Ratiometric

比率法
  • 文章类型: Journal Article
    肼(N2H4)是化工生产中广泛使用的重要化工原料。然而,由于它的波动性,水溶性,和高毒性,N2H4的气体形式和水溶液都会造成严重的污染,从而对植物产生不利影响,从而造成重大的环境风险。微生物,和人类健康。因此,准确检测环境中的N2H4对于维护公众健康至关重要。在这项研究中,我们合成了一种基于咔唑和半鸟嘌呤基团的比例荧光探针(BCaz-Cy2)。该探针显示出简单的合成程序,快速响应时间,高灵敏度和选择性以及显着的检测信号。它能够有效检测各种基质中的N2H4,例如水,食物,土壤和植物样品,从而显着扩大N2H4探针的应用范围。
    Hydrazine (N2H4) is a crucial chemical raw material extensively utilized in chemical production. However, due to its volatility, water solubility, and high toxicity, both the gaseous form and aqueous solution of N2H4 pose significant environmental risks by causing severe pollution that can adversely impact plants, microorganisms, and human health. Therefore, accurate detection of N2H4 in the environment is imperative for safeguarding public health. In this study, we synthesized a ratiometric fluorescent probe (BCaz-Cy2) based on Carbazole and Hemicyanine groups. This probe exhibits simple synthesis procedure, rapid response time, high sensitivity and selectivity as well as remarkable detection signals. It enables effective detection of N2H4 in various matrices such as water, food, soil and plant samples thereby significantly expanding the scope of applications for N2H4 probes.
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  • 文章类型: Journal Article
    开发用于快速检测水样中乙酰丙酮(AP)的高性能传感器是必要的,因为它释放到环境中可能会导致许多人类健康和环境问题。在这里,我们首先通过顺序增长策略将HOF与ZIF-8集成来设计混合动力。通过在ZIF-8和HOF中分别引入发蓝光的SiQD以及发绿光和红光的Tb3+和Eu3+,所得ZIF-8@SiQDs@HOF@Eu3+@Tb3+在484、545和620nm处包含三个发射峰,所有这些都可以用作低浓度AP的关闭响应峰,检出限为0.79ppm。然而,在高浓度的环境中,观察到484nm的开启信号。于是,三元发射的比率荧光强度在不同浓度范围内变化,伴随着从红色到鲑鱼到李子到紫色到最后的蓝色的荧光颜色演变。此外,制作了便携式传感膜,用于快速报警,在复杂的环境中敏感和视觉的AP测定。因此,这种具有宽颜色变化和强抗干扰性的三发射传感器可以促进进一步的研究,以提高选择性,多模态荧光检测的灵敏度和固有的自校正以及传感操作的简便性。
    The development of high-performance sensors for rapidly detecting acetylacetone (AP) in water samples is necessary because its release into the environment can result in many vital problems for human health and environment. Herein, we first designed a hybrid by integrating HOF with ZIF-8 through a sequential growth strategy. By separately introducing blue-emitting SiQDs and green- and red-emitting Tb3+ and Eu3+ into ZIF-8 and HOF, the resultant ZIF-8@SiQDs@HOF@Eu3+@Tb3+ comprised three emission peaks at 484, 545 and 620 nm, all of which could be employed as switch-off responsive peaks to low concentrations of AP with a detection limit of 0.79 ppm. However, in environments with high concentrations of AP, a turn-on signal at 484 nm was observed. Thereupon, the ratiometric fluorescence intensity of the ternary emission varied within different concentration ranges, accompanied by the fluorescence color evolution from red to salmon to plum to purple to final blue. Moreover, a portable sensing film was fabricated for rapid warning, sensitive and visual determination of AP in complicated environments. Therefore, this triple-emission sensor with wide color variations and strong anti-interference advantages could promote further research to improve the selectivity, sensitivity and inherent self-correction of multimodal fluorescence detection and the ease of sensing operation.
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  • 文章类型: Journal Article
    背景:由于氰化物(CN-)对环境和人类健康具有重大危害,监测水和食物样本中的氰化物含量至关重要。此外,CN-的实时可视化可以进一步了解其在活细胞中的关键生理和毒理学作用。基于小型有机探针的荧光法是检测CN-的有效方法。在这种方法中,一种三苯胺-xhantane缀合物用于检测许多样品,如污水,土壤,发芽的马铃薯,杏子,和活细胞。
    结果:我们报告了一种基于三苯胺-xhantane衍生物的新型比率近红外荧光探针,用于许多样品中的CN传感。该探针仅对一系列分析物中的CN-离子显示出高选择性。向探针的二氰基乙烯基部分添加氰化物会破坏π-缀合,然后中断内部电荷转移。因此,探针的发射峰从655到495nm高色移动。发射强度(I495)与氰化物水平呈线性相关,检测限为0.036μM。与许多探头相比,该探头具有许多优点,如近红外荧光,比率响应,低细胞毒性(85.0%的细胞活力高达50.0μM的探针),良好的膜渗透性,快速响应时间(4.0分钟),高选择性,良好的光稳定性,和抗干扰能力。
    结论:尽管文献中已经报道了各种探针,使用三苯胺-xhantane单元作为CN-探针还有待探索。该探针可以检测污水等许多样品中的痕量氰化物,土壤,发芽的土豆,和杏子。此外,它已成功用于活细胞中氰化物的比率荧光生物成像。
    BACKGROUND: As cyanide (CN-) is a significant hazard to the environment and human health, it is essential to monitor cyanide levels in water and food samples. Moreover, real-time visualization of CN-could provide an additional understanding of its critical physiological and toxicological roles in living cells. The fluorescence approach based on small organic probes is an effective way for the detection of CN-. In this approach, a triphenylamine-xhantane conjugate was applied to detect in many samples such as sewage water, soil, sprouted potato, apricot seed, and living cells.
    RESULTS: We report a new ratiometric near-infrared fluorescent probe based on a triphenylamine-xhantane derivative for CN-sensing in many samples. The probe displays high selectivity for only CN- ions among a series of analytes. The addition of cyanide to the dicyanovinyl moiety of the probe disrupts π-conjugation followed by the interruption of internal charge transfer. Consequently, the emission peak of the probe shifts hypsochromically from 655 to 495 nm. There is a linear correlation between the emission intensity (I495) and cyanide level, with a detection limit of 0.036 μM. The probe has many advantages over many probes, such as NIR fluorescence, ratiometric response, low cytotoxicity (85.0 % cell viability up to 50.0 μM of the probe), good membrane permeability, fast response time (4.0 min), high selectivity, good photostability, and anti-interference capability.
    CONCLUSIONS: Although various probes have been reported in the literature, the use of triphenylamine-xhantane unit as CN- probe has yet to be explored. The probe can detect trace levels of cyanide in many samples such as sewage water, soil, sprouted potatoes, and apricot seeds. Furthermore, it is successfully utilized for the ratiometric fluorescent bioimaging of cyanide in living cells.
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  • 文章类型: Journal Article
    Buprofezin(BUP)是一种广泛用于农业控制半翅目害虫的昆虫生长调节剂,尤其是甜瓜蚜虫,山雀,由于其效率和低毒性。虽然得到了中国政府的批准,其在食品中的最大残留限量(MRL)受到严格管制,和用于检测BUP的常规技术具有若干限制。我们的研究报告了使用超分子荧光探针DP@ALB成功检测BUP,以查尔酮基荧光染料DP和白蛋白为宿主构建。该探头具有成本低等优点,具有高荧光颜色变化的视觉信号输出,快速反应,和高灵敏度。此外,便携式测试条可以方便地进行现场BUP检测,并简化了实际样品的现场监测。该研究实现了葡萄果实BUP的精确定性和定量分析,地下水和土壤,回收率令人满意。Further,证明了传感器在体外检测L929活细胞中BUP的生物学适用性。这一研究突破了传统分析方法的局限性,为食品和环境监测和农药残留检测提供了有效和可靠的方法。
    Buprofezin (BUP) is an insect growth regulator widely used in agriculture to control hemipteran pests, particularly the melon aphid, Aphis gossypii, due to its efficiency and low toxicity. Although approved by the Chinese government, its maximum residue limit (MRL) in food is strictly regulated, and conventional techniques for detecting BUP have several limitations. Our study reports successful BUP detection using a supramolecular fluorescent probe DP@ALB, constructed with chalcone-based fluorescent dye DP and albumin as the host. The probe offers advantages such as low cost, visual signal output with high fluorescence color variation, rapid response, and high sensitivity. Additionally, portable test strips enable convenient on-site BUP detection and simplifying field monitoring of spiked real samples. The study achieves precise qualitative and quantitative BUP analysis in grape fruit, groundwater, and soil with satisfactory recoveries. Further, the biological applicability of sensor for the in vitro detection of BUP in L929 living cells was demonstrated. This research breakthrough overcomes the limitations of traditional analytical methods, offering an efficient and reliable approach for food and environmental monitoring and pesticide residue detection.
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  • 文章类型: Journal Article
    吡丙醚(PPF)荧光探针的开发是至关重要的,因为它对人类健康的潜在威胁。然而,PPF的化学惰性和低溶解度对使用荧光探针检测水溶液中的PPF提出了重大挑战。在这里,我们最初提出了一种基于2-(4-(二甲基氨基)苯基)-3-羟基-6,7-二甲氧基-4H-色烯-4-酮(HOF)和血清白蛋白(SA)的配合物作为双模荧光探针,HOF@SA。该探针利用指示剂置换测定(IDA)在低PPF浓度(<10µM)下从探针中释放染料HOF,并将游离染料HOF嵌入高浓度(>10µM)的PPF胶束中。这导致PPF的双模式荧光响应特性:低浓度下的关闭响应和高浓度下的比率响应。对用于PPF检测的HOF@SA的感测行为的调查显示出快速响应(<60s),高灵敏度(LOD〜4.7ppb),高选择性,和优良的视觉检测能力(从青色到黄色)。此外,借助便携式设备,该方法能够分析环境和食品样品中的PPF。这些结果促进了用于环境和食品中PPF分析的荧光探针方法的发展。
    The development of a fluorescent probe for pyriproxyfen (PPF) is crucial due to its potential threat to human health. However, the chemical inertness and low solubility of PPF present significant challenges for the detection of PPF in aqueous solutions using fluorescent probes. Herein, we have originally proposed a complex based on 2-(4-(dimethylamino)phenyl)-3-hydroxy-6,7-dimethoxy-4 H-chromen-4-one (HOF) and serum albumin (SA) as a dual-mode fluorescent probe, HOF@SA. This probe utilizes an indicator displacement assay (IDA) to release the dye HOF from the probe at low PPF concentrations (< 10 µM) and embeds the free dye HOF into the micelle of PPF at high concentrations (> 10 µM). This results in dual-mode fluorescent response characteristics for PPF: a turn-off response at low concentrations and a ratiometric response at high concentrations. An investigation of sensing behavior of HOF@SA for PPF detection exhibits rapid response (< 60 s), high sensitivity (LOD ∼4.7 ppb), high selectivity, and excellent visual detection capability (from cyan to yellow). Moreover, with the aid of a portable device, this method enables to analyze PPF in environmental and food samples. These results promote the advancement of a fluorescent probe approach for PPF analysis in environment and food.
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  • 文章类型: Journal Article
    次氯酸(HClO)作为一种活性氧(ROS)在许多生物过程中起着至关重要的作用。有机荧光探针对HClO的检测引起了极大的兴趣,由于它们相对较高的选择性和灵敏度,令人满意的时空分辨率和良好的生物相容性。构建荧光探针检测HClO具有斯托克斯位移大的优点,宽排放间隙,近红外发射和良好的水溶性仍然具有挑战性。在这项工作中,开发了一种新的HClO比率荧光探针(称为HCY)。基于FRET的HCY通过结合香豆素和黄酮荧光团构建。在没有HClO的情况下,HCY存在FRET过程,然而,在HClO存在下FRET被抑制,因为共轭双键断裂。由于供体的发射光谱和受体的吸收光谱的良好匹配,FRET系统出现有利的能量转移效率。HCY具有较高的灵敏度和较快的响应时间。在低检测限的情况下,建立了荧光强度与HClO浓度之比之间的线性关系。更重要的是,HCY也用于RAW264.7细胞中HClO的荧光图像。
    Hypochlorous acid (HClO) as a kind of reactive oxygen species (ROS) plays a vital role in many biological processes. Organic fluorescence probes have attracted great interests for the detection of HClO, due to their relatively high selectivity and sensitivity, satisfactory spatiotemporal resolution and good biocompatibility. Constructing fluorescence probes to detect HClO with advantages of large Stokes shift, wide emission gap, near infrared emission and good water solubility is still challenging. In this work, a new ratiometric fluorescence probe (named HCY) for HClO was developed. FRET-based HCY was constructed by bonding a coumarin and a flavone fluorophore. In absence of HClO, HCY exists FRET process, however, FRET is inhibited in the presence of HClO because the conjugated double bond broke. Due to the good match of the emission spectrum of the donor and the absorption spectrum of the acceptor, the FRET system appears favorable energy transfer efficiency. HCY showed high sensitivity and rapid response time. The linearity between the ratios of fluorescence intensity and concentration of HClO was established with a low limit of detection. What\'s more, HCY was also applied for fluorescence images of HClO in RAW264.7 cells.
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  • 文章类型: Journal Article
    褪黑激素(MT)的识别和定量对于与昼夜节律破坏相关的疾病的早期诊断至关重要。在这里,通过使用丝氨酸和苹果酸作为还原剂和碳源的改进的水热处理合成了新型的蓝色发射碳点(BCD)。通过策略性地构建MT传感系统,将BCD与载有铂/钌纳米颗粒(PtRu/CN)的C3N4纳米片集成在一起,从而将获得的BCD的出色光学特性用于比率传感。在这个系统中,H2O2激活PtRu/CN的过氧化物酶样活性以产生·OH和1O2,用于将无色邻苯二胺(OPD)氧化为黄色2,3-二氨基吩嗪(DAP),并在565nm处发射荧光。同时,通过静态猝灭和内部滤波效应(IFE)过程,生成的DAP猝灭了439nm处的BCD的荧光发射。然而,MT快速清除所产生的自由基以逆转比率荧光信号。开发的BCD/PtRu/CN/OPD/H2O2传感平台可对浓度为0.06至600μmol/L的MT进行定量分析,检测限低为23.56nmol/L。此外,成功开发了基于智能手机的MTRGB传感,用于快速可视化和便携式处理。更广泛地说,提出了制备具有灵敏荧光传感特性的碳点的新见解,希望将来考虑。
    The identification and quantification of melatonin (MT) are crucial for early diagnosis of disorders associated with circadian rhythm disruption. Herein, novel blue-emissive carbon dots (BCDs) were synthesized through an improved hydrothermal treatment using serine and malic acid as reductant and carbon source. The excellent optical properties of the as-obtained BCDs were used for ratiometric sensing by strategically constructing a MT sensing system integrating BCDs with C3N4 nanosheets loaded with platinum/ruthenium nanoparticles (PtRu/CN). In this system, H2O2 activated the peroxidase-like activity of PtRu/CN to generate •OH and 1O2 for oxidizing the colorless o-phenylenediamine (OPD) into yellow 2,3-diaminophenazine (DAP) with fluorescence emission at 565 nm. Concurrently, the fluorescence emission of BCDs at 439 nm was quenched by the generated DAP via the static quenching and inner filter effect (IFE) process. However, MT rapidly scavenged the generated free radicals to reverse the ratio fluorescence signal. The developed BCDs/PtRu/CN/OPD/H2O2 sensing platform enabled quantitative analysis of MT at concentrations ranging from 0.06 to 600 μmol/L with a low detection limit of 23.56 nmol/L. Moreover, smartphone-based RGB sensing of MT was successfully developed for rapid visualization and portable processing. More broadly, novel insights into the preparation of carbon dots with sensitive fluorescence sensing properties were presented, promising for future considerations.
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  • 文章类型: Journal Article
    在这里,基于原位荧光反应和原位形成红色荧光二硫苏糖醇-铜纳米颗粒(DTT-CuNPs)的组合反应,提出了一种新型的超灵敏检测邻苯二胺(OPD)的比率策略。这里,Cu2+既用作氧化剂又用作前体。脱氢抗坏血酸(DHAA)通过AA和Cu2+的氧化还原反应形成。然后,DHAA与OPD反应,通过原位荧光反应产生蓝色荧光喹喔啉(OXD),发射峰在434nm处。由于DTT与未被AA消耗的残留Cu2+之间的配位反应,在666nm处具有发射峰的红色发射DTT-CuNP立即产生。在434nm处OXD的荧光强度(FI)紧密依赖于OPD的浓度,可用作OPD检测的响应信号。同时,DTT-CuNPs在666nm处的FI无明显变化,可以用作OPD检测的参考信号。因此,Cu2+/AA/DTT传感系统的比值(F434/F666)成功地用于量化OPD,表现出0.2µM至60µM的宽线性范围,LOD为0.09µM。
    Herein, a novel ratiometric strategy for ultra-sensitive detection of o-phenylenediamine (OPD) was proposed based on combinatorial reactions of in-situ fluorogenic reaction and in-situ formation of red fluorescent dithiothreitol-copper nanoparticles (DTT-CuNPs). Here, Cu2+ is used both as an oxidant and as a precursor. Dehydroascorbic acid (DHAA) is formed via redox reaction of AA and Cu2+. Then, DHAA reacts with OPD to yield blue fluorescent quinoxaline (OXD) with emission peak at 434 nm through in-situ fluorogenic reaction. Red emitting DTT-CuNPs with emission peak at 666 nm is instantly generated due to the coordination reaction between DTT and the residual Cu2+ which is not consumed by AA. The fluorescence intensity (FI) of OXD at 434 nm is closely relied on the concentration of OPD, which can be used as a response signal for OPD detection. Meanwhile, FI of DTT-CuNPs at 666 nm has no significant change, which can be used as a reference signal for OPD detection. Thus, the ratio (F434/F666) of the Cu2+/AA/DTT sensing system is successfully employed to quantify OPD, exhibiting a wide linear range from 0.2 µM to 60 µM, with LOD of 0.09 µM.
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  • 文章类型: Journal Article
    基于比率自供电光电化学平台,开发了一种新型的微囊藻毒素RR(MC-RR)高精度传感器。详细来说,设计了具有良好光电活性的有缺陷的MoS2/Ti3C2纳米复合材料作为传感器的光电阳极,以增强信号并提高检测灵敏度。为了有效地消除外部干扰,这种比率装置的关键点是引入了空间分辨技术,其中包括检测部分和参考部分,生成参考信号和响应信号,分别。此外,输出功率作为检测信号,而不是传统的光电流或光电压。Further,引入过硫酸钾作为电子受体,有利于提高电子传输效率,阻碍电子-空穴复合,显著提升了传感器的性能。最后,采用适体作为识别元件捕获MC-RR分子。制备的传感器的线性范围为10-12至10-6M,检出限为5.6×10-13M(S/N=3)。它具有良好的精度,选择性,和灵敏度,在自供电传感领域对高能量输出样品的现场精确分析中显示出巨大的前景。
    A novel high-precision aptasensor of microcystin-RR (MC-RR) is developed based on a ratiometric self-powered photoelectrochemical platform. In detail, the defective MoS2/Ti3C2 nanocomposite with good photoelectric activity was designed to serve as the photoanode of the sensor for enhancing the signal and improving the detection sensitivity. In order to effectively eliminate external interferences, the key point of this ratiometric device is the introduction of the spatial-resolved technique, which includes the detection section and the reference section, generating reference signals and response signals, respectively. Moreover, output power was used as the detection signal, instead of the traditional photocurrent or photovoltage. Further, potassium persulfate was introduced as electron acceptor, which was beneficial for improving the electron transport efficiency, hindering electron-hole recombination, and significantly promoting the performance of the sensor. Finally, aptamer was adopted as recognition element to capture MC-RR molecules. The prepared sensor had a linear range from 10-12 to 10-6 M, and the detection limit was 5.6 × 10-13 M (S/N = 3). It has good precision, selectivity, and sensitivity, which shows great prospects in the on-site accurate analysis of samples with high energy output in the self-powered sensing field.
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  • 文章类型: Journal Article
    快速、准确地识别肿瘤边界对胶质瘤的治疗至关重要,但是由于神经胶质瘤细胞的侵袭性,这很困难。本文旨在探索一种基于无标记表面增强拉曼散射(SERS)技术的快速诊断策略,用于术中定量检测胶质瘤细胞比例。以银纳米粒子为基底,我们对包含正常脑组织和不同浓度患者来源的神经胶质瘤细胞的模拟临床样本进行了深入的SERS分析.结果显示了655和717cm-1的两个通用特征峰,无论个体差异如何,这与神经胶质瘤细胞比例密切相关。根据两个峰的强度比,通过使用人工神经元网络模型和多项式回归模型,建立了定量神经胶质瘤细胞的比例SERS策略.这种策略准确地估计了神经胶质瘤细胞在模拟临床样品(R2=0.98)和冷冻样品(R2=0.85)中的比例。更重要的是,它准确地促进了新获得的样本中肿瘤边缘的勾画。一起来看,这种基于SERS的方法确保了在手术切除期间快速和更详细地识别肿瘤边缘,这可能有利于术中决策和病理评估。
    Rapid and accurate identification of tumor boundaries is critical for the cure of glioma, but it is difficult due to the invasive nature of glioma cells. This paper aimed to explore a rapid diagnostic strategy based on a label-free surface-enhanced Raman scattering (SERS) technique for the quantitative detection of glioma cell proportion intraoperatively. With silver nanoparticles as substrate, an in-depth SERS analysis was performed on simulated clinical samples containing normal brain tissue and different concentrations of patient-derived glioma cells. The results revealed two universal characteristic peaks of 655 and 717 cm-1, which strongly correlated with glioma cell proportion regardless of individual differences. Based on the intensity ratio of the two peaks, a ratiometric SERS strategy for the quantification of glioma cells was established by employing an artificial neuron network model and a polynomial regression model. Such a strategy accurately estimated the proportion of glioma cells in simulated clinical samples (R2 = 0.98) and frozen samples (R2 = 0.85). More importantly, it accurately facilitated the delineation of tumor margins in freshly obtained samples. Taken together, this SERS-based method ensured a rapid and more detailed identification of tumor margins during surgical resection, which could be beneficial for intraoperative decision-making and pathological evaluation.
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