herein, we present a simple and effective ratiometric fluorescence imaging method for the visualizing and quantitative detection UO₂²⁺ ions by cellphone-based optical platform. The sensing solution was prepared by mixing label-free red carbon dots (r-CDs) and blue carbon dots (b-CDs) together with a fixed photoluminescence intensity ratio of 4:1. When UO₂²⁺ ions were added, the fluorescence of r-CDs can be selectively quenched, while the fluorescence of b-CDs remains stable without spectral changes. With the gradually increase the amounts of UO₂²⁺ ions, the different response of dual-color CDs resulted in a signification color evolution from deep red to dark purple under the ultraviolet (UV) light illumination. Then, a cellphone-based optical platform was constructed for directly imaging the color change of the samples, and the built-in Colorpicker APP quickly output the red, green and blue (RGB) channel values of these images within one second. Interesting, there was a linear relationship between the ratio of red and blue (R/B) channel values and UO₂²⁺ ions concentration from 0 μmol/L to 30.0 μmol/L (R² = 0.92804) with the detection limit of ∼8.15 μmol/L (signal-to-noise ratio of 3). In addition, the optical platform has also been applied to the quantification of UO₂²⁺ ions in tap water and river water sample. With the advantage of low-cost, portable, easy to operation, we anticipate that this method would greatly improve the accessibility of UO₂²⁺ ions detection even in resource-limited areas.     

Field-portable ratiometric fluorescence imaging of dual-color label-free carbon dots for uranyl ions detection with cellphone-based optical platform

Under the public spotlight, uranyl (UO₂²⁺) ions has attracted considerable attention for the extreme radioactive and chemical toxicity to ourselves and our environment. Herein, we present a simple and effective ratiometric fluorescence imaging method for the visualizing and quantitative detection UO₂²⁺ ions by cellphone-based optical platform. The sensing solution was prepared by mixing label-free red carbon dots (r-CDs) and blue carbon dots (b-CDs) together with a fixed photoluminescence intensity ratio of 4:1. When UO₂²⁺ ions were added, the fluorescence of r-CDs can be selectively quenched, while the fluorescence of b-CDs remains stable without spectral changes. With the gradually increase the amounts of UO₂²⁺ ions, the different response of dual-color CDs resulted in a signification color evolution from deep red to dark purple under the ultraviolet (UV) light illumination. Then, a cellphone-based optical platform was constructed for directly imaging the color change of the samples, and the built-in Colorpicker APP quickly output the red, green and blue (RGB) channel values of these images within one second. Interesting, there was a linear relationship between the ratio of red and blue (R/B) channel values and UO₂²⁺ ions concentration from 0 μmol/L to 30.0 μmol/L (R² = 0.92804) with the detection limit of ~8.15 μmol/L (signal-to-noise ratio of 3). In addition, the optical platform has also been applied to the quantification of UO₂²⁺ ions in tap water and river water sample. With the advantage of low-cost, portable, easy to operation, we anticipate that this method would greatly improve the accessibility of UO₂²⁺ ions detection even in resource-limited areas.     

The green synthesis of carbon quantum dots and applications for sulcotrione detection and anti-pathogen activities

In this study, we synthesized simple, cheap, and stable nitrogen (N)-doped carbon quantum dots (N-CQDs) from Moringa oleifera roots. The N-CQDs exhibited an intense blue fluorescence and a quantum yield (QY) of up to 43.4%. When excited at 350 nm, the highest generated wavelength was observed at 445 nm. These N-CQDs were then successfully used to detect sulcotrione (limit of detection = 2 μg/mL); the method was reliable and exhibited good feasibility for measurements in real samples. When the N-CQDs concentration was 11.0 μL/mL, inhibitory rates against the pathogens, Corynespora cassiicola and Phytophtora nicotianae were 82.8% and 75.3%, respectively. To investigate N-CQDs safety for plant growth, different concentrations were investigated using sorghum seedlings, with N-CQDs exhibiting very low toxicity toward plant growth. Thus, these findings provide a basis for the development of N-CQDs as green pesticides.     

Dual functions of nitrogen and phosphorus co-doped carbon dots for drug-targeted delivery and two-photon cell imaging

Heteroatom-doping carbon dots (CDs) have excellent fluorescence properties. In the paper, nitrogen (N) and phosphorus (P) co-doped CDs (N, P-CDs) were prepared through the hydrothermal method and characterized by TEM, PXRD, FT-IR, ¹³C NMR, XPS, UV–vis, and fluorescence spectra. The optical properties and drug (doxorubicin) - delivery performance of N, P-CDs were also studied. The results showed that the average size of N, P-CDs was 3.64 nm and the quantum yield was 30 %. The N, P-CDs had down- and up-conversion fluorescence properties, and the luminescence mechanism of the N, P-CDs was explained. The drug loading capacity of N, P-CDs was 39.11 %, and the drug delivery system (N, P-CDs-DOX) had low cytotoxicity, sustained release, and pH-targeted properties. The in vitro release of N, P-CDs-DOX belonged to the Weibull model and Fick diffusion, exhibiting the same release model and mechanism with free DOX. The N, P-CDs could deliver DOX successfully, which was demonstrated by the co-collocation of N, P-CDs and DOX in SH-SY5Y cells through single/two-photon imaging. N, P-CDs could potentially be used in drug-targeted delivery and cell imaging.     

Leek-derived codoped carbon dots as efficient fluorescent probes for dichlorvos sensitive detection and cell multicolor imaging

A biomass nitrogen and sulfur codoped carbon dots (NS-Cdots) was prepared by a simple and clean hydrothermal method using leek, and was employed as efficient fluorescent probes for sensitive detection of organophosphorus pesticides (OPs). The leek-derived NS-Cdots emitted blue fluorescence, but was quenched by H₂O₂. Due to acetylcholinesterase/choline oxidase–based cascade enzymatic reaction that produces H₂O₂ and the inhibition effect of OPs on acetylcholinesterase activity, a NS-Cdots-based fluorescence “off-on” method to detect OPs-dichlorvos (DDVP) was developed. More sensitivity and wider linear detection range were achieved from 1.0 × 10⁻⁹ to 1.0 × 10⁻³ M (limit of detection = 5.0 × 10⁻¹⁰ M). This developed method was applied to the detection of DDVP in Chinese cabbage successfully. The average recoveries were in the range of 96.0~104.0% with a relative standard deviation of less than 3.3%. In addition, the NS-Cdots fluorescent probes were also employed successfully in multicolor imaging of living cells, manifesting that the NS-Cdots fluorescent probes have great application potential in agricultural and biomedical fields.

Graphical Abstract

     

Synthesis and application of fluorescent N,S co-doped carbon dots based on on-off-on quenching mode for the collaboration detection of iron ions and ascorbic acid

Nitrogen and sulfur co-doped carbon dots (NS-CDs) were synthesized by one-step solvothermal method using oleic acid as the medium, ʟ-cystine and citric acid monohydrate as precursors. Based on the “on-off-on” fluorescence quenching mode, a novel method was established for determination of both Fe³⁺ and ascorbic acid. The synthesized NS-CDs can be employed as fluorescence chemical sensors for the direct determination of free iron in the aqueous phase and indirect determination of the ascorbic acid contents of vitamin C tablets with linear ranges of 0–10 μM (n = 3) and 0–30 μM (n = 3), and detection limits of 36.6 and 102.5 nM, respectively. These results demonstrate that the proposed method exhibits good selectivity and linearity.     

Thiourea functionalized CdSe/CdS quantum dots as a fluorescent sensor for mercury ion detection

CdSe/CdS quantum dots(QDs) functionalized by thiourea(TU) were synthesized and used as a fluorescent sensor for mercury ion detection.The TU-functionalized QDs were prepared by bonding TU via electrostatic interaction to the core/shell CdSe/CdS QDs after capping with thioglycolic acid(TGA).It was observed that the fluorescence of the functionalized QDs was quenched upon the addition of Hg~(2+).The quantitative detection of Hg~(2+) with this fluorescent sensor could be conducted based on the linear relationship between the extent of quenching and the concentration of Hg~(2+) added in the range of1-300 μg L~(-1).A detection limit of 0.56 μg L~(-1) was achieved.The sensor showed superior selectivity for Hg~(2+) and was successfully applied to the determination of mercury in environmental samples with satisfactory results.     

可视化辅助碳点荧光比色法检测水中痕量汞离子

利用巯基功能化碳点(M-CDs)构建用于检测水中Hg^2+的荧光探针。红外光谱证实M-CDs被巯基(-SH)成功修饰,透射电镜显示M-CDs的平均粒径约为4.88 nm。XRD晶型表征显示M-CDs具有类石墨烯结构。由于银硫醇盐的团聚作用,M-CDs溶液中加入Ag^+可快速形成M-CDs/Ag的棕色沉淀,并引起M-CDs的荧光猝灭。用PBS缓冲液(0.01 mol/L,pH 7.4)溶解沉淀物而形成检测Hg^2+的荧光传感器。在传感体系中加入Hg^2+后,M-CDs荧光明显恢复。在Hg^2+浓度为0.01~0.55 nmol/L范围内,检测体系荧光恢复强度与Hg^2+浓度成良好线性关系,检测限(LOD,3σ/k)4.2 pmol/L。该探针对Hg^2+表现出良好的选择性,同时可以通过可视化辅助判断探针的选择性。该传感器可用于对实际水样的检测,为Hg^2+污染监测提供技术依据。     

氮掺杂荧光碳点用于Co2+的超灵敏检测及细胞成像

首次以金银花和乙二胺为原料,通过水热法合成出性能优异的氮掺杂碳点(N-CDs)。制备的N-CDs具有丰富的官能团、良好的水溶性、低细胞毒性、高的荧光稳定性和良好的生物相容性。在最佳条件下,N-CDs能够高选择性地检出Co²⁺,N-CDs的荧光强度在0.5～3.6 nmol·L^-1范围内被Co²⁺线性猝灭,检出限低至1.38 nmol·L^-1,其猝灭机制属于内滤效应和静态猝灭。该方法也已成功应用于实际样品的精确分析。此外,N-CDs还可用于细胞成像及细胞内Co²⁺传感。     

高稳定性黑米碳点的绿色合成及其细胞成像应用

以绿色廉价的黑米为碳源,采用简单的水热法一步合成了碳点(carbon dots,CDs)。所合成的CDs不仅对pH、NaCl溶液和温度变化不敏感,并且不受多种金属离子的影响,表现出优异的稳定性。同时,CDs在较短波长范围(410~470 nm)表现出激发不依赖的发射行为,在较长波长范围(470~510 nm)又表现出弱激发依赖的发射行为。由于其优异的荧光特性、稳定性和低毒性,我们将其应用于人口腔角质形成细胞(Hok)、宫颈癌细胞(Hela)和骨髓间充质干细胞(MC3T3)的体外成像。     

高稳定性黑米碳点的绿色合成及其细胞成像应用

以绿色廉价的黑米为碳源,采用简单的水热法一步合成了碳点(carbon dots,CDs)。所合成的CDs不仅对pH、NaCl溶液和温度变化不敏感,并且不受多种金属离子的影响,表现出优异的稳定性。同时,CDs在较短波长范围(410~470 nm)表现出激发不依赖的发射行为,在较长波长范围(470~510 nm)又表现出弱激发依赖的发射行为。由于其优异的荧光特性、稳定性和低毒性,我们将其应用于人口腔角质形成细胞(Hok)、宫颈癌细胞(Hela)和骨髓间充质干细胞(MC3T3)的体外成像。     

Red carbon dots as label-free two-photon fluorescent nanoprobes for imaging of formaldehyde in living cells and zebrafishes

Direct,in situ selective detection of intracellular formaldehyde(FA)is of great significance for understanding its function in FA-related diseases.Herein,red carbon dots(RCD)are reported as label-free two-photon fluorescent nanoprobes for detecting and imaging of FA.Upon addition of FA,the-NH2 groups of RCD could quickly and specially react with aldehydes to form Schiff base and then the strong fluorescence of RCD with blue-shift emission is recovery due to the destruction of the hydrogen bond interaction between RCD and water.In addition,the nanoprobes exhibit outsta nding photo stability,rapid response(<1 min),high sensitivity(~9.9μmol/L)and excellent selectivity toward FA over other aldehyde group compounds.Notably,owing to the good cell-membrane permeability and biocompatibility,as well as the large two-photon absorption cross-section,the as-prepared RCD can be used as label-free nanoprobes for selectively detecting and imaging FA in living cells and zebrafishes through one-photon and two-photon excitation.Moreover,RCD could stain the tissue of zebrafishes at depths interval of up to 240μm under two-photon excitation.This research implied that RCD are promising tools for directly and in situ imaging FA in vivo,thus providing critical insights into FA-related pathophysiological processes.     

荧光磁性碳点对卵巢癌细胞的靶向成像与检测

利用高温碳化法制备了荧光磁性钆掺杂碳点(Gd-CDs),其具有明亮的绿色荧光发射,荧光量子产率为32.6%,T1弛豫效率高达 9.02 L·mmol^-1·s^-1。将 Gd-CDs与卵巢癌特异性抗体 Anti-HE4连接,得到的 Anti-HE4/Gd-CDs纳米探针能对 SKOV-3卵巢癌细胞进行特异性的荧光成像和 T1加权成像,其荧光信号强度与 SKOV-3的细胞浓度成正比,对 SKOV-3细胞的检测限为658 cell·mL^-1。以该方法检测了血液样品中的SKOV-3细胞。     

荧光磁性碳点对卵巢癌细胞的靶向成像与检测

利用高温碳化法制备了荧光磁性钆掺杂碳点(Gd-CDs),其具有明亮的绿色荧光发射,荧光量子产率为32.6%,T1弛豫效率高达 9.02 L·mmol^-1·s^-1。将 Gd-CDs与卵巢癌特异性抗体 Anti-HE4连接,得到的 Anti-HE4/Gd-CDs纳米探针能对 SKOV-3卵巢癌细胞进行特异性的荧光成像和 T1加权成像,其荧光信号强度与 SKOV-3的细胞浓度成正比,对 SKOV-3细胞的检测限为658 cell·mL^-1。以该方法检测了血液样品中的SKOV-3细胞。     

Purification of denatured bovine serum albumin coated CdTe quantum dots for sensitive detection of silver(I) ions

CdTe quantum dots (QDs) were synthesized in aqueous solution with 3-mercaptopropionic acid as the stabilizer. Chemically reduced bovine serum albumin (BSA) was used to modify the surface of the QDs. Experimental results showed that the denatured BSA (dBSA) could be effectively conjugated to the surface of CdTe QDs. Column chromatography was used to purify the conjugates and determine the optimal ratio of dBSA to QDs. Further experimental results showed that the conjugation of QDs by dBSA efficiently improved the photoluminescence quantum yield, the chemical stability of QDs and their stability against photobleaching. A facile and sensitive method for determination of silver(I) ions was proposed based on the fluorescence quenching of the dBSA–QDs. Under the optimal conditions, the relative fluorescence intensity decreased linearly with the concentration of the silver(I) ions in the range 0.08–10.66 μM. The detection limit was 0.01 μM. This study provides a new method for the detection of metal cations. Figure In this work, denatured BSA was used to modify the surface of CdTe QDs by a simple and rapid method. And the conjugates of dBSA-QDs were purified by column of Sephadex G-100. After the purification of the conjugates, the sensitivity was greatly increased as silver (I) ions probe.     

Facile synthesis of tomato-based carbon nanodots and its utilization in sensitive detection of tartrazine

Carbon nanodots (CDs) with superior fluorescence performance were obtained by hydrothermal method using tomatoes as raw materials. When the ultraviolet absorption band of tartrazine and the fluorescence spectrum of CDs have complementary overlaps, the fluorescent internal filter effect (IFE) occurred. Furthermore, the degree of quenching of fluorescence intensity of CDs has an excellent linear correlation with tartrazine concentration. And based on this principle, a method for detecting tartrazine was established. As the decrease of fluorescence intensity, tartrazine can be measured in the linear range of 0.1 μM–40 μM. The detection limit is 39 nM, and the recovery rate is 90.7%～114.5%. The established protocol was also effectively employed to assay tartrazine in beverage samples, indicating that it has great potential for food color analysis.