量子点室温磷光探针检测生物体液中的头孢哌酮钠舒巴坦钠

以水相合成的3-巯基丙酸包覆的Mn掺杂ZnS量子点(MPA-Mn/ZnS QDs)作为室温磷光探针, 基于头孢哌酮钠舒巴坦钠(CPZ-SBT)作为一种电子受体, 可通过电子转移有效猝灭Mn/ZnS QDs的室温磷光效应, 构建了一种测定痕量CPZ-SBT的方法. 当CPZ-SBT浓度为0.7~84 μg/L时, 其与MPA-Mn/ZnS QDs的磷光强度之间呈良好线性关系, 相关系数为0.99, 该方法的检出限为0.14 μg/L.     

基于Mn掺杂ZnS量子点室温磷光法检测盐酸巴马汀

本文以3-巯基丙酸(3-Mercaptopropionic Acid,MPA)为稳定剂,采用水相合成法制备了Mn掺杂ZnS量子点(Mn∶ZnS QDs),基于Mn∶ZnS QDs的室温磷光性质,盐酸巴马汀(Palmatine Hydrochloride,PaH)可与Mn∶ZnS QDs发生静电作用,使得Mn∶ZnS QDs发生室温磷光猝灭效应,从而发展了一种高效、快速检测人体体液中痕量PaH的新方法。实验结果表明,当PaH的浓度在0.75~30μmol/L范围时,其浓度与室温磷光猝灭强度(ΔIRTP)呈良好的线性关系,相关系数为0.996,检出限为0.35μmol/L,加标回收率为94.0%~103.3%。     

基于Mn掺杂ZnS量子点室温磷光法测定水样中百草枯

利用水相合成法制备了3-巯基丙酸(3-Mercaptopropionic Acid,MPA)包裹的Mn掺杂ZnS量子点(Quantum Dots,QDs),基于该量子点的室温磷光性质,构建了一种快速、灵敏检测水样中百草枯(Paraquat,PQ)含量的新方法。方法无需添加任何除氧剂和诱导剂等复杂的预处理过程。在pH=7.4的磷酸盐缓冲溶液中,PQ通过静电作用可以猝灭Mn掺杂ZnS QDs在波长590nm处的磷光,且在一定范围内PQ的浓度与磷光猝灭强度(P0/P)呈良好的线性关系,线性范围为2.5~50μg/L,相关系数为0.994,方法检出限为0.769μg/L。该方法适用于不同水样中百草枯的痕量检测。     

基于室温磷光量子点/硼酸基联吡啶盐纳米复合材料检测果糖

以Mn掺杂的ZnS(Mn-ZnS)室温磷光(RTP)量子点的磷光为信号,以2-溴甲基苯硼酸与4,4ˊ-联吡啶为原料合成的硼酸基联吡啶盐(BBV)为受体,带负电的量子点与带正电BBV通过静电作用形成Mn-ZnS/BBV纳米复合材料,Mn-ZnS量子点磷光猝灭,加入果糖,BBV与果糖形成阴离子硼酸酯,降低了对量子点猝灭效率,RTP恢复.考察了时间、pH值对Mn掺杂的ZnS QDs/BBV纳米复合材料磷光强度的影响,在最优条件下,此传感器检测果糖的线性范围为0.05~1.00 mmol/L,检出限为0.01 mmol/L,相关系数r为0.99.本磷光分析法简便快速、灵敏度高,有望应用于食品、医药行业中果糖含量的检测分析.     

基于Mn掺杂ZnS量子点的室温磷光猝灭法测定H2O2

以N-乙酰基-L-半胱氨酸为稳定剂,合成了具有独特光学性质的水溶性Mn掺杂ZnS量子点(QDs)。该量子点在室温不除氧的条件下即可发射较强的磷光信号,最大发射波长位于592nm处。在pH=7.0的磷酸盐缓冲溶液中,H2O2对量子点有显著的磷光猝灭作用,且在一定的范围内H2O2的浓度与磷光猝灭值(P0/P)呈现良好的线性关系,以此建立了测定H2O2的新方法。在最佳的实验条件下,该方法的检出限为1.0×10-6 mol/L,线性范围为1.0×10-5～2.5×10-2 mol/L,相关系数为0.9978。通过测定猝灭过程的时间分辨磷光光谱,推断猝灭机理为动态猝灭。     

胸腺嘧啶修饰的Mn:ZnS量子点作为室温磷光传感器用于Hg~(2+)的检测

采用胸腺嘧啶修饰的Mn:ZnS量子点作为室温磷光传感器检测Hg~(2+)。量子点溶液在加入Hg~(2+)后,磷光强度迅速下降并在15 min内达到稳定。Hg~(2+)对量子点的磷光猝灭方式是动态猝灭与静态猝灭相结合,Hg~(2+)与量子点在激发态相互作用导致量子点动态猝灭,并且在静态猝灭过程中,Hg~(2+)和胸腺嘧啶在基态相互作用形成T-Hg~(2+)-T的发夹结构产生了不发光的络合物。在最优反应条件下,量子点的磷光强度随Hg~(2+)的浓度在2～18μmol/L范围内呈良好的线性关系(R~2=0.9992)。     

CdTe/CdS量子点荧光探针测定痕量锑

以巯基乙酸为稳定剂,在水溶液中合成了CdTe/CdS量子点(QDs),并基于QDs与锑混合后发生荧光猝灭作用,建立了以CdTe/CdS QDs作为荧光探针检测微量锑的新方法。研究表明,在pH值为4.80的柠檬酸-柠檬酸钠中,反应时间为10min时,锑浓度在0.03~2.50μg/mL范围与CdTe/CdS QDs的荧光猝灭程度呈良好的线性关系,相关系数为0.9969,检出限为2.60×10-3μg/mL。     

ZnSe量子点作为荧光探针测定微量Ag~+

以谷胱甘肽为稳定剂,在水相中合成了ZnSe量子点(QDs)。基于Ag+对ZnSe QDs的荧光猝灭作用,建立了以QDs作为荧光探针测定微量Ag+的新方法。结果表明:在优化条件下,Ag+的浓度在7.85~157.01μg·L-1范围内和F0/F有良好的线性关系,相关系数r为0.9989,检测限为0.12μg·L-1。由Stern-Volmer方程获得了反应的猝灭常数和双分子猝灭速率常数,由双倒数方程获得了Ag+与ZnSe QDs相互作用的结合常数、结合位点数,并判断出其作用机理为静态猝灭。根据热力学方程计算热力学参数,结果表明Ag+与ZnSe QDs的相互作用为自发过程,主要为静电作用力。     

基于牛血清白蛋白修饰的金纳米簇的荧光光谱法快速测定维生素B12药片中Co2+的含量

采用化学还原法合成牛血清白蛋白(BSA)修饰的金纳米簇(AuNCs),基于Co²⁺对AuNCs的荧光猝灭作用,提出了一种快速、简便、灵敏测定Co²⁺含量的方法。以柠檬酸为还原剂、BSA为保护剂、氯金酸为原料合成AuNCs。分取0.20 mL AuNCs溶液,加入0.6 mL pH 9.0碳酸钠-碳酸氢钠缓冲溶液,用水稀释至1.00 mL,在发射波长630 nm处测量上述体系(空白体系)的荧光强度F₀。取10片维生素B₁₂药片,研磨后,分取0.127 0 g,用水溶解并稀释至100 mL,分取10μL于空白体系中,混匀后静置反应5 min,测量荧光强度F,利用荧光强度的差值ΔF(ΔF=F₀-F)进行定量。结果显示：合成的AuNCs分布均匀,Co²⁺对AuNCs体系有荧光猝灭作用,属于动态猝灭过程。添加10倍Co²⁺浓度的干扰离子,Fe²⁺、Pb²⁺、Al³⁺、Zn     

蛋白胨碳量子点“关-开”型荧光探针检测食品中草酸

采用水热法,使用碳源蛋白胨制得荧光碳量子点（CQDs）。使用透射电镜、X射线光电子能谱（XPS）和红外光谱对其进行了表征。该CQDs溶液的荧光能够被Cu²⁺猝灭,草酸能够使CQDs的荧光恢复。据此建立了碳量子点“关-开”型荧光探针测定草酸的新方法。荧光恢复程度与草酸浓度在8～65μg/mL范围内呈线性关系,检出限为1.8μg/mL。通过紫外光谱、荧光光谱和荧光寿命探究了CQDs对草酸的荧光响应机理。Cu²⁺能够对CQDs的荧光产生动态猝灭,C₂O₄^2-与Cu²⁺结合,减少了溶液中游离的Cu²⁺,导致CQDs的荧光恢复。该方法可用于实际样品西红柿和圣女果中草酸的分析检测。     

高灵敏CdTe量子点探针的构建及与金属离子的作用

采用变性的牛血清白蛋白(dBSA)对水相合成的CdTe量子点进行修饰, 构建了高灵敏金属离子探针, 研究了其对重金属离子的检测性能并对机理进行了探讨. 通过优化反应条件, 合成了具有高量子产率的以巯基乙酸为稳定剂的水溶性CdTe量子点, 并采用变性的牛血清白蛋白分别对不同粒径的CdTe量子点进行修饰, 确定变性的牛血清白蛋白与不同粒径量子点之间的最佳比例. 在纯化变性的牛血清白蛋白修饰的量子点(dBSA-QDs)的基础上, 研究了该量子点与不同金属离子的作用. 结果表明, 量子点经修饰后, 其量子产率、 抗光漂白性及稳定性得到显著提高; 而且dBSA-QDs的荧光可被重金属离子有效猝灭, 与巯基乙酸稳定的量子点(TGA-QDs)相比, 检测灵敏度显著提高.     

Doped zinc sulfide quantum dots based phosphorescence turn-off/on probe for detecting histidine in biological fluid

We report a turn-on phosphorescence probe for detection of histidine based on Co²⁺-adsorbed N-acetyl-l-cysteine (NAC) capped Mn: ZnS quantum dots (QDs) which is directly synthesized by the hydrothermal method. The phosphorescence of NAC-Mn: ZnS QDs is effectively quenched by Co²⁺ attributing to the adsorption of Co²⁺ onto the surface of QDs with a concomitant in suppressing the recombination process of hole and electron of QDs. The phosphorescence of Co²⁺-adsorbed NAC-Mn: ZnS QDs can be recovered by binding of Co²⁺ with histidine. The quenching and regeneration of the phosphorescence of NAC-Mn: ZnS QDs have been studied in detail. The as-prepared QDs-based probe is applied to determine histidine with a linear range of 1.25–30 μM and a detection limit of 0.74 μM. The relative standard deviation for eleven repeat detections of 20 μM histidine is 0.65%. Co²⁺-adsorbed NAC-Mn: ZnS QDs show high sensitivity and good selectivity to histidine over other amino acids, metal ions and co-existing substances. The proposed QDs probe has been successfully applied to determination of histidine in human urine samples with good recoveries of 98.5–103%.     

A Convenient “Turn On-off” Phosphorescent Nanosensor for Detection of Biotin Based on Quantum Dots/CTAB

A switchable room-temperature phosphorescence(RTP) nanosensor based on an MPA-capped Mn-doped ZnS QDs/CTAB composite system(MPA=3-mercaptopropionic acid; CTAB=cetyltrimethyl ammonium bromide; QDs=quantum dots) was established for the detection of biotin. The phosphorescence intensity of QDs/CTAB could be regularly quenched with the increase of biotin. Under optimal conditions, this method yielded two linear ranges of 2-20 μg/L and 20-140 μg/L with respective correlation coefficients of 0.993 and 0.990, as well as a detection limit of 0.93 μg/L. Therefore, the analytical potential of the proposed nanosensor was evaluated by detecting biotin in urine and biotin tablets. This approach yielded satisfactory results because of the effective elimination of background fluorescence and light scattering from the sample matrix. This approach provides a practical method for biotin detection.     

ZnS:Mn/ZnS量子点在DNA定量分析中的应用

以巯基乙酸为稳定剂,采用成核掺杂的方法在水溶液中一步制备得到具有核壳结构的ZnS:Mn/ZnS量子点.研究了荧光、室温磷光产生的机理.基于DNA对量子点发光的增强效应,以ZnS:Mn/ZnS量子点作为标记探针建立了测定DNA的荧光、室温磷光的分析方法.考察了量子点浓度、EDC/NHS用量和反应时间等条件对DNA测定的影...     

Ascorbic Acid Induced Enhancement of Room Temperature Phosphorescence of Sodium Tripolyphosphate‐Capped Mn‐Doped ZnS Quantum Dots: Mechanism and Bioprobe Applications

Although quantum dot (QD)‐based room temperature phosphorescence (RTP) probes are promising for practical applications in complex matrixes such as environmental, food and biological samples, current QD‐based‐RTP probes are not only quite limited but also exclusively based on the RTP quenching mechanism. Here we report an ascorbic acid (AA) induced phosphorescence enhancement of sodium tripolyphosphate‐capped Mn‐doped ZnS QDs, and its application for turn‐on RTP detection. The chelating ability allows AA to extract the Mn and Zn from the surface of the QDs and to generate more holes which are subsequently trapped by Mn²⁺, while the reducing property permits AA to reduce Mn³⁺ to Mn²⁺ in the excited state, thereby enhancing the excitation and orange emission of the QDs. The enhanced RTP intensity of the QDs increases linearly with the concentration of AA in the range of 0.05–0.8 μM . Thus, a QD‐based RTP probe for AA is developed. The proposed QD‐based turn‐on RTP probe avoids tedious sample pretreatment, and offers good sensitivity and selectivity for AA in the presence of the main relevant metal ions and other molecules in biological fluids. The limit of detection (3s) of the developed method is 9 nM AA, and the relative standard deviation is 4.8 % for 11 replicate detections of 0.1 μM AA. The developed method is successfully applied to the analysis of real samples of human urine and plasma for AA with quantitative recoveries from 96 to 105 %.     

镉(Ⅱ)-半胱氨酸配合物对CdS量子点的荧光增强作用及其在离子检测中的应用

合成了弱配体柠檬酸三钠修饰的CdS量子点(Cit-CdS QDs), 透射电子显微镜表征结果表明, Cit-CdS QDs的粒径分布均匀(4~6 nm), 分散性好。 研究了金属离子(银(Ⅰ)离子、镉(Ⅱ)离子)、巯基化合物(巯基乙酸、半胱氨酸)以及金属离子(银(Ⅰ)离子、镉(Ⅱ)离子)与巯基化合物形成的配合物对Cit-CdS QDs荧光的影响。 发现金属离子(银离子、镉离子)与巯基化合物(巯基乙酸、半胱氨酸)形成的水溶性配合物可以显著增强Cit-CdS QDs的荧光, 配合物对Cit-CdS QDs的增强程度比单独的金属离子或巯基化合物均要高, 而且配合物修饰的CdS QDs对铜(Ⅱ)离子的响应要高于单独用金属离子或巯基化合物修饰的量子点。 建立了铜(Ⅱ)离子高灵敏度荧光检测方法, 该方法检测范围宽(1.0×10^-8~1.0×10^-6 mol/L), 检测限低(1.0×10^-9 mol/L)且具有很好的选择性, 拓展了配合物作为量子点修饰剂的应用。     

On-off-on luminescent pyrophosphate probe based on the use of Mn-doped ZnS quantum dots and using Eu(III) as a mediator

A selective phosphorescent on-off-on probe with long decay lifetime has been designed for the detection of pyrophosphate ions (PPi). The detection scheme is based on the use of europium(III)-modulated Mn(II)-doped ZnS quantum dots capped with N-acetyl-L-cysteine. Both the aggregation of quantum dots and electron transfer induced by Eu(III) ions cause phosphorescence to be quenched (“off” state). Phosphorescence is, however, restored on addition of PPi to the system (“on” state). The effect is attributed to the removal of Eu(III) from the carboxy groups on the surface of the quantum dots owing to the stronger interaction between PPi and Eu(III). A linear relationship exists between phosphorescence intensity (best measured at excitation/emission wavelengths of 316/594 nm) and PPi concentration in the 400 nM to 6000 nM with a detection limit of 145 nM. An additional attractive feature is provided by the long-lived phosphorescence (1920 μs) of the quantum dots. It can be used to eliminate interference by short-lived fluorescence in biological samples by performing time resolved measurements. The probe was applied to the determination of PPi in spiked in urine samples and gave recoveries in the range from 98 to 105% with RSDs of <2.0%.

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Graphical abstract Schematic of a long-lived phosphorescent on-off-on probe for the sensitive and selective detection of pyrophosphate ions (PPi). It is based on the use of Eu(III)-modulated Mn(II)-doped ZnS quantum dots (QDs). Phosphorescence is quenched of QDs after the addition of Eu³⁺but restored after the addition of PPi.