一步微波法合成碳点及其荧光性质研究

近年来合成水溶性的荧光碳点受到越来越多研究者的关注。相对于传统的镉基、硅基量子点和有机染料,碳点毒性低,性质稳定,可以进行化学修饰,并且可以和多种有机,无机,生物分子相容,在众多领域中得到广泛应用。以抗坏血酸为原料经过一步微波反应制备了荧光碳点。并通过X射线衍射(XRD),透射电镜(TEM),紫外-可见吸收光谱,荧光光谱,傅里叶红外光谱(FTIR)进行表征。结果显示以抗坏血酸为原料制备的碳点近似球形,大小均匀,分散性良好,无团聚现象,荧光强度大;表面富含羧基和羟基,发射波长依赖于激发波长,并且具有很强的亲水性。在pH 3～11的范围内具有良好的荧光性能。     

氮掺杂高量子产率荧光碳点的制备及其体外生物成像研究

为获得高量子产率的碳点,以柠檬酸为碳源,苯二胺的3种同分异构体为氮源,采用两步溶剂热法制备了氮掺杂荧光碳点。利用透射电子显微镜(TEM)、紫外-可见吸收光谱(UV-Vis)、荧光光谱、红外光谱(FTIR)、X射线光电子能谱(XPS)对样品进行表征,并考察了碳点的细胞毒性和体外生物成像。实验结果表明:3种高量子产率碳点(Y=52%,60.4%,53.2%)的粒径均一,具有较好的分散性,平均尺寸分别为4.5,5.3,5.2 nm。碳点表面含有羟基、羧基、胺基等基团,在紫外光激发下均能发出明亮的蓝色荧光,并具有稳定的荧光性能。细胞实验表明:3种碳点具有较好的生物相容性,能够快速进入细胞并成功应用于细胞的荧光成像。     

Sulfur doped carbon nitride quantum dots with efficient fluorescent property and their application for bioimaging

Heteroatom doping can drastically alter electronic characteristics of carbon nitride quantum dots, thus resulting in unusual properties and related applications. Herein, we used sulfur as the doping element and investigated the influence of doping on the electronic distribution of carbon nitride and the corresponding fluorescent property. A simple synthetic strategy was applied to prepare sulfur-doped carbon nitride (S-g-C₃N₄) quantum dots through ultrasonic treatment of bulk S-g-C₃N₄. Characterization results demonstrated that the prepared S-g-C₃N₄ quantum dots with an average size of 2.0 nm were successfully prepared. Fluorescent properties indicated that S-g-C₃N₄ quantum dots have an emission peak at 460 nm and cover the emission spectra region up to 550 nm. Furthermore, the fluorescent intensity is greatly increased due to the sonication of bulk S-g-C₃N₄ into quantum dots. As a result, S-g-C₃N₄ quantum dots not only show a blue cell imaging, but have a bright green color. Therefore, S-g-C₃N₄ quantum dot is a promising candidate for bioimaging benefiting from the efficient fluorescent property, good biocompatibility, and low toxicity.     

Comparison of Carbon Dots Prepared in Deep Eutectic Solvent and Water/Deep Eutectic Solvent: Study of Fluorescent Detection of Fe3+ and Cetirizine and their Photocatalytic Antibacterial Activity

In this study, two solvents (deep eutectic and water/deep eutectic solvents) were used for N-doped carbon dots (N-CDs) preparation by microwave irradiation. The solvent can influence surface chemical composition, quantum yield, morphology, and fluorescence of CDs. N-CDs synthesized in water/deep eutectic solvent (DES) had better quantum yield (24.5%) with respect to N-CDs synthesized in deep eutectic solvent (17.4%). These carbon dots were used as a rapid and high sensitive “off–on” fluorescent probe for the determination of Fe³⁺ ion and cetirizine. Morphology and structure of the N-CDs were characterized by FT-IR, UV–Vis, XRD and TEM. Linear range and detection limit for N-CDs synthesis in deep eutectic solvent for cetirizine were 0.08–48 µM and 15 nM, respectively and for N-CDs synthesis in water/deep eutectic solvent were 0.03–50 µM and 10 nM, respectively. Applicability of this nanoprobe was tested in cetirizine determination in serum sample. Antibacterial activities of the two synthesized N-CDs were also investigated using agar disk diffusion method.

     

Versatile Fluorescent Carbon Dots from Citric Acid and Cysteine with Antimicrobial,Anti-biofilm,Antioxidant, and AChE Enzyme Inhibition Capabilities

Nanostructured fluorescent particles derived from natural molecules were prepared by a green synthesis technique employing a microwave method. The precursors citric acid (CA) and cysteine (Cys) were used in the preparation of S- and N-doped Cys carbon dots (Cys CDs). Synthesis was completed in 3 min. The graphitic structure revealed by XRD analysis of Cys CDs dots had good water dispersity, with diameters in the range of 2–20 nm determined by TEM analysis. The isoelectric point of the S, N-doped CDs was pH value for 5.2. The prepared Cys CDs displayed excellent fluorescence intensity with a high quantum yield of 75.6?±?2.1%. Strong antimicrobial capability of Cys CDs was observed with 12.5 mg/mL minimum bactericidal concentration (MBC) against gram-positive and gram-negative bacteria with the highest antimicrobial activity obtained against Staphylococcus aureus. Furthermore, Cys CDs provided total biofilm eradication and inhibition abilities against Pseudomonas aeruginosa at 25 mg/mL concentration. Cys CDs are promising antioxidant materials with 1.3?±?0.1 μmol Trolox equivalent/g antioxidant capacity. Finally, Cys CDs were also shown to inhibit the acetylcholinesterase (AChE) enzyme, which is used in the treatment of Alzheimer’s disease, even at the low concentration of 100 μg/mL.

     

Temperature dependence of photoluminescence of semiconductor quantum dots upon indirect excitation in a SiO2 dielectric matrix

The processes of excitation and relaxation of confined excitons in semiconductor quantum dots upon indirect high-energy excitation have been considered. The temperature behavior of photoluminescence of quantum dots in a SiO₂ dielectric matrix has been described using a model accounting for the process of population of quantum-dot triplet states upon excitation transfer through mobile excitons of the matrix. Analytical expressions that take into account the two-stage and three-stage schemes of relaxation transitions have been obtained. The applicability of these expressions for analyzing fluorescence properties of semiconductor quantum dots has been demonstrated using the example of silicon and carbon nanoparticles in the thin-film SiO₂ matrix. It has been shown that the complex character of the temperature dependences of the photoluminescence upon indirect excitation can be an indication of a multistage relaxation of excited states of the matrix and quantum dots. The model concepts developed in this study allow one to predict the form of temperature dependences of the photoluminescence for different schemes of indirect excitation of quantum dots.

     

基于明胶制备碳量子点及其光学性能的研究

通过水热法采用热解明胶制备出有蓝色荧光的碳量子点,并通过单因素优化实验对制备碳量子点的温度、时间进行优化以选择出制备碳量子点的最佳条件,结果表明在水热反应温度为200 ℃,反应时间为6 h时制备的碳量子点的荧光性能最强。同时,利用透射电子显微镜(TEM)、傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)、Ｘ射线衍射(XRD)、紫外-可见吸收光谱(UV)及荧光光谱(PL)等手段对最佳条件下制备的碳量子点进行测试与表征,结果表明,该方法制备的碳量子点量子产率为39.4%,与不掺杂的碳量子点相比其量子产率相对较高,这可能是因为有N元素的存在使得量子产率有所提高;所制备的碳量子点不仅具有丰富的含氧官能团而且抗光漂白性能良好,形态主要是均匀分散的球形,没有明显的晶格条纹,这与相关文献报道的碳量子点的形态相一致,其在250～300 nm有较弱的吸收,但无明显的特征吸收峰,这可能是由于C=O基团的n-π*跃迁引起的;此外,还讨论了氙灯照射时间、pH、碳量子点浓度、不同类型溶剂及离子强度等因素对碳量子点荧光性能的影响,研究结果表明,氙灯照射时间及离子强度对碳量子点荧光性能几乎无影响,在过酸或过碱的条件下其荧光强度相对较弱,原因可能是在过酸或过碱的条件下发生质子化或非质子化的作用导致其荧光强度减弱;且碳量子点溶液随着其浓度的增加,荧光强度先增加后减小;而对于溶剂类型而言,其在极性溶剂中的荧光强度大于其在非极性溶剂中的荧光强度,说明该方法制备的碳量子点具有良好的水溶性。     

Glycosylated Quantum Dots for the Selective Labelling of <Emphasis Type="Italic">Kluyveromyces bulgaricus</Emphasis> and <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis> Yeast Strains

Highly fluorescent CdTe quantum dots (QDs) stabilized by thioglycolic acid (TGA) were prepared by an aqueous solution approach and used as fluorescent labels in detecting yeast cells. Sugars (mannose, galactose or glucose) were adsorbed on CdTe@TGA QDs and the interaction of these nanoparticles with yeast cells was studied by fluorescence microscopy. Results obtained demonstrate that galactose and mannose functionalized QDs associate respectively with Kluyveromyces bulgaricus and Saccharomyces cerevisiae yeast strains due to saccharide/lectin specific recognition. Glucose-functionalized CdTe QDs, which are not recognized by cell lectins, preferentially localize in the bud scars of S. cerevisiae.     

氮掺杂碳量子点的合成及作为荧光探针对Hg~(2+)的检测

与传统量子点相比,碳量子点作为一种新型的荧光碳纳米材料,由于其良好的生物相容性、易于表面功能化、低毒性等优点受到了广泛关注。采用柠檬酸为碳源,氨水为氮源,热解法制备出水溶性好的氮掺杂碳量子点(NCDs)。透射电镜(TEM)观察NCDs的粒径在3nm左右;X射线光电子能谱(XPS)和傅里叶红外光谱(FIIR)证明NCDs的表面被羧基、氨基、羟基、羰基等官能团功能化,说明NCDs有很好的水溶性。研究还发现Hg~(2+)对NCDs的荧光有良好的猝灭作用,可作为荧光探针检测水中Hg~(2+)含量。在PBS缓冲液中(0.1mol·L~(-1) pH 7.0),NCDs的荧光猝灭率(F/F0)与汞离子浓度在0.001~0.1μmol·L~(-1)之间存在良好的线性关系,检出限为2.1nmol·L~(-1)。该方法灵敏度高、选择性好、方法简便,可应用于Hg~(2+)快速、灵敏的检测。     

One step synthesis of ultra-high quantum yield fluorescent carbon dots for “on-off-on” detection of Hg2+ and biothiols

In this paper, the carbon dots (CDs) with strong blue fluorescence were synthesized through hydrothermal method, which using folic acid, ammonium citrate and ethylenediamine as precursors. The prepared CDs with a high absolute quantum yield of 81.94% and showed excellent stability in high concentration salt solution and different pH conditions. With the addition of Hg²⁺, the signal of CDs was selectively quenched. At the same time, the CDs-Hg²⁺ system could be recovered after the introduction of biothiols. Moreover, the fluorescence of CDs showed a good linear relationship with Hg²⁺ (1–15 µM), and the detection limit as low as 0.08 µM. In addition, the prepared CDs with low toxicity could be used to detect Hg²⁺ in living cells and actual water samples.

     

Detection of Fe3+ and Hg2+ Ions by Using High Fluorescent Carbon Dots Doped With S And N as Fluorescence Probes

In this paper, carbon quantum dots (N-S-CDs) containing sulfur and nitrogen were synthesized using citric acid and thiourea. The average particle size of N-S-CDs is 8 nm. The N-S-CDs surface contains various of functional groups, which has good water solubility. The fluorescence quantum yield of N-S-CDs is as high as 36.8%. N-S-CDs emits strong blue fluorescence in aqueous solution and has good photostability in neutral and alkaline NaCl solution. N-S-CDs has unique selectivity and high sensitivity to Fe³⁺ and Hg²⁺ ions, and the lowest detection limits are 1.4 μM and 0.16 μM, respectively. Under the interference of other metal ions, Fe³⁺ and Hg²⁺ ions can still effectively and stably quench the fluorescence of N-S-CDs. In addition, in the detection of actual samples, N-S-CDs can effectively detect Fe³⁺ and Hg²⁺ ions in tap water and lake water.

     

壳聚糖基聚合物碳点荧光材料合成及其自组装载药应用

荧光碳点具有化学稳定性好、毒性小、可表面功能化等优点,引起了人们极大的兴趣。近年来,由高分子多糖合成的聚合物碳点成为另一研究热点。本文通过水热法合成了一种壳聚糖基荧光聚合物碳点材料（P（CS-g-mPEG-CA）CDs）,并用于载药研究。基于壳聚糖和聚乙二醇既是碳点的碳源也是碳点的钝化试剂,本文选择壳聚糖接枝聚乙二醇单甲醚和柠檬酸衍生物作为聚合物碳点的碳源,以提高聚合碳点的量子产率。另外,聚合物碳点还可以保留聚乙二醇与壳聚糖分子结构,为其在载药方面的应用提供有利条件。采用红外光谱、紫外光谱、X射线衍射、光电子能谱、透射电子显微镜和光致发光光谱对P（CS-g-mPEG-CA）CDs进行了结构表征以及pH值稳定性的测试。结果表明,所合成的P（CS-g-mPEG-CA）CDs具有较高的荧光量子产率（66.81%）、较长的荧光寿命（15.247 ns）、良好的pH稳定性。以阿霉素为模型药物,利用该聚合物碳点进行了负载研究,结果表明,当聚乙二醇单甲醚取代度为11.9%时,聚合物碳点的载药量最高为51.3%,最大药物释放率为28.7%,此外,药物的装载和释放可以通过mPEG的接枝率进行控制。采用MTT法评价了聚合物的碳点对鼻咽癌细胞（CNE-2）的毒性作用。研究表明,空白聚合物碳点无明显细胞毒性,CNE-2细胞存活率随着载药胶束的增加而降低,说明载药胶束对CNE-2细胞有较强的抑制作用。可见该P（CS-g-mPEG-CA）CDs在荧光标记、药物递送、荧光示踪系统和控制释放方面,具有一定的应用前景。     

壳聚糖碳点的水热法制备及其对金属离子的选择性研究

以壳聚糖为碳源通过水热法合成碳点,对影响碳点荧光强度的水热温度、水热时间和壳聚糖质量分数进行考察。通过紫外分光光度计、荧光分光光度计、原子力显微、Fourier红外光谱仪、X-ray光电子能谱、X射线衍射仪对壳聚糖碳点的光学性质、化学结构、晶体结构、形貌结构等进行表征分析。结果表明,在水热温度200℃、水热时间9 h、壳聚糖质量分数2%的条件下制备得到的壳聚糖碳点量子产率为32.86%。碳点呈现出主要尺寸为3～10 nm的球形颗粒状,且在波长335 nm激发下,发射峰位于410 nm(蓝)。对金属离子的选择性研究分析表明,Fe~(3+)对碳点溶液的荧光猝灭效应最显著,说明碳点对Fe~(3+)具有较好敏感性和高选择性,且荧光猝灭效率对Fe~(3+)浓度在0～100μmol/L范围内呈现线性响应,因此有望将碳点作为荧光探针应用于Fe~(3+)的检测表征。     

Imaging of Bacterial and Fungal Cells Using Fluorescent Carbon Dots Prepared from <Emphasis Type="Italic">Carica papaya</Emphasis> Juice

In this paper, we have described a simple hydrothermal method for preparation of fluorescent carbon dots (C-dots) using Carica papaya juice as a precursor. The synthesized C-dots show emission peak at 461 nm with a quantum yield of 7.0 %. The biocompatible nature of C-dots was confirmed by a cytotoxicity assay on E. coli. The C-dots were used as fluorescent probes for imaging of bacterial (Bacillus subtilis) and fungal (Aspergillus aculeatus) cells and emitted green and red colors under different excitation wavelengths, which indicates that the C-dots can be used as a promising material for cell imaging.     

A New Dual-peak Fluorescent Probe for Water Content Detection Made From Taxus

In this paper, the leaves of Taxus were used as the sole carbon source, and two kinds of carbon dots blue and red, with different properties, were synthesized by the hydrothermal method under different conditions. The red carbon dots were quenched in the water, and the blue carbon dots had stable fluorescence properties in water environment. The bimodal fluorescence probe formed by mixing could accurately and stably measure the water content in ethanol, which was in the range of 82.5%-100%, is highly correlated with the fluorescence intensity ratio (I₄₈₁/I₆₇₈) of mixed carbon dots under 390 nm excitation light, with R²?=?0.995 and the detection limit as low as 0.31%. The experimental materials are environmentally friendly, low in cost, and simple to operate, as well as the water content measured by proportional fluorescence has high accuracy, which provides a new method for measuring moisture in ethanol.

     

适配体传感法快速测定啤酒中赭曲霉毒素A

应用自组装方式,构建了金纳米粒子/核酸适体/氨基碳量子点荧光传感赭曲霉毒素A高灵敏检测方法。在pH 3.0酒石酸-HCl缓冲溶液中,巯基修饰的赭曲霉毒素A核酸适体在金纳米粒子表面自组装,形成金纳米粒子/核酸适体复合物,再在pH 7.0的磷酸盐缓冲溶液中,氨基碳量子点在金纳米粒子/核酸适体复合物上自组装,形成金纳米粒子/核酸适体/氨基碳量子点复合物荧光传感检测体系。金纳米粒子的摩尔吸光系数大、能带宽使其具有强烈的荧光猝灭功能,氨基碳量子点形成金纳米粒子/核酸适体/氨基碳量子点后发生荧光猝灭, 此时体系的荧光为背景荧光,其强度记为F₀;由于金纳米粒子/核酸适体/氨基碳量子点复合物荧光传感检测体系中核酸适体对赭曲霉毒素A具有特异性识别与结合功能,向金纳米粒子/核酸适体/氨基碳量子点复合物荧光传感检测体系溶液中加入赭曲霉毒素A后,赭曲霉毒素A则与复合物中核酸适体立即发生特异性结合并释放出氨基碳量子点,体系荧光恢复,其荧光强度记为F。依据体系荧光强度的变化(F-F₀)与赭曲霉毒素A浓度之间的关系,建立赭曲霉毒素A核酸适体荧光传感检测方法。研究了金纳米粒子和核酸适体摩尔比、孵化时间、pH等因素对传感器性能的影响,确定了最优条件为金纳米粒子∶核酸适体t为1∶190、孵化时间为6 min、pH 7.0时;在最优条件下,赭曲霉毒素A浓度在0.005～1.00 ng·mL-1范围与体系荧光强度变化呈良好线性关系,线性回归方程为：F-F₀=6.499+211.6c(c为赭曲霉毒素A的浓度,单位：ng·mL-1),相关系数r为0.995 5,按3倍标准差与工作曲线的斜率的比值(3σ/k)计算,得检测限为3 pg·mL-1。在实际样品中的回收率在93.3%～108.9%,相对标准偏差小于5%,能满足啤酒样品中赭曲霉毒素A快速检测要求。对13个市售啤酒样品进行检测,其中6个样品检出赭曲霉毒素A,污染率为46.15%。受污染样品的赭曲霉毒素A含量在0.008～0.63 ng·mL-1范围。该荧光传感法检测赭曲霉毒素A具有灵敏性好、特异性高、常见真菌毒素无干扰、方法简单、快速,便于大众化推广应用的优点。     

Dual-Color Quantum Dot–Encoded Nanoprobe for DNA Assays and Cell Imaging

In this article, a novel dual-color quantum dot–encoded fluorescent nanoprobe was prepared by the reverse microemulsion method and layer-by-layer assembly method. First, red fluorescence–emitting CdTe quantum dots were encapsulated in silica nanoparticles by the reverse microemulsion method. Yellow fluorescence–emitting quantum dots were deposited on the surface of silica nanoparticles to form a dual-color quantum dot@silica beads/quantum dot nanoprobe. Then capture DNA was linked to a QSQ nanoprobe via covalent bonding. We utilized the quantum dot@silica beads/quantum dot nanoprobe to capture and detect the mutant BRAF DNA sequence through the competitive immunoassay method. The resulting quantum dot@silica beads/quantum dot nanoprobe-capture DNA conjugates showed sequence-specific hybridization with target DNA. Furthermore, a multispectral imaging system was utilized to distinguish the quantum dot optical code in the quantum dot@silica beads/quantum dot nanoprobe. The quantum dot@silica beads/quantum dot nanoprobe was used in human osteoblast-like HepG2 cell imaging. The proposed quantum dot@silica beads/quantum dot nanoprobe and decoding analysis method could be used for targeting imaging, biological assays, and early detection of cancer.     

Rapid Visualization of Latent Fingerprints with Color‐Tunable Solid Fluorescent Carbon Dots

Latent fingerprints (LFPs) imaging is the most important approach to identify individuals, and there is a persisting need for the development of simple, rapid, accurate, and universal LFPs recognition methods. The nitrogen‐ and sulfur‐doped solid fluorescent carbon dots (N,S‐SFCD) are synthesized with a simple microwave‐assisted method by using l ‐glutathione and citric acid as precursors. The obtained N,S‐SFCD has a uniform size from 2 to 7 nm with quantum yield over 48%. The presence of heteroatoms and functional groups on the surface endows the N,S‐SFCD with good dispersibility and strong fluorescence emission, and overcomes the typical aggregation‐induced fluorescence quenching, thus allowing the N,S‐SFCD to be used in both solution and their powder forms. Furthermore, the color‐tunable fluorescence, electrostatic interaction with fingerprints, and good stability enable N, S‐SFCD to act as an excellent chemosensor for fluorescence imaging. LFPs are detected with high resolution through powder method, and their second‐ and third‐level substructures are clearly identified. The method is validated for LFPs visualization on various substrates, and aged (7, 15, and 30 d) LFPs can also be successfully stained with N,S‐SFCD. The results demonstrate that the N,S‐SFCD as a developer has great potential in LFPs imaging for forensic investigations.     

Ultrasensitive fluorescent probe for copper ion based on cadmium selenide/cadmium sulfide quantum dots capped with dimercaprol

A new ultrasensitive copper ion fluorescent probe based on cadmium selenide/cadmium sulfide quantum dots capped with dimercaprol is described. Dimercaprol was bonded to the quantum dots through a surface ligand exchange to form dimercaprol-capped quantum dots whose fluorescence could be quenched by the coordination of dimercaprol on quantum dots’ surface with copper ion. The fluorescent probe based on dimercaprol-capped quantum dots showed a very good linear response range to copper ion from 0.1 to 50?µg?L^?1 with the detection limit of 0.087?µg?L^?1. The proposed method exhibited excellent sensitivity and selectivity due to the specific and strong affinity of dimercaprol with copper ion and the unique photoluminescence properties of quantum dots. The possible quenching mechanism was discussed and the probe was successfully applied to the determination of ultratrace copper in real samples.     

Novel Glutathione-Capped Cadmium Telluride Quantum Dots-Based Off–On Fluorescence Sensor for Highly Sensitive and Selective Monitoring of Histidine

A novel glutathione-capped cadmium telluride quantum dots-based fluorescence “off–on” sensor was designed and applied for highly sensitive and selective monitoring of histidine in aqueous solution. To provide a platform for histidine detection, manganese ion was first employed as an effective quencher to decrease the fluorescence of glutathione-capped cadmium telluride quantum dots because of the binding of manganese ion to glutathione on the surface of quantum dots and the electron transfer from the photoexcited glutathione-capped cadmium telluride quantum dots to manganese ion. Due to its high binding affinity with manganese ion, histidine can make the manganese ion to be dissociated from the surface of glutathione-capped cadmium telluride quantum dots to form more stable complex with histidine in solution, and set free the luminescent glutathione-capped cadmium telluride quantum dots, thereby recovering the fluorescence of glutathione-capped cadmium telluride quantum dots. Experimental results showed that the recovered fluorescence intensity was directly proportional to the concentration of histidine in the range of 0.006 to 465.0 µg mL^?1 with a correlation coefficient (R) of 0.9977, and the detection limit (3σ/K) was 1.82 ng mL^?1. Relevant experiments also revealed that the fluorescence sensor gives excellent selectivity for histidine over other common amino acids. To further investigate perfect analysis performance, this sensor was utilized to determine histidine in synthetic samples with satisfactory results.