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Breakthroughs in nanostructured-based chemical sensors for the detection of toxic metals 用于检测有毒金属的纳米结构化学传感器取得突破性进展
IF 4.1 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-09-10 DOI: 10.1016/j.talo.2024.100354
Tinsae F. Gezahegn , Abera D. Ambaye , Tewolde M. Mekoyete , Mope E. Malefane , Kabir O. Oyedotun , Touhami Mokrani

Globally, trace metals toxicity in wastewater poses health problems for humans even at truncated concentrations and warrants investigation. This review study focuses on the suitable cutting-edge advancements in nanotechnology-based electrochemical sensor technology for the apprehension of selected toxic metal ions such as arsenic(As), cadmium(Cd), chromium(Cr), lead(Pb), and uranium(Ur)) in wastewater samples. The discussion includes an examination of synthesis techniques for sensors based on Nanomaterials (NMs). Moreover, these electrochemical sensors are scrutinized to study the complex principles that describe their problem solving achievement, such as susceptibility, determination limit, duplicability, repeatability, and selectivity in wastewater matrices for trace metal detection. Most importantly, the discussion also considers the interactions between NMs, electrochemistry, and sensing mechanisms, providing a comprehensive view of the cooperative developments promoting improved advanced sensor technology. This review critically investigates the existing literature to assess and capture the progress landscape of nano-based electrochemical sensors. Ultimately, this review paper could significantly play a role towards the use of these attractive nano-based electrode materials in revamping paradigms for environmental monitoring and advancing precision in trace metal sensing in wastewater.

在全球范围内,废水中的痕量金属即使在浓度很低的情况下也会对人类健康造成危害,因此有必要进行研究。本综述研究的重点是基于纳米技术的电化学传感器技术在检测废水样本中砷(As)、镉(Cd)、铬(Cr)、铅(Pb)和铀(Ur)等特定有毒金属离子方面的最新进展。讨论包括对基于纳米材料 (NM) 的传感器合成技术的研究。此外,还对这些电化学传感器进行了仔细研究,以了解其解决问题的复杂原理,如在废水基质中检测痕量金属时的易感性、测定极限、可重复性、可重复性和选择性。最重要的是,讨论还考虑了非金属、电化学和传感机制之间的相互作用,为促进先进传感器技术改进的合作发展提供了一个全面的视角。本综述对现有文献进行了批判性研究,以评估和把握基于纳米的电化学传感器的进展情况。最终,这篇综述论文将对这些极具吸引力的纳米电极材料在环境监测范式改革和提高废水中痕量金属传感精度方面的应用起到重要作用。
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引用次数: 0
Comprehensive numerical prototyping of paper-based microfluidic devices using open-source tools 利用开源工具对纸质微流体设备进行综合数值原型制作
IF 4.1 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-09-02 DOI: 10.1016/j.talo.2024.100350
Gabriel S. Gerlero , Zahar I. Guerenstein , Nicolás Franck , Claudio L.A. Berli , Pablo A. Kler

Paper-based microfluidics has emerged as a promising field with diverse applications ranging from medical diagnostics to environmental monitoring. Despite significant progress in research and development, the translation of paper-based prototypes into practical end-user devices remains limited. This limitation stems from challenges related to devices not being sufficiently portable and autonomous, which paper-based microfluidics is expected to overcome. Yet for this purpose, we note the lack of comprehensive numerical modeling tools capable of simulating the intricate physicochemical phenomena involved in order to optimize the development process; hence, in this study, we introduce porousMicroTransport, a novel simulation package integrated with the open-source platform OpenFOAM®, designed to address these challenges. porousMicroTransport offers efficient solvers for fluid flow and transport phenomena in microfluidic porous media, including capillarity models and (bio)chemical reactions. Moreover, under horizontal flow conditions, porousMicroTransport application field can be extended to any porous media. We demonstrate the software’s effectiveness in two example cases, showcasing its ability to accurately reproduce complex phenomena involved in paper-based devices. By virtue of being an easy-to-use and computationally efficient tool, porousMicroTransport facilitates the design and optimization of devices, potentially enabling more devices to meet the WHO’s REASSURED criteria for point-of-care testing. We anticipate that this tool will accelerate the development and deployment of robust and portable diagnostic devices, bridging the gap between research and practical applications.

纸基微流体技术已成为一个前景广阔的领域,其应用范围从医疗诊断到环境监测等多种多样。尽管在研究和开发方面取得了重大进展,但将纸基原型转化为实用的最终用户设备仍然有限。这种限制源于设备的便携性和自主性不足,而纸质微流体技术有望克服这些挑战。然而,我们注意到,目前缺乏全面的数值建模工具来模拟所涉及的复杂物理化学现象,以优化开发过程;因此,在本研究中,我们介绍了 porousMicroTransport,这是一款集成了开源平台 OpenFOAM® 的新型模拟软件包,旨在应对这些挑战。此外,在水平流动条件下,porousMicroTransport 的应用领域可以扩展到任何多孔介质。我们在两个示例中演示了该软件的有效性,展示了其准确再现纸质设备中复杂现象的能力。porousMicroTransport 是一款简单易用、计算效率高的工具,它有助于设备的设计和优化,使更多的设备符合世界卫生组织的 REASSURED 标准。我们预计,该工具将加速坚固耐用的便携式诊断设备的开发和部署,缩小研究与实际应用之间的差距。
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引用次数: 0
Fabrication of nanomolecular platform based immunosensor for non-invasive electrochemical detection of oral cancer: An in vitro study 基于纳米分子平台的免疫传感器的制作,用于口腔癌的无创电化学检测:体外研究
IF 4.1 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-09-01 DOI: 10.1016/j.talo.2024.100352
Meenakshi Choudhary , Vinay Kumar , Ashik Babu Parambath , Shruti Caplash , Birendra Kumar Yadav , Satbir Kaur , Sapna Ratan Shah , Kavita Arora

Silver nanoparticles (AgNPs)-Chitosan (Chi) functionalized cysteine (cys)-SAM (self-assembled monolayer) based electrochemical, label free, ultrasensitive, non-invasive immunosensing nanomolecular platform has been fabricated for the detection of novel OC biomarker S-100. This has been achieved through bio-functionalization of AgNPs-Chi/cys/mini gold slides by covalent immobilization of anti-S100 antibodies. Cyclic voltammetric (CV) studies establish successful fabrication of anti-S100/AgNPs-Chi/Au nanomolecular platform. Differential pulse voltammetric (DPV) measurements reveal that anti-S100/Chi-AgNPs/Au is able to sense 50 fg mL-1 – 500 ng mL-1 of S100 in buffer and in spiked saliva samples within 120 s interaction time having improved favorable shelf life and specificity. The fabricated platform is very selective and able to detect S100 in OC patient/s saliva samples warrants realization of simple non-invasive electrochemical immunosensor for in situ or on-site applications (especially for remote areas) for early diagnosis of OC while offering bio-compatibility at low cost.

为检测新型 OC 生物标志物 S-100,我们制作了基于银纳米粒子(AgNPs)-壳聚糖(Chi)-半胱氨酸(cys)-SAM(自组装单层)的电化学、无标记、超灵敏、非侵入性免疫传感纳米分子平台。这是通过共价固定抗 S100 抗体对 AgNPs-Chi/cys/mini 金片进行生物功能化实现的。循环伏安法(CV)研究证实了抗 S100/AgNPs-Chi/Au 纳米分子平台的成功制备。差分脉冲伏安法(DPV)测量结果表明,抗 S100/Chi-AgNPs/Au 能够在 120 秒的相互作用时间内感知缓冲液和加标唾液样品中 50 fg mL-1 - 500 ng mL-1 的 S100,并具有更好的保存期限和特异性。所制作的平台具有很高的选择性,能够检测 OC 患者/唾液样本中的 S100,因此可以实现简单的无创电化学免疫传感器,用于原位或现场应用(尤其是偏远地区),对 OC 进行早期诊断,同时具有低成本的生物兼容性。
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引用次数: 0
Biocompatible bright orange emissive carbon dots: Multifunctional nanoprobes for highly specific sensing toxic Cr(VI) ions and mitochondrial targeting cancer cell imaging 生物相容性亮橙色发光碳点:用于高特异性感测有毒六价铬离子和线粒体靶向癌细胞成像的多功能纳米探针
IF 4.1 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-30 DOI: 10.1016/j.talo.2024.100353
Ramar Rajamanikandan , D.S. Prabakaran , Kandasamy Sasikumar , Joo Seon Seok , Gyeongchan Lee , Heongkyu Ju

Although several luminescent-based nanostructured materials are used as cellular imaging probes, creating a biocompatible subcellular imaging probe can be challenging. Instantaneously, it is crucial and urgently needed for certain fluorescent nanoprobes to identify possibly harmful heavy metal ions. We present a straightforward one-pot preparation of bright orange emissive (quantum yield approximately 16 %) Nitrogen/Sulfur co-doped carbon dots (N/S CDs) from citric acid and methylene blue as raw materials that will serve as a specific Cr(VI) ions sensor and an effective mitochondrial labeling in cancer cells. They had several benefits including low ecological impact, facile synthesis, good water solubility, photostability, and high stability. We found that N/S CDs photoluminescence (PL) could be reduced when Cr(VI) ions were present near them, and the PL reduction occurred highly sensitively to the presence of Cr(VI) compared to other metal ions including Cr(III) ions. This specific reduction of PL was due to the non-fluorescent complex formation through the inner filter effect (IFE). The established fluorescence-based sensing technique could serve for Cr(VI) ion quantification with exceptional sensing efficiency in the wide linear range of 7 to 70 μM (R2 = 0.9873), with the limit of detection of 53.5 nM. It was also revealed that the current fluorescent probe could be encouragingly utilized to quantify the concentration of Cr(VI) ions in various water specimens such as tap water. In addition, they were shown to function as a mitochondria-targeting nanoprobe in human cancer cells (ME 180 cells and Hela cells) for cell imaging. Concludingly, it was envisioned that these fluorescent nanoprobes could find a use in real-time monitoring of Cr(VI) ions in water-based ecosystems with ultrahigh sensitivity and cell image tracking via mitochondria labeling as biocompatible nanoprobes.

尽管有几种基于发光的纳米结构材料被用作细胞成像探针,但制造一种生物相容性亚细胞成像探针仍具有挑战性。当下,迫切需要某些荧光纳米探针来识别可能有害的重金属离子。我们介绍了一种以柠檬酸和亚甲基蓝为原料、一次性制备亮橙色发射型(量子产率约为 16%)氮/硫共掺杂碳点(N/S CD)的方法,该方法可用作特定的六(VI)铬离子传感器和有效的癌细胞线粒体标记。它们具有生态影响小、合成简便、水溶性好、光稳定性和高稳定性等优点。我们发现,当 N/S CD 附近存在六价铬离子时,N/S CD 的光致发光(PL)会减弱,与包括三价铬离子在内的其他金属离子相比,PL 的减弱对六价铬离子的存在非常敏感。这种特定的聚光减少是由于通过内滤光片效应(IFE)形成了非荧光复合物。已建立的基于荧光的传感技术可用于六价铬离子的定量分析,在 7 至 70 μM 的宽线性范围内具有极高的传感效率(R2 = 0.9873),检测限为 53.5 nM。研究还发现,目前的荧光探针可用于量化自来水等各种水样中六价铬离子的浓度,效果令人鼓舞。此外,在人类癌细胞(ME 180 细胞和 Hela 细胞)的细胞成像中,它们还可作为线粒体靶向纳米探针发挥作用。总之,这些荧光纳米探针作为生物相容性纳米探针,可用于实时监测水基生态系统中的六(Cr)离子,并通过线粒体标记实现超高灵敏度和细胞图像跟踪。
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引用次数: 0
Design and preparation of a fluorescent molecularly imprinted membrane for the selective detection of pepsin enzyme as a biomarker for gastroesophageal reflux disease 设计和制备用于选择性检测胃蛋白酶的荧光分子印迹膜,作为胃食管反流病的生物标记物
IF 4.1 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-26 DOI: 10.1016/j.talo.2024.100351
Aya M. Mostafa , Stephen J. Barton , Stephen P. Wren , James Barker

A novel fluorescent molecularly imprinted polymer membrane (FMIM) has been developed for the selective binding and qualitative detection of pepsin enzyme, a biomarker indicative of gastroesophageal reflux disease (GERD). This study utilises the high selectivity offered by molecular imprinting techniques to capture pepsin enzyme within complex biological matrices, such as human saliva. Additionally, fluorescent carbon dots integrated into the membrane matrix provide instant visual detection of pepsin. Various combinations of functional monomers and cross-linkers were systematically evaluated to investigate their impact on the binding capacity and mechanical stability of the resultant FMIMs. The optimum performance was achieved with a mixture of two hydrophilic monomers, namely N-(hydroxymethyl)acrylamide and acrylamide, in conjunction with N,N-methylenebis(acrylamide) as the cross-linking agent. The developed FMIM demonstrated a binding capacity of 21.56 mg g-1, surpassing that of the fluorescent non-imprinted membrane (FNIM) at 8.49 mg g-1. Moreover, the binding of FMIM to pepsin was tested against other competitor enzymes to verify its selectivity. Furthermore, comprehensive characterisation of both FMIM and FNIM was conducted using various analytical techniques to ensure their structural integrity and functionality. Ultimately, the developed FMIM exhibited effective binding of pepsin in standard solutions and samples, enabling enrichment and visual detection of the biomarker enzyme.

我们开发了一种新型荧光分子印迹聚合物膜(FMIM),用于选择性结合和定性检测胃蛋白酶,胃蛋白酶是胃食管反流病(GERD)的一种生物标志物。这项研究利用分子印迹技术提供的高选择性,在复杂的生物基质(如人类唾液)中捕获胃蛋白酶。此外,集成到膜基质中的荧光碳点可提供胃蛋白酶的即时视觉检测。我们系统地评估了功能单体和交联剂的各种组合,以研究它们对最终 FMIMs 的结合能力和机械稳定性的影响。两种亲水性单体(即 N-(羟甲基)丙烯酰胺和丙烯酰胺)的混合物与 N,N-亚甲基双(丙烯酰胺)作为交联剂的组合达到了最佳性能。所开发的 FMIM 的结合能力为 21.56 mg g-1,超过了 8.49 mg g-1 的荧光非压印膜(FNIM)。此外,还测试了 FMIM 与胃蛋白酶和其他竞争酶的结合情况,以验证其选择性。此外,还使用各种分析技术对 FMIM 和 FNIM 进行了全面表征,以确保其结构完整性和功能性。最终,开发的 FMIM 在标准溶液和样品中显示出与胃蛋白酶的有效结合,实现了生物标记酶的富集和可视检测。
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引用次数: 0
Evaluation of cannabis product mislabeling: The development of a unified cannabinoid LC-MS/MS method to analyze e-liquids and edible products 评估大麻产品的错误标签:开发用于分析电子液体和食用产品的统一大麻素 LC-MS/MS 方法
IF 4.1 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-24 DOI: 10.1016/j.talo.2024.100349
Ashleigh E. Outhous , Alaina K. Holt , Justin L. Poklis , Michelle R. Peace

The 2018 Agricultural Improvement Act federally legalized the cultivation of hemp and manufacture and sale of cannabidiol (CBD). The overproduction of CBD led to a significant drop in price. To maintain profitability, manufacturers began producing synthetic and semi-synthetic cannabinoids, marketing them as “legal” and “hemp-derived” due to their synthesis from CBD. The cannabis industry is adaptable, and laboratories have struggled to keep up with the rapid emergence of new compounds. This has resulted in products with unlabeled or mislabeled cannabinoids, causing unexpected adverse events. A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for the separation and quantitation of 21 cannabinoids. The method was applied in the analysis of 55 commercially available products. Results demonstrate significant issues with quality assurance and labeling in the unregulated cannabis market. Many products either did not contain the cannabinoids listed on their labels or contained cannabinoids that were not listed. When cannabinoids were present, their concentrations were often incorrect, with some products showing high concentrations that could pose a potential health risk. Moreover, safety, dosing, and other pharmacological data of these newly proliferated cannabinoids are lacking. Reports of adverse events are increasing to poison controls centers and emergency departments following cannabis product use. Often, the actual cannabinoids involved in the case reprots are not determined. It is critical to develop more comprehensive testing methodologies to determine the content of cannabis products and to implement stronger quality assurance measures and regulations to protect the public from low-quality and potentially dangerous products.

2018 年《农业改进法案》在联邦范围内将大麻种植以及大麻二酚(CBD)的生产和销售合法化。CBD 的过度生产导致价格大幅下跌。为了保持盈利能力,制造商开始生产合成和半合成大麻素,并以 "合法 "和 "大麻衍生 "的名义进行营销,因为它们是由 CBD 合成的。大麻产业的适应性很强,实验室一直在努力跟上新化合物的快速出现。这导致产品中的大麻素未加标识或标识错误,引发意想不到的不良事件。我们开发了一种液相色谱-串联质谱(LC-MS/MS)方法,用于分离和定量 21 种大麻素。该方法被用于分析 55 种市售产品。结果表明,在不受监管的大麻市场上,质量保证和标签存在重大问题。许多产品要么不含标签上列出的大麻素,要么含有未列出的大麻素。即使含有大麻素,其浓度也往往不正确,一些产品显示的高浓度可能对健康构成潜在风险。此外,这些新增产的大麻素的安全性、剂量和其他药理数据也缺乏。毒物控制中心和急诊科接到的使用大麻产品后发生不良事件的报告越来越多。通常情况下,无法确定病例中涉及的实际大麻素。关键是要制定更全面的检测方法来确定大麻产品的含量,并实施更有力的质量保证措施和法规,以保护公众免受劣质和潜在危险产品的危害。
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引用次数: 0
Carbon quantum dots from natural sources as sustainable probes for metal ion sensing: Preparation, characterizations and applications 将天然来源的碳量子点作为金属离子传感的可持续探针:制备、表征和应用
IF 4.1 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-23 DOI: 10.1016/j.talo.2024.100348
Mahmoud Hamed , Sampath Chinnam , Alaa Bedair , Samy Emara , Fotouh R. Mansour

Carbon Quantum Dots from Natural Sources (NACQDs) is a novel type of carbon-based material that have garnered significant attention due to their remarkable features, including luminescence, photostability, nanoscale size, water solubility, low toxicity, biocompatibility, and cost-effectiveness. The synthesis of NACQDs involves a diverse range of natural sources, such as fruits, foods, beverages, human and animal derivatives, vegetables, leaves, and waste materials. Various synthesis methods, including electrochemical approach, chemical oxidation, hydrothermal carbonization, ultrasonic techniques, microwave-assisted synthesis, solvothermal method, laser ablation technique, thermolysis, and atmospheric plasma-based synthesis, have been explored to tailor the size and properties of NACQDs. Characterization techniques like Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TЕM), ultraviolet absorption, fluorescence properties, and nuclear magnetic resonance (NMR) have provided invaluable insights into the physical and chemical characteristics of NACQDs. This review highlights the immense potential of NACQDs in metal ion sensing applications and underscores the need for further investigation to enhance their reproducibility and precise control over their properties. NACQDs hold great promise as versatile nanomaterials for metal ion sensing and are poised to revolutionize diverse fields, ranging from environmental monitoring to biomedical diagnostics and chemical analysis.

天然来源碳量子点(NACQDs)是一种新型碳基材料,因其发光、光稳定性、纳米级尺寸、水溶性、低毒性、生物相容性和成本效益等显著特点而备受关注。NACQDs 的合成涉及多种天然来源,如水果、食品、饮料、人类和动物衍生物、蔬菜、树叶和废料。为了定制 NACQDs 的尺寸和性质,人们探索了各种合成方法,包括电化学方法、化学氧化、水热碳化、超声波技术、微波辅助合成、溶热法、激光烧蚀技术、热解和基于大气等离子体的合成。傅立叶变换红外光谱 (FTIR)、X 射线衍射 (XRD)、透射电子显微镜 (TЕM)、紫外线吸收、荧光特性和核磁共振 (NMR) 等表征技术为了解 NACQDs 的物理和化学特性提供了宝贵的见解。本综述强调了 NACQDs 在金属离子传感应用中的巨大潜力,并强调了进一步研究以提高其可重复性和精确控制其特性的必要性。作为金属离子传感的多功能纳米材料,NACQDs 前景广阔,有望在环境监测、生物医学诊断和化学分析等多个领域掀起一场革命。
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引用次数: 0
Reduction with zinc — Impact on the determination of nitrite and nitrate ions using microfluidic paper-based analytical devices 锌还原--对使用微流控纸质分析装置测定亚硝酸盐和硝酸盐离子的影响
IF 4.1 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-08-10 DOI: 10.1016/j.talo.2024.100347
Mika I. Umeda , Kaewta Danchana , Takatoshi Fujii , Eiichi Hino , Yusuke Date , Kaoru Aoki , Takashi Kaneta

We used a microfluidic paper-based analytical device (μPAD) to investigate the influence that zinc reduction exerts on the determination of nitrite and nitrate ions in natural water samples. The μPAD consists of layered channels for the reduction of nitrate to nitrite with zinc powder and the subsequent detection of nitrite with Griess reagent. The amount of zinc, number of layers, and reaction time for the reduction were optimized to obtain an intense signal for nitrate. Initially, the sensitivity to nitrate corresponded to 55% that of nitrite, which implied an incomplete reduction. We found, however, that zinc decreased the sensitivity to nitrite in both the μPAD and spectrophotometry. The sensitivity to nitrite was decreased by 48% in spectrophotometry and 68% in the μPAD following the reaction with zinc. One of the reasons for the decreased sensitivity is attributed to the production of ammonia, as we elucidated that both nitrite and nitrate produced ammonia via the reaction with zinc. The results suggest that the total concentration of nitrite and nitrate must be corrected by constructing a calibration curve for nitrite with zinc, in addition to developing curves for nitrate with zinc and for nitrite without zinc. Using these calibration curves, the absorbance at different concentration ratios of nitrite and nitrate ions could be reproduced via calculation using the calibration curves with zinc for nitrite and nitrate. Eventually, the developed μPAD was applied to the determination of nitrite and nitrate ions in natural water samples, and the results were compared with those using a conventional spectrophotometric method. The results of the μPAD are in good agreement with those of conventional spectrophotometry, which suggests that the μPAD is reliable for the measurement of nitrite and nitrate ions in natural water samples.

我们利用微流体纸基分析装置(μPAD)研究了锌还原对天然水样中亚硝酸盐和硝酸根离子测定的影响。μPAD 由分层通道组成,用于用锌粉将硝酸盐还原成亚硝酸盐,然后用格里丝试剂检测亚硝酸盐。对锌的用量、层数和还原反应时间进行了优化,以获得强烈的硝酸盐信号。最初,对硝酸盐的灵敏度为亚硝酸盐的 55%,这意味着还原不完全。但我们发现,锌降低了μPAD和分光光度法对亚硝酸盐的灵敏度。与锌反应后,分光光度法对亚硝酸盐的敏感性降低了 48%,μPAD 降低了 68%。灵敏度降低的原因之一是氨的产生,因为我们发现亚硝酸盐和硝酸盐都会通过与锌的反应产生氨。结果表明,亚硝酸盐和硝酸盐的总浓度必须通过构建一条含锌亚硝酸盐的校准曲线来校正,此外还必须绘制含锌硝酸盐和不含锌亚硝酸盐的曲线。利用这些校准曲线,通过计算亚硝酸盐和硝酸盐的含锌校准曲线,可以再现亚硝酸盐和硝酸盐离子在不同浓度比时的吸光度。最后,将开发的 μPAD 应用于天然水样中亚硝酸盐和硝酸盐离子的测定,并将结果与传统的分光光度法进行了比较。结果表明,μPAD 与传统分光光度法的结果非常吻合,这表明μPAD 可以可靠地测定天然水样中的亚硝酸盐和硝酸盐离子。
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引用次数: 0
Comparison of head space solid phase micro extraction with conventional and comprehensive gas chromatography mass spectrometry for volatile profiling of Irish whiskey 用于爱尔兰威士忌挥发性成分分析的顶空固相微萃取与常规和综合气相色谱质谱法的比较
IF 4.1 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-07-17 DOI: 10.1016/j.talo.2024.100346
Thomas J. Kelly , David T. Mannion , Christine O'Connor , Kieran N. Kilcawley

Whiskey is a traditional distilled product produced on the island of Ireland that is currently experiencing a major expansion in export volume. Different styles of Irish whiskey exist, however only some very limited published information exists on the volatile congener profile of the different styles of Irish whiskey. Such information is potentially indispensable from a quality, flavour and authenticity perspective. As gas chromatography is the established analytical method of choice to identify volatile congeners, this study compared headspace-solid phase microextraction (HS-SPME) using conventional gas chromatography single quadrupole mass spectrometry, to HS-SPME and HS-SPME-Arrow using comprehensive two-dimensional gas chromatography (GC×GC) modulated using reverse flow in tandem with time-of-flight mass spectrometry (TOFMS) detection. Six representative Irish whiskey samples were evaluated consisting of new make spirit and mature whiskies representing Single Malts, Pot Stills and Blends. The number of volatile congeners identified in these samples by HS-SPME/HS-SPME Arrow GC×GC-TOFMS was approximately twice that detected by conventional HS-SPME GCMS. In total 145 unique individual volatile congeners, excluding ethanol were identified, with the majority consisting of esters, but also benzenes, alcohols, aldehydes, terpenoids, furans, ketones, alkanes, alkenes, norisoprenoids, acetals, acids, lactones and phenols. The use of HS-SPME Arrow GC×GC-TOFMS significantly enhances the number of volatile congeners that can be identified and therefore provides much more information that can convey insights into product quality, consistency, flavour and also for authentication purposes.

威士忌是爱尔兰岛上生产的一种传统蒸馏产品,目前出口量正在大幅增长。爱尔兰威士忌有不同的风格,但关于不同风格的爱尔兰威士忌的挥发性同系物概况,目前仅有一些非常有限的公开信息。从质量、风味和真实性的角度来看,这些信息可能是不可或缺的。由于气相色谱法是鉴别挥发性同系物的首选分析方法,因此本研究将使用传统气相色谱单四极杆质谱法的顶空固相微萃取 (HS-SPME) 与使用综合二维气相色谱 (GC×GC) 的 HS-SPME 和 HS-SPME-Arrow 与使用反向流串联飞行时间质谱 (TOFMS) 检测的 HS-SPME 和 HS-SPME-Arrow 进行了比较。对六种具有代表性的爱尔兰威士忌样品进行了评估,其中包括新酿酒和成熟威士忌,分别代表单一麦芽威士忌、蒸馏威士忌和混合威士忌。通过 HS-SPME/HS-SPME Arrow GC×GC-TOFMS 在这些样品中鉴定出的挥发性同系物数量约为传统 HS-SPME GCMS 检测到的同系物数量的两倍。除乙醇外,总共鉴定出 145 种独特的挥发性同系物,其中大部分是酯类,但也包括苯、醇、醛、萜类、呋喃、酮、烷、烯、去甲异戊烯、乙醛、酸、内酯和酚。HS-SPME Arrow GC×GC-TOFMS 的使用大大增加了可鉴定的挥发性同系物的数量,因此可提供更多的信息,有助于深入了解产品质量、一致性、风味以及鉴定目的。
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引用次数: 0
Rapid classification of rice according to storage duration via near-infrared spectroscopy and machine learning 通过近红外光谱和机器学习,根据储存时间对大米进行快速分类
IF 4.1 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-07-14 DOI: 10.1016/j.talo.2024.100343
Chen Zhai , Wenxiu Wang , Man Gao , Xiaohui Feng , Shengjie Zhang , Chengjing Qian

Rice is the most important staple crop for more than half of the world's population. As rice quality can deteriorate during storage, methods that can effectively classify rice according to its storage duration are essential. However, existing methods of assessing rice storage time are time-consuming, laborious, and incompatible with modern industrial processing technologies. Therefore, we investigated the ability of near-infrared spectroscopy combined with machine learning algorithms to distinguish rice storage duration. A total of 482 rice samples were analyzed, which included 74, 100, and 308 samples produced during 2015–2016, 2017–2018, and 2020–2021, respectively. Five pre-processing methods were initially applied to the spectra to enhance the accuracy of the discrimination model. Subsequently, two-dimensional correlation spectroscopy and competitive adaptive reweighted sampling (CARS) were used to extract the characteristic spectra associated with storage time. Finally, three pattern recognition methods (K-nearest neighbor analysis, linear discriminant analysis, and least squares support vector machine (LS-SVM)) were compared for their effectiveness in constructing classification models. The results indicated that the best model for identifying the storage duration of rice was established after spectral pre-processing with the standard normal variate and first derivative, using the CARS algorithm to select feature wavelengths, and applying the LS-SVM modeling method, which together yielded correct identification rates of 99.72 % and 91.67 % for the calibration and validation sets, respectively. Thus, we propose near-infrared spectroscopy coupled with machine learning algorithms as an effective approach for classifying rice according to storage duration, which can facilitate evaluations of rice freshness in the market.

大米是世界上一半以上人口最重要的主食作物。由于大米在储存过程中质量会下降,因此根据储存时间对大米进行有效分类的方法至关重要。然而,现有的大米储存时间评估方法费时、费力,而且与现代工业加工技术不兼容。因此,我们研究了近红外光谱与机器学习算法相结合来区分大米储藏时间的能力。共分析了 482 份大米样品,其中包括 2015-2016 年、2017-2018 年和 2020-2021 年分别生产的 74 份、100 份和 308 份样品。最初对光谱采用了五种预处理方法,以提高判别模型的准确性。随后,使用二维相关光谱法和竞争性自适应再加权采样法(CARS)提取与存储时间相关的特征光谱。最后,比较了三种模式识别方法(K-近邻分析、线性判别分析和最小二乘支持向量机(LS-SVM))在构建分类模型方面的有效性。结果表明,在使用标准正态变分和一阶导数进行光谱预处理、使用 CARS 算法选择特征波长并应用 LS-SVM 建模方法后,建立了识别水稻储藏期的最佳模型,在校准集和验证集上的正确识别率分别为 99.72 % 和 91.67 %。因此,我们建议将近红外光谱仪与机器学习算法相结合,作为一种根据储存时间对大米进行分类的有效方法,从而促进市场上对大米新鲜度的评估。
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