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Enhancement of signal intensity of elements in human blood serum using a metal mesh-enhanced CO2 laser-induced breakdown spectroscopy in ambient He gas 在环境 He 气体中使用金属网增强 CO2 激光诱导击穿光谱仪增强人体血清中元素的信号强度
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-05-02 DOI: 10.1016/j.talo.2024.100322
Ali Khumaeni , Wahyu Setia Budi , Rinda Hedwig , Kazuyoshi Kurihara , Masahiko Tani , Koo Hendrik Kurniawan

Accurate and reliable identification and analysis of the elemental composition of human blood serum is of utmost importance. The present investigation included the analysis of human blood serums for elemental composition using a metal mesh-supported CO2 laser-induced breakdown spectroscopy under a helium gas environment at atmospheric pressure. In this study, a pulsed transversely excited atmospheric CO2 laser with a wavelength of 10.64 µm and a pulse duration of 200 ns was applied to irradiate the human blood serum film placed on a copper metal to induce a luminous plasma. A significant increment of elemental signal intensity occurs by introducing a metal mesh covering the serum film. Qualitative and quantitative analyses have been conducted on the human blood serum's major, minor, and trace elements. The concentrations of elements in the human blood are estimated to be 9160 parts per million (ppm) for carbon (C), 174 ppm for calcium (Ca), 600 ppm for potassium (K), 1410 ppm for magnesium (Mg), 343 ppm for phosphorus (P), 2180 ppm for sodium (Na), and 48 ppm for iron (Fe). The results of the CO2 LIBS method demonstrate a high level of concurrence with the results obtained by the conventional XRF method.

准确可靠地鉴定和分析人体血清中的元素组成至关重要。本研究包括在常压氦气环境下使用金属网支持的二氧化碳激光诱导击穿光谱分析人体血清的元素组成。在这项研究中,波长为 10.64 µm、脉冲持续时间为 200 ns 的脉冲横向激励大气 CO2 激光被用来照射放置在铜金属上的人体血清膜,以诱发发光等离子体。通过引入覆盖血清膜的金属网,元素信号强度明显增加。对人体血清中的主要元素、次要元素和微量元素进行了定性和定量分析。据估计,人体血液中的元素浓度为:碳(C)9160ppm、钙(Ca)174ppm、钾(K)600ppm、镁(Mg)1410ppm、磷(P)343ppm、钠(Na)2180ppm、铁(Fe)48ppm。CO2 LIBS 方法得出的结果与传统 XRF 方法得出的结果高度一致。
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引用次数: 0
Sensitive assessment of bilirubin using various color space signals derived from captured images of microfluidic paper-based analytical devices 利用从微流控纸质分析装置捕获的图像中提取的各种色彩空间信号灵敏评估胆红素
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-04-28 DOI: 10.1016/j.talo.2024.100323
Mohamed Farag , Ashraf A. Mohamed , Souad A. Elfeky , Abdelnaby M. Salem

Many neonates’ manifest hyperbilirubinemia and jaundice during the first week following birth because of bilirubin accumulation in the blood. Newborns with severe hyperbilirubinemia develop neurotoxicity. Therefore, sensitive, accurate, cost-effective, and timely determination of bilirubin levels is highly desired. Herein, we present three simple systems of bilirubin assessment based on spectrophotometric, and digital imaging tools. Image-capturing devices pose a formidable challenge to sophisticated spectrophotometers and field-monitoring devices because of their simplicity and sensitivity. The first and second systems of bilirubin assessment, in solution, relied on spectrophotometric and conventional color responses of digital images collected with conventional or android smartphone camera, with LODs of 0.060–0.082 and LOQs of 0.200–0.273 ppm bilirubin. The third system utilized a microfluidic paper-based analytical device (μ-PAD) that is patterned with a wax printer on Whatman grade-1 chromatographic papers, with linear calibration graphs of up to 2.70,s and LODs of 0.035–0.040 and LOQs of 0.117–0.133 μg bilirubin/μ-PAD.

由于胆红素在血液中蓄积,许多新生儿在出生后一周内会出现高胆红素血症和黄疸。患有严重高胆红素血症的新生儿会出现神经中毒。因此,灵敏、准确、经济、及时地测定胆红素水平是非常必要的。在此,我们介绍三种基于分光光度法和数字成像工具的简单胆红素评估系统。图像捕捉设备因其简便性和灵敏度,对复杂的分光光度计和现场监测设备构成了巨大的挑战。第一套和第二套胆红素评估系统是在溶液中利用分光光度计和传统色彩反应对传统或安卓智能手机摄像头采集的数字图像进行评估,LOD 为 0.060-0.082,LOQ 为 0.200-0.273 ppm 胆红素。第三个系统采用了微流控纸质分析装置(μ-PAD),该装置用蜡打印机在 Whatman 1 级色谱纸上绘制图案,线性校准图高达 2.70,s,最低检测限为 0.035-0.040 微克胆红素/μ-PAD,最低检测限为 0.117-0.133 微克胆红素/μ-PAD。
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引用次数: 0
Magnetic covalent organic frameworks combined with HPLC for determination of alkylphenols 磁性共价有机框架与高效液相色谱法相结合测定烷基酚
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-04-28 DOI: 10.1016/j.talo.2024.100320
Ting Cheng , Yan-Xin Chen , Zi-Yu Li , Jia-Hui Zhu , Jie Zhao , Yu-Shen Liu , Lu-Liang Wang

Alkylphenols are widely applied in the field of industry and agriculture, but their endocrine disrupting properties harm to human health. Moreover, alkylphenols often exhibit the low content in complex samples. Thus, we proposed magnetic covalent organic framework composites (Fe3O4@TatTpa) for efficient magnetic solid phase extraction (MSPE) of alkylphenols via hydrogen bonding, π-π and hydrophobic interactions. In combination with HPLC detection, good linearity (0.006–10 µg mL−1) with R2 (≥0.997) and low limit of detections (1.8–6 × 10−3 µg mL−1) were realized for alkylphenols. The proposed method was successfully employed to determine alkylphenols in soft drink, black oolong tea, and watermelon samples with satisfactory recoveries (86.1–118.5 %) and relative standard deviations (6.3–14.8 %).

烷基酚广泛应用于工业和农业领域,但其扰乱内分泌的特性会损害人类健康。此外,烷基酚在复杂样品中的含量通常较低。因此,我们提出了磁性共价有机框架复合材料(Fe3O4@TatTpa),通过氢键、π-π和疏水相互作用实现烷基酚的高效磁性固相萃取(MSPE)。结合高效液相色谱检测,烷基酚的线性关系良好(0.006-10 µg mL-1),R2(≥0.997),检测限低(1.8-6 × 10-3 µg mL-1)。该方法成功地测定了软饮料、黑乌龙茶和西瓜样品中的烷基酚,回收率(86.1-118.5%)和相对标准偏差(6.3-14.8%)均令人满意。
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引用次数: 0
Current trends and challenges in amniotic fluid of biomarkers in trace amounts 羊水中痕量生物标记物的当前趋势和挑战
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-04-27 DOI: 10.1016/j.talo.2024.100324
Xiangyin Liu, Leyi Li, He Wang, Ruizhi Liu, Han Zhang

The dynamic changes of amniotic fluid during pregnancy are crucial for the development, protection, defense and nutrition of the fetus. Amniotic fluid contains a variety of trace biomarkers, such as microRNA, free DNA, reactive oxygen species, interleukin and metabolomics, etc., which are of great significance for fetal health, diagnosis and drug control of various diseases. This article reviews the latest advances in the detection of microbial markers in amniotic fluid, and introduces the methods of amniotic fluid collection and attention. In addition, the biological approach to amniotic fluid testing is discussed. Finally, the challenges of amniotic fluid sample testing are discussed, with a view to promoting the clinical application of amniotic fluid in the field of assisted reproduction.

孕期羊水的动态变化对胎儿的发育、保护、防御和营养至关重要。羊水中含有多种微量生物标志物,如 microRNA、游离 DNA、活性氧、白细胞介素和代谢组学等,对胎儿健康、各种疾病的诊断和药物控制具有重要意义。本文综述了羊水中微生物标志物检测的最新进展,介绍了羊水的采集方法和注意事项。此外,还讨论了羊水检测的生物学方法。最后,讨论了羊水样本检测所面临的挑战,以期促进羊水在辅助生殖领域的临床应用。
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引用次数: 0
An initial study of cell separation based on mechanical properties using a sponge-like monolithic polymer 基于海绵状整体聚合物机械性能的细胞分离初步研究
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-04-26 DOI: 10.1016/j.talo.2024.100321
Kengo Tsuji , Tetsuya Tanigawa , Yusei Tsutsumi , Takuya Kubo , Noritada Kaji

We developed a novel cell separation method based on the mechanical properties using a sponge-like monolithic polymer (SPM) in a spin-column format capable of high throughput and mass processing for cell diagnosis and separation. The continuous large flow pores of the monolithic skeleton around 200 μm were expected to act as a sieving matrix for large flexible molecules such as cells larger than 10 μm in diameter, based not only on the size but also on the mechanical deformability of the cells. The passage rates of rigid polystyrene beads ranging in size from 1 to 10 μm were investigated and demonstrated that the spin column acted as a separation matrix rather than a size-based cut-off filter in the 60 and 200 μm pores of the SPM. Two cell types, adherent cells (HeLa cells) and suspension cells (THP-1 cells), showed different passage behavior in the spin column, and 70 % and 30 % of the cells, respectively, were trapped in the column and never eluted. To investigate how the mechanical deformability of the cells affects the passage behavior, glutaraldehyde treatment, which denatured the proteins and changed the elastic moduli, was performed and compared. As a result, the fixed cells drastically reduced the passage rate and became trapped inside the SPM column. These initial studies explored a new application field of SPM for high throughput cell separation based on the mechanical properties of the cells despite the same size, and contribute to a new cell assay method prior to cell transplantation.

我们利用海绵状整体聚合物(SPM)的机械特性开发出了一种新型细胞分离方法,该方法采用旋柱形式,能够进行高通量和大规模处理,用于细胞诊断和分离。整体骨架上约 200 μm 的连续大流动孔有望成为筛分大柔性分子(如直径大于 10 μm 的细胞)的基质,这不仅基于细胞的大小,还基于细胞的机械变形能力。研究了尺寸从 1 微米到 10 微米不等的硬质聚苯乙烯珠的通过率,结果表明,在 SPM 的 60 微米和 200 微米孔中,旋转柱起到了分离基质的作用,而不是基于尺寸的截止过滤器。两种细胞类型,即粘附细胞(HeLa 细胞)和悬浮细胞(THP-1 细胞),在纺丝柱中表现出不同的通过行为,分别有 70% 和 30% 的细胞被截留在柱中,从未被洗脱出来。为了研究细胞的机械变形性如何影响其通过行为,我们对使蛋白质变性并改变弹性模量的戊二醛处理进行了比较。结果,固定的细胞大大降低了通过率,并被困在 SPM 柱内。这些初步研究探索了 SPM 在高通量细胞分离方面的新应用领域,其基础是细胞的机械特性(尽管大小相同),并为细胞移植前的新细胞检测方法做出了贡献。
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引用次数: 0
Dynamic cell photo-manipulation technology for the molecular and mechanical regulation analyses of collective cell migration 用于细胞集体迁移的分子和机械调控分析的动态细胞光操纵技术
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-04-25 DOI: 10.1016/j.talo.2024.100319
Kazuhiro Tatematsu , Shota Yamamoto , Masao Kamimura , Kazuo Yamaguchi , Jun Nakanishi

Collective cell migration is an essential biological process. Migration behaviors of multiple cellular units depend on the mechanical and chemical properties of their scaffolds and the geometry of the cells. However, the mechanisms by which these properties synergistically regulate the collective cell characteristics remain unknown. A robust method is required to analyze collective cell migration. Therefore, in this study, we developed a new method for collective cell migration analysis using defined chemical, mechanical, and geometrical properties. Our method is based on a poly(acrylic acid) hydrogel, whose surface is functionalized with photocleavable poly(ethylene glycol) and a cell-adhesive peptide. By controlling the UV irradiation of the photoactivatable hydrogel, we created geometrically controlled cellular clusters and induced collective migration. Furthermore, chemical and mechanical cues exposed to cell clusters were manipulated depending on the surface density of the cell-adhesive peptide and crosslinking density of the hydrogel. As a proof of concept, we also demonstrated that the collective migration of epithelial cells was synergistically regulated by the chemical and mechanical properties of the scaffold. Our results suggest the new photoactivatable substrate as a promising tool for advanced molecular and mechanobiological analyses of collective cell migration.

细胞集体迁移是一个重要的生物过程。多个细胞单位的迁移行为取决于其支架的机械和化学特性以及细胞的几何形状。然而,这些特性协同调节细胞集体特性的机制仍然未知。我们需要一种可靠的方法来分析细胞的集体迁移。因此,在本研究中,我们开发了一种新方法,利用定义的化学、机械和几何特性进行细胞集体迁移分析。我们的方法基于一种聚丙烯酸水凝胶,其表面由可光裂解的聚乙二醇和细胞粘附肽功能化。通过控制光可激活水凝胶的紫外线照射,我们创建了几何形状可控的细胞集群,并诱导了细胞的集体迁移。此外,我们还根据细胞粘附肽的表面密度和水凝胶的交联密度,对暴露于细胞集群的化学和机械线索进行了操作。作为概念验证,我们还证明了上皮细胞的集体迁移受支架的化学和机械特性的协同调节。我们的研究结果表明,这种新型光活化基质是一种很有前途的工具,可用于对细胞集体迁移进行先进的分子和机械生物学分析。
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引用次数: 0
Promising optical chemical sensor for detecting Al(III) ions in water based on organic fluorophore 基于有机荧光团检测水中铝(III)离子的前景光明的光学化学传感器
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-04-12 DOI: 10.1016/j.talo.2024.100317
Reham Ali , Wael A. El-Sayed

In the present work, an optical sensing scheme was designed to detect the Al(III) ions based on a fluorescent probe. The synthesized probe N-(3-chloro)-salicylaldimine CSI receptor was developed using turn-on fluorescence enhancement. During the treatment process of Al(III) ions, the emission of the CSI probe was increased at 545 nm due to the formation of a 1:1 complex between the chemosensor and the Al(III) ions at room temperature. The gradual addition of Al(III) ions to the studied solution gradually enhanced the CSI emission. The other metal ions, including alkali, alkaline metal ions, and some transition metal ions, had no noticeable impact on the fluorescent intensity. The limit of detection (LOD) and (LOQ) were determined as 0.427 nM and 1.28 nM, respectively. The detection limit for this sensor is very low, demonstrating its remarkable selectivity and ultra-sensitivity. These impressive characteristics allow the detection of Al(III) ions at concentrations as low as 1.28 × 10−3 to 1 μM while highly selective even in the presence of other metal ions. EDTA solution at a concentration of 1 µM was used to make the sensor reversible. We also provide the fact that the CSI probe can be a promising optical chemical for detecting Al(III) ions in real samples.

在本研究中,设计了一种基于荧光探针检测铝(III)离子的光学传感方案。合成的探针 N-(3-氯)-水杨醛亚胺 CSI 受体是利用开启荧光增强技术开发的。在处理 Al(III)离子的过程中,由于化学传感器与 Al(III)离子在室温下形成了 1:1 的复合物,CSI 探针在 545 纳米波长处的发射增加。在研究溶液中逐渐加入 Al(III)离子会逐渐增强 CSI 的发射。其他金属离子,包括碱、碱金属离子和一些过渡金属离子,对荧光强度没有明显影响。检测限(LOD)和 LOQ 分别为 0.427 nM 和 1.28 nM。该传感器的检测限非常低,表明其具有显著的选择性和超灵敏度。这些令人印象深刻的特性使得 Al(III)离子的检测浓度可低至 1.28 × 10-3 至 1 μM,同时即使在存在其他金属离子的情况下也具有高度选择性。为了使传感器具有可逆性,我们使用了浓度为 1 µM 的 EDTA 溶液。我们还提供了一个事实,即 CSI 探针是一种很有前途的光学化学试剂,可用于检测实际样品中的铝(III)离子。
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引用次数: 0
Interlaboratory validation and one-year retrospective review of hemp and marijuana decision-point assays 大麻和大麻决定点测定的实验室间验证和一年回顾性审查
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-04-09 DOI: 10.1016/j.talo.2024.100318
Ya-Chih Cheng , James T. Miller , Kay McClain , Charles Cline , Sarah Kerrigan

After the passage of the Agriculture Improvement Act of 2018 (Farm Bill) that defined hemp as Cannabis sativa L. if it contained ≤0.3 % Δ9-THC on a dry weight basis, forensic laboratories were faced with the challenge of distinguishing marijuana from hemp in seized drug samples. This study reports the results of an interlaboratory validation of a previously developed qualitative decision-point assay for the differentiation of illegal marijuana from legal hemp, utilizing gas chromatography-mass spectrometry (GC–MS) with a 1 % Δ9-THC threshold. The method was validated in terms of selectivity, linearity, carryover, precision, accuracy, extract stability, dilution integrity, and measurement uncertainty. Other elements such as decarboxylation rate and potential for CBD interference were also evaluated. Specificity and positive predictive value were both 100 % using known cannabis reference materials. A total of 8 false negative results were observed among the 280 analyses, resulting in an overall assay sensitivity of 94 % and a negative predictive value of 95 %. The small number of false negative results near the 1 % threshold were attributed to decarboxylation inefficiency in some laboratories. While qualitative in nature, the measurement uncertainty of the assay at the 0.3 % Δ9-THC cutoff (legal threshold) using a 95.45 % confidence interval (k = 2) ranged from 12.2 % to 21.8 % among laboratories (equivalent to 0.3 % ± 0.04 % to 0.07 % Δ9-THC by weight). A one-year retrospective study across three agencies and fifteen laboratories was undertaken. Among the three agencies participating in the original study, 93–96 % of all suspected cannabis seizures yielded results above the administrative threshold of 1 % Δ9-THC (n = 3,288). The interlaboratory method development highlighted differences in performance between sites, ultimately improving the overall robustness of the method. Observations highlight the need for site-specific validation and vigilance. While multi-agency collaborations and interlaboratory validations are valuable, they do not replace the necessity for full, independent, and rigorous validation.

2018 年农业改进法案》(Farm Bill)将大麻定义为干重≤0.3% Δ9-四氢大麻酚(Δ9-THC)的大麻,该法案通过后,法医实验室面临着在缉获的毒品样本中区分大麻和大麻的挑战。本研究报告了实验室间对之前开发的定性决策点检测方法进行验证的结果,该方法利用气相色谱-质谱法(GC-MS)区分非法大麻和合法大麻,Δ9-THC 的阈值为 1%。该方法在选择性、线性、携带、精确度、准确度、提取物稳定性、稀释完整性和测量不确定性等方面都得到了验证。此外,还评估了其他因素,如脱羧率和 CBD 干扰的可能性。使用已知的大麻参考材料,特异性和阳性预测值均为 100%。在 280 项分析中,共观察到 8 项假阴性结果,因此总体检测灵敏度为 94%,阴性预测值为 95%。少量接近 1% 临界值的假阴性结果是由于某些实验室脱羧效率低下造成的。虽然属于定性分析,但在 0.3% Δ9-THC临界值(法定临界值)下,采用 95.45% 置信区间(k = 2),各实验室的测量不确定性在 12.2% 到 21.8% 之间(相当于 0.3% ± 0.04% 到 0.07% Δ9-THC(按重量计))。对三个机构和 15 个实验室进行了为期一年的回顾性研究。在参与最初研究的三个机构中,所有疑似大麻缉获量中有 93-96% 的结果高于 1% Δ9-THC(n = 3,288)的管理阈值。实验室间方法开发突出了不同地点之间的性能差异,最终提高了方法的整体稳健性。观察结果凸显了针对具体地点进行验证和保持警惕的必要性。虽然多机构合作和实验室间验证很有价值,但它们并不能取代全面、独立和严格验证的必要性。
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引用次数: 0
Application of high-performance thin layer chromatography mass spectrometry (HPTLC MS) in foodomics authenticity 高效薄层色谱质谱法(HPTLC MS)在食品组学真实性中的应用
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-04-04 DOI: 10.1016/j.talo.2024.100315
Neha Sharma , Anurag , Harjeet Singh , Alok Sharma

Background

Chemometric analysis is also a powerful tool that can be used in the preliminary stages of analytical methods optimization, but is also efficient in data processing. These new approaches may be the key to the analysis of proteins, carbohydrate, sphignolipids, polyphenols in different food components. Although there are challenges in identifying and annotating those compounds due to the limited availability of analytical standards and structural diversity.

Scope and approach

Chromatograms are a useful tool for learning more about the chemical make-up of the food being tested. This information can occasionally be implicit or presented in a subtle way. Therefore, to extract it, chemometric tools and data mining techniques are needed. A chromatogram's fingerprint allows for the possibility of performing both identity and quality testing on food. This viewpoint aims to offer a current assessment of chromatographic fingerprinting technique in the area of food authentication. Additionally, this methodology's limitations, absence from official analytical methods, and future directions are discussed. Novel techniques have been employed in the past few decades, ranging from high-pressure thin liquid chromatography (HPTLC) to mass spectrometry (MS) and other spectroscopic methods. In the last decade research developments, and the application of analytical methods in qualitative and quantitative studies of food components and their adulterants is reviewed in the present work. High-pressure Thin liquid chromatography (HPTLC) is hyphenated with high resolution mass spectrometry is particularly addressed due to its applicability in the targeted/untargeted metabolomic analysis of all food components.

Key findings and conclusions

In the current study, the HPTLC-MS technique was used to examine food components and food adulteration. The HPTLC-MS hyphenated techniques were found to be an extremely helpful method for the detection of food adulterants as well as the various food components, such as protein, carbohydrates, lipids, essential oils, and flavonoids, which were found to be effective as medicinally.

背景化学计量分析也是一种强大的工具,不仅可用于分析方法优化的初步阶段,而且在数据处理方面也很有效。这些新方法可能是分析不同食品成分中蛋白质、碳水化合物、脂质、多酚的关键。尽管由于分析标准的有限性和结构的多样性,在鉴定和注释这些化合物方面还存在挑战。这些信息有时可能是隐含的或以微妙的方式呈现。因此,要提取这些信息,需要使用化学计量学工具和数据挖掘技术。通过色谱指纹图谱,可以对食品进行身份和质量检测。本文旨在对食品鉴定领域的色谱指纹图谱技术进行现状评估。此外,还讨论了这种方法的局限性、官方分析方法的缺失以及未来的发展方向。在过去的几十年里,从高压薄层液相色谱法(HPTLC)到质谱法(MS)和其他光谱方法,各种新技术层出不穷。本报告回顾了过去十年的研究进展,以及分析方法在食品成分及其掺假物的定性和定量研究中的应用。高压薄层液相色谱法(HPTLC)与高分辨质谱法的结合尤其受到关注,因为它适用于对所有食品成分进行有针对性/无针对性的代谢组学分析。研究发现,HPTLC-MS 联用技术是检测食品掺假物以及各种食品成分(如蛋白质、碳水化合物、脂类、精油和黄酮类化合物)的一种非常有用的方法,这些成分具有药用功效。
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引用次数: 0
A thiourea dihydropyridine as a highly selective and sensitive “turn-on” fluorescent chemosensor for mercury(II) ion in water and its application for cell imaging 硫脲二氢吡啶作为水中汞(II)离子的高选择性、高灵敏度 "开启 "荧光化学传感器及其在细胞成像中的应用
Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-03-24 DOI: 10.1016/j.talo.2024.100316
Islah Muttaqin , Waroton Paisuwan , Thitiporn Pattarakankul , Tanapat Palaga , Mongkol Sukwattanasinitt , Anawat Ajavakom

The existence of extremely toxic mercury contaminants in the environment, even at very low concentrations, poses severe human health issues. Mercury exposure may lead to various diseases, such as prenatal brain damage, cognitive severe, motion disorders, and Minamata diseases. Hence, developing an effective and selective method to detect Hg2+ in the environment and biological samples is of great interest. Amongst various Hg2+ detection techniques, fluorescent chemosensors offer more convenient procedures, affordable cost, high selectivity, and the capability to perform cell imaging for Hg2+ detection. Herein, a novel "turn-on" fluorescent chemosensor, Thiourea-DHP derivative (TUD), highly selective to Hg2+, was successfully developed. TUD was synthesized by cyclotrimerization of β-amino acrylate, followed by the thioacylation of the resulting dihydropyridine (DHP) with dimethylamino thiocarbonyl chloride. The Hg2+ detection by TUD displayed an astonishing naked-eye blue fluorescence signal under blacklight, exhibiting an LOD of 69 nM or 14 ppb at pH 7.4 in the HEPES buffer. Hg2+-induced hydrolytic desulfurization of the low fluorescent TUD to produce the strongly fluorescent urea-DHP (UD) is proposed as a mechanism for this fluorescence enhancement. The formation of UD was confirmed by 1H NMR, 13C NMR, and HRMS. This detecting system of TUD provided excellent percentage recovery (>97 %) for the analysis of Hg2+ contaminants in real-environmental water samples. Besides, the TUD probe showed nontoxic properties in living cells towards RAW264.7 murine macrophage cell line even at high concentrations (100 µM). Our proposed TUD probe demonstrated superior sensitivity in pure aqueous media compared to current mercury-desulfurization fluorescent chemosensors. This sensing system proved effective for analysing Hg2+ contaminants in real-environmental water samples. Additionally, the nontoxic TUD probe successfully revealed the remarkable biocompatibility for Hg2+ detection in living cells.

环境中存在毒性极强的汞污染物,即使浓度很低,也会对人类健康造成严重危害。接触汞可能会导致各种疾病,如产前脑损伤、严重的认知障碍、运动障碍和水俣病。因此,开发一种有效且具有选择性的方法来检测环境和生物样本中的 Hg2+ 是非常有意义的。在各种 Hg2+ 检测技术中,荧光化学传感器具有操作简便、成本低廉、选择性高、可进行细胞成像等优点。本研究成功开发了一种新型 "开启式 "荧光化学传感器--硫脲-DHP 衍生物(TUD),它对 Hg2+ 具有高选择性。TUD 是由β-氨基丙烯酸酯环化合成的,然后用二甲基氨基硫代羰酰氯对生成的二氢吡啶(DHP)进行硫代酰化。在黑光灯下,TUD 对 Hg2+ 的检测显示出惊人的裸眼蓝色荧光信号,在 pH 值为 7.4 的 HEPES 缓冲液中,检测限为 69 nM 或 14 ppb。Hg2+ 诱导的低荧光 TUD 水解脱硫产生强荧光脲-DHP(UD)被认为是这种荧光增强的机制。1H NMR、13C NMR 和 HRMS 证实了 UD 的形成。这种 TUD 检测系统对实际环境水样中 Hg2+ 污染物的分析具有极高的回收率(97%)。此外,即使在高浓度(100 µM)下,TUD 探针在活细胞中对 RAW264.7 鼠巨噬细胞系也显示出无毒性。与目前的汞脱硫荧光化学传感器相比,我们提出的 TUD 探针在纯水介质中表现出更高的灵敏度。事实证明,这种传感系统能有效分析实际环境水样中的 Hg2+ 污染物。此外,无毒 TUD 探针成功揭示了在活细胞中检测 Hg2+ 的显著生物相容性。
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