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Bimetallic MOFs-derived four-in-one CeCuOx/C nanozyme and its application for colorimetric detection of cysteine based on oxidase mimics 双金属 MOFs 衍生的四合一 CeCuOx/C 纳米酶及其在基于氧化酶模拟物的半胱氨酸比色检测中的应用
Q3 Chemistry Pub Date : 2024-02-01 DOI: 10.1016/j.talo.2024.100292
Wen-Xuan Jia, Ming-Ming Tao, Xin-Yu Wang, Yan-Feng Huang, Ying Li

To address the limitations of natural enzymes, more and more artificial enzymes have been developed. As the most appropriate candidate, metal organic frameworks (MOFs) and MOFs-based derivatives have generated extensive interest due to their remarkable properties and potential applications in enzymes mimicry. In this work, Ce/Cu mixed metal oxides-carbon composite (CeCuOx/C) was synthesized through a simple oxidation method with bimetallic MOFs CeCu-BTC as precursors. It was found that the prepared CeCuOx/C possess four different enzyme-like activities, including peroxidase, oxidase, laccase and phosphatase mimetic activities. The kinetics parameters and potential influence factors of enzyme-like activities were studied and CeCuOx/C exhibited high catalytic activity, excellent stability, and reusability. Additionally, a cysteine detecting method was established via oxidase-like activity of CeCuOx/C. The linear response to the cysteine was in the range of 50 to 900 μM, and the limit of detection was 3.24 μM. The spiking recoveries were in the range 93.5–100.2 % for cysteine in artificial human urine samples and the relative standard deviations were found within the ranges of 1.2–2.9 %. This work presents a new approach for the design of multi-enzyme mimics and develops the potential of CeCuOx/C for biological sensing.

为了解决天然酶的局限性,越来越多的人工酶被开发出来。作为最合适的候选材料,金属有机框架(MOFs)和基于MOFs的衍生物因其卓越的性能和在酶模拟中的潜在应用而引起了广泛的兴趣。本研究以双金属 MOFs CeCu-BTC 为前驱体,通过简单的氧化方法合成了 Ce/Cu 混合金属氧化物-碳复合材料(CeCuOx/C)。研究发现,所制备的 CeCuOx/C 具有四种不同的类酶活性,包括过氧化物酶、氧化酶、漆酶和磷酸酶模拟活性。研究了类酶活性的动力学参数和潜在影响因素,结果表明 CeCuOx/C 具有催化活性高、稳定性好和可重复使用等特点。此外,还通过 CeCuOx/C 的类氧化酶活性建立了一种半胱氨酸检测方法。半胱氨酸的线性范围为 50 至 900 μM,检出限为 3.24 μM。人工人体尿样中半胱氨酸的加标回收率为 93.5%-100.2%,相对标准偏差为 1.2%-2.9%。这项工作为多酶模拟物的设计提供了一种新方法,并开发了 CeCuOx/C 在生物传感方面的潜力。
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引用次数: 0
Electroanalysis overview: The determination of the poisoner's poison, thallium 电分析概述:毒药铊的测定
Q3 Chemistry Pub Date : 2024-01-29 DOI: 10.1016/j.talo.2024.100291
Robert D. Crapnell, Craig E. Banks

In this overview, we explore the electroanalytical determination of the poisoner's poison: thallium. Thallium was named after the Greek word "thallos," meaning "green shoot" or "twig," due to its bright green spectral emission lines. It is toxic, tasteless, odourless and dissolves into water, and has been used by murderers as a challenging poison to detect and there is the need for the analytical determination of thallium. Laboratory based analytical instrumentation provide a routine methodology to measure thallium, but there is scope to develop in-the-field analytical measurements that are comparable to laboratory equipment and in some cases, they can provide even more sensitive analytical approaches. Electrochemistry can support such endeavours, where instrumentation are readily portable where electroanalytical sensors provide highly selective and sensitive outputs but yet are economical to support on-site analysis. In this review, we provide an electroanalytical overview of the current research directed toward the measurement of thallium and offer insights to future research.

在本综述中,我们将探讨电分析法测定毒药的方法:铊。铊的名字来源于希腊语 "thallos",意为 "绿芽 "或 "树枝",这是因为它具有明亮的绿色光谱发射线。铊有毒、无味、无臭,可溶解于水,曾被谋杀犯用来作为一种难以检测的毒药,因此有必要对铊进行分析测定。基于实验室的分析仪器提供了测量铊的常规方法,但还可以开发与实验室设备相当的现场分析测量方法,在某些情况下,它们甚至可以提供更灵敏的分析方法。电化学可为此类工作提供支持,因为仪器便于携带,电分析传感器可提供高选择性和高灵敏度的输出结果,而且经济实惠,可支持现场分析。在本综述中,我们将概述目前针对铊测量的电分析研究,并对未来研究提出见解。
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引用次数: 0
Metal oxide/g-C3N4 nanocomposites chemiresistive gas sensors: A review on enhanced performance 金属氧化物/g-C3N4 纳米复合材料化学电阻式气体传感器:性能提升综述
Q3 Chemistry Pub Date : 2024-01-26 DOI: 10.1016/j.talo.2024.100290
Vahid Khoramshahi , Majid Azarang , Morteza Nouri , Abbas Shirmardi , Ramin Yousefi

Metal-oxide-semiconductors (MOS) gas sensors are widely used for detecting and measuring the concentration of various gases in different applications. Changing the electrical resistance when the MOS surface reacts with a specific gas is the basis of the operation of the gas sensor of MOS. They offer versatility in detecting various gases and fabricating them suitable for supervising energy efficiency, monitoring health and safety, and controlling hazardous emissions. However, traditional MOS sensors suffer from poor selectivity and usually require high operating temperatures. To overcome these limitations, researchers have explored strategies such as doping, bimetallic/co-doping, and composite structures with conductive polymers and 2D materials such as polyaniline (PANI), polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), reduced graphene oxide (rGO), graphitic carbon nitride (g-C3N4), and graphene. Among the 2D materials, g-C3N4 stands out due to its distinct characteristics, including chemical stability, porosity structure, abundance, lack of toxicity, and numerous surface defects. The exfoliated structure and surface defects of g-C3N4 provide active sites for adsorbing atmospheric oxygen and facilitating reactions with specific gas molecules. This review introduces MOS gas sensors, covering their fabrication methods and electrical measurements. It then attentions on the properties of g-C3N4, synthesis methods, and its potential for composition with the MOS. The review highlights the enhanced gas sensing performance achieved by MOS/g-C3N4 nanocomposites to detect different gases.

金属氧化物半导体(MOS)气体传感器在不同的应用中被广泛用于检测和测量各种气体的浓度。MOS 表面与特定气体反应时电阻的变化是 MOS 气体传感器工作的基础。MOS 气体传感器具有检测各种气体的多功能性,适用于监督能源效率、监测健康和安全以及控制有害气体排放。然而,传统的 MOS 传感器选择性差,通常需要较高的工作温度。为了克服这些局限性,研究人员探索了各种策略,如掺杂、双金属/共掺杂,以及与导电聚合物和二维材料(如聚苯胺(PANI)、聚甲基丙烯酸甲酯(PMMA)、聚乙烯醇(PVA)、还原氧化石墨烯(rGO)、氮化石墨碳(g-C3N4)和石墨烯)的复合结构。在二维材料中,g-C3N4 因其化学稳定性、多孔结构、丰度、无毒性和众多表面缺陷等显著特点而脱颖而出。g-C3N4 的剥离结构和表面缺陷为吸附大气中的氧气和促进与特定气体分子的反应提供了活性位点。本综述介绍了 MOS 气体传感器,包括其制造方法和电学测量。然后重点介绍 g-C3N4 的特性、合成方法及其与 MOS 构成的潜力。综述重点介绍了 MOS/g-C3N4 纳米复合材料在检测不同气体方面所实现的增强气体传感性能。
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引用次数: 0
Gut-liver interaction study on an all-polydimethylsiloxane microfluidic device integrating intestinal paracellular permeability assay 全聚二甲基硅氧烷微流控装置与肠道旁通透性测定相结合的肠道与肝脏相互作用研究
Q3 Chemistry Pub Date : 2024-01-21 DOI: 10.1016/j.talo.2024.100289
Ryuya Kida , Alan Rajendran , Mamiko Tsugane , Jean-Charles Duclos-Vallée , Maxime M Mahe , Sakina Bensalem , Hiroaki Suzuki , Bruno Le Pioufle

Microphysiological systems (MPSs) have attracted increasing attention as a method for simulating in vitro drug efficiency. In particular, the interaction between liver and intestine tissues is one of the primary targets since they are closely involved in drug absorption and metabolism. However, most of the intestine-liver MPSs reported previously require pumps, electrodes, and porous membranes for co-culture of cells and evaluation of intestinal permeability (i.e., Trans-Epithelial Electrical Resistance, TEER), requiring complex manufacturing processes and operations. In this study, we report an all-polydimethylsiloxane (PDMS) co-culture microfluidic device, connecting microchamber-based paracellular transport assay on gut microtissues to liver tissues matured on the same device. On one side of the device, HepaRG cells are confined within thin parallel grooves that induce their differentiation into hepatocytes. The other side of the device is connected with microchannels to the liver side and includes the gut tissues, organized above microchambers. Such microchambers allow the evaluation of paracellular permeability by fluorescence imaging. Thanks to the microfluidic device we investigated changes in intestinal permeability induced by differentiated hepatocyte excretion and found that Caco-2 permeability was decreased when co-culture with HepaRG. Due to its simplicity and straightforward implementation, this method is anticipated as an innovative and efficient approach to assess tissue barrier function in multi-organ on-chip experiments.

微观生理学系统(MPS)作为一种模拟体外药物效率的方法,已经引起了越来越多的关注。特别是肝脏和肠道组织之间的相互作用是主要目标之一,因为它们密切参与药物的吸收和代谢。然而,之前报道的大多数肠肝 MPS 都需要泵、电极和多孔膜来共同培养细胞和评估肠道渗透性(即跨上皮电阻,TEER),需要复杂的制造工艺和操作。在这项研究中,我们报告了一种全聚二甲基硅氧烷(PDMS)共培养微流控装置,它将基于微室的肠道微组织旁细胞转运检测与在同一装置上成熟的肝组织连接起来。在装置的一侧,HepaRG 细胞被限制在平行的细槽中,诱导其分化为肝细胞。装置的另一侧通过微通道与肝脏一侧相连,包括肠道组织,组织在微室之上。这种微室可以通过荧光成像评估细胞旁通透性。借助微流控装置,我们研究了分化肝细胞排泄物引起的肠道通透性变化,发现与 HepaRG 共同培养时,Caco-2 的通透性降低。这种方法简单易行,有望成为在芯片上进行多器官实验时评估组织屏障功能的一种创新而有效的方法。
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引用次数: 0
NNNPERFUME: Detection of 8-oxoguanine DNA glycosylase activity based on primer exchange reaction and functionalized hemin/G-quadruplex DNAzyme NNNPERFUME:基于引物交换反应和功能化海明/G-四链DNA酶的8-氧鸟嘌呤DNA糖基化酶活性检测
Q3 Chemistry Pub Date : 2024-01-14 DOI: 10.1016/j.talo.2024.100288
Kaiting Xiao , Yanming Lai , Xingxing Liu, Shengjie Li, Wenxu Yuan, Ziyun Wang, Pan Pan, Yongkui Li, Heng Xiao

Background

8-oxoguanine DNA glycosylase can maintain genomic stability and integrity. However, it can interfere with the regular DNA damage repair process, possibly leading to the development of cancer and various other human diseases when its activity becomes abnormal. Current methods for detecting 8-oxoguanine DNA glycosylase activity often suffer from low sensitivity, time-consuming procedures, labor-intensive requirements, and the need for specialized equipment and trained professionals for execution. Consequently, there is an urgent need for a portable, user-friendly 8-oxoguanine DNA glycosylase assay that offers swift results and supports real-time testing.

Results

We've developed a PERFUME method that combines primer exchange reaction and functionalized G-quadruplex/hemin DNAzyme for sensitive detection of Fpg, a typical 8-oxoguanine DNA glycosylase. Utilizing a single probe and T4 Polynucleotide Kinase (PNK) simplifies the experiment to a one-step reaction at 37 °C in 3 h, reducing sample consumption and improving sensitivity. We chose functionalized hemin cofactors, significantly improving catalytic efficiency and enhancing detection capability. This biosensor detects Fpg activity with a sensitivity as low as 0.11 U mL−1, displaying exceptional sensitivity, selectivity, and interference resistance in human serum and bacterial cell extracts under isothermal conditions. The biosensor demonstrates remarkable selectivity and ability for Fpg inhibitors screening. In addition, this biosensor enables reading the sample's RGB values using a smartphone, facilitating accurate quantification of Fpg activity without the necessity for specialized equipment.

Significance

PERFUME simplifies Fpg detection by using a single hairpin and PNK in a one-step process. We utilize FUME to enhance catalytic efficiency, it surpassing the performance of traditional G-quadruplex/hemin DNAzyme methods. This approach excels in analyzing Fpg in human serum and bacterial extracts. It allows quantitative Fpg detection using UV–Vis and smartphones under isothermal conditions, making it valuable for clinical diagnosis.

背景8-氧鸟嘌呤 DNA 糖基化酶可以维持基因组的稳定性和完整性。然而,当它的活性出现异常时,会干扰正常的 DNA 损伤修复过程,可能导致癌症和其他各种人类疾病的发生。目前检测 8-氧鸟嘌呤 DNA 糖基化酶活性的方法往往存在灵敏度低、程序耗时、劳动密集型要求以及需要专业设备和训练有素的专业人员来执行等问题。结果我们开发了一种 PERFUME 方法,该方法结合了引物交换反应和功能化 G-四链/海明 DNA 酶,可灵敏检测典型的 8-氧鸟嘌呤 DNA 糖基化酶 Fpg。利用单一探针和 T4 多核苷酸激酶(PNK)将实验简化为 37°C 下一步反应,只需 3 小时,从而减少了样品消耗,提高了灵敏度。我们选用了功能化的海明辅助因子,大大提高了催化效率和检测能力。在等温条件下,该生物传感器检测 Fpg 活性的灵敏度低至 0.11 U mL-1,在人血清和细菌细胞提取物中显示出卓越的灵敏度、选择性和抗干扰性。该生物传感器在筛选 Fpg 抑制剂方面具有显著的选择性和能力。此外,该生物传感器还能使用智能手机读取样品的 RGB 值,从而无需专业设备即可准确量化 Fpg 活性。我们利用 FUME 提高了催化效率,其性能超过了传统的 G-四链/hemin DNA 酶方法。这种方法在分析人血清和细菌提取物中的 Fpg 方面表现出色。它可以在等温条件下利用紫外可见光和智能手机对 Fpg 进行定量检测,因此在临床诊断中很有价值。
{"title":"NNNPERFUME: Detection of 8-oxoguanine DNA glycosylase activity based on primer exchange reaction and functionalized hemin/G-quadruplex DNAzyme","authors":"Kaiting Xiao ,&nbsp;Yanming Lai ,&nbsp;Xingxing Liu,&nbsp;Shengjie Li,&nbsp;Wenxu Yuan,&nbsp;Ziyun Wang,&nbsp;Pan Pan,&nbsp;Yongkui Li,&nbsp;Heng Xiao","doi":"10.1016/j.talo.2024.100288","DOIUrl":"10.1016/j.talo.2024.100288","url":null,"abstract":"<div><h3>Background</h3><p>8-oxoguanine DNA glycosylase can maintain genomic stability and integrity. However, it can interfere with the regular DNA damage repair process, possibly leading to the development of cancer and various other human diseases when its activity becomes abnormal. Current methods for detecting 8-oxoguanine DNA glycosylase activity often suffer from low sensitivity, time-consuming procedures, labor-intensive requirements, and the need for specialized equipment and trained professionals for execution. Consequently, there is an urgent need for a portable, user-friendly 8-oxoguanine DNA glycosylase assay that offers swift results and supports real-time testing.</p></div><div><h3>Results</h3><p>We've developed a PERFUME method that combines <strong>p</strong>rimer <strong>e</strong>xchange <strong>r</strong>eaction and <strong>f</strong>unctionalized G-q<strong>u</strong>adruplex/he<strong>m</strong>in DNAzym<strong>e</strong> for sensitive detection of Fpg, a typical 8-oxoguanine DNA glycosylase. Utilizing a single probe and T4 Polynucleotide Kinase (PNK) simplifies the experiment to a one-step reaction at 37 °C in 3 h, reducing sample consumption and improving sensitivity. We chose functionalized hemin cofactors, significantly improving catalytic efficiency and enhancing detection capability. This biosensor detects Fpg activity with a sensitivity as low as 0.11 U mL<sup>−1</sup>, displaying exceptional sensitivity, selectivity, and interference resistance in human serum and bacterial cell extracts under isothermal conditions. The biosensor demonstrates remarkable selectivity and ability for Fpg inhibitors screening. In addition, this biosensor enables reading the sample's RGB values using a smartphone, facilitating accurate quantification of Fpg activity without the necessity for specialized equipment.</p></div><div><h3>Significance</h3><p>PERFUME simplifies Fpg detection by using a single hairpin and PNK in a one-step process. We utilize FUME to enhance catalytic efficiency, it surpassing the performance of traditional G-quadruplex/hemin DNAzyme methods. This approach excels in analyzing Fpg in human serum and bacterial extracts. It allows quantitative Fpg detection using UV–Vis and smartphones under isothermal conditions, making it valuable for clinical diagnosis.</p></div>","PeriodicalId":436,"journal":{"name":"Talanta Open","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S266683192400002X/pdfft?md5=2888c2a68f62e637d2c8f099a2588def&pid=1-s2.0-S266683192400002X-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139471093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Quantitative analysis of Δ9-tetrahydrocannabinol (Δ9-THC) in cannabis plants using the Fast Blue BB (FBBB) and 4-aminophenol (4-AP) colorimetric tests 使用快速蓝 BB (FBBB) 和 4-氨基苯酚 (4-AP) 比色测试法定量分析大麻植物中的Δ9-四氢大麻酚 (Δ9-THC)。
Q3 Chemistry Pub Date : 2024-01-10 DOI: 10.1016/j.talo.2024.100287
Nicole B. Valdes, Roberta Gorziza, José R. Almirall

The Fast Blue BB (FBBB) and 4-aminophenol (4-AP) colorimetric tests have been reportedly used for the qualitative determination of Δ9-THC in plants and for the differentiation between marijuana and hemp-type cannabis. We report the miniaturization of the FBBB colorimetric reaction on a silicone treated filter paper substrate and the analytical figures of merit for a quantitative determination of Δ9-THC for the first time. The reaction between Δ9-THC and FBBB forms a red chromophore that fluoresces when irradiated with visible (480 nm) or UV (365 nm) light, providing a 3-fold increase in sensitivity. Portable instruments are introduced for the objective color determination for both tests and for the fluorescence reading of the THC + FBBB complex. We report a fluorescence signal with Δ9-THC, Δ8-THC, and CBN. The limit of detection (LOD) was determined to be 1.6 ng/μL with precision ∼12 % RSD for standard Δ9-THC solutions ranging between 5 and 20 ng/μL. The linear dynamic range for this test is reported between 1.6 ng/μL and 20 ng/μL for the portable fluorescence detector. The miniaturization of both colorimetric tests and the increased sensitivity of the FBBB test using fluorescence analysis, coupled to portable instruments allows for limited quantitative analysis of cannabis plants in the field.

据报道,快速蓝 BB(FBBB)和 4-氨基苯酚(4-AP)比色试验已被用于植物中 Δ9-THC 的定性测定以及大麻和大麻类大麻的区分。我们首次报道了在硅胶处理的滤纸基底上进行 FBBB 比色反应的微型化以及定量测定 Δ9-THC 的分析数据。Δ9-THC 与 FBBB 反应生成红色发色团,在可见光(480 纳米)或紫外线(365 纳米)照射下发出荧光,使灵敏度提高了 3 倍。我们引入了便携式仪器,用于客观测定两种测试的颜色以及 THC+FBBB 复合物的荧光读数。我们报告了 Δ9-THC、Δ8-THC 和 CBN 的荧光信号。对于 5-20 纳克/微升的标准 Δ9-THC 溶液,检测限 (LOD) 为 1.6 纳克/微升,精度为 12% RSD。便携式荧光检测器的线性动态范围为 1.6 ng/μL 至 20 ng/μL。这两种比色测试的微型化和使用荧光分析的 FBBB 测试灵敏度的提高,再加上便携式仪器,使得在现场对大麻植物进行有限的定量分析成为可能。
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引用次数: 0
Introducing an innovative immobilized optode based on PVC-ETH-5294 matrix for environmentally friendly sensing of lead ions 介绍一种基于 PVC-ETH-5294 矩阵的创新型固定光电二极管,用于以环境友好型方式传感铅离子
Q3 Chemistry Pub Date : 2023-12-30 DOI: 10.1016/j.talo.2023.100285
Reem F. Alshehri , Alaa S. Amin , Eman R. Darwish

A novel selective membrane optode was prepared to determine of ultra-trace amounts of lead. This state-of-the-art optode amalgamates a bespoke ionophore, 4-(thiazol-2-yldiazenyl)benzene-1,3-diol (TDBD), with ETH-5294, assuming the role of a chromoionophore. This potent composition converges with sodium tetraphenylborate (NaTPB) and dioctyl phthalate (DOP), harmoniously enclosed within a matrix of poly(vinyl chloride) (PVC). The influence of various parameters on the preparation of the optode and the determination of Pb2+ was investigated and optimized. Evidently, the optode unfurls an expansive linear dynamic expanse, spanning an astonishing range from 6.0 × 10−9 to 8 × 10−5 M. Remarkably, it retains an astonishingly low degree of detection and quantification, registering at 1.75 and 5.85 × 10−9 M, respectively. The response time of the optode was 4.0 min. The optodes versatility extends its embrace towards rejuvenation, permitting multiple rounds of service via 0.2 M HNO3 solutions. The effect of potential interference ions on the Pb2+ determination was illustrated. The results showed that the prepared optode was very selective to lead ions so that it had no significant response to common ions such as Mg2+, Mn2+, Cd2+, Ni2+, Fe2+, Fe3+, Hg2+, Cu2+, and Co2+. The optode was applied successfully to determine of Pb2+ indifferent food, biological and environmental samples and result obtained is comparable to atomic absorption spectrometry method.

我们制备了一种新型选择性膜光电二极管,用于测定超痕量铅。这种最先进的光电二极管将一种定制的离子载体--4-(噻唑-2-基二氮基)苯-1,3-二醇(TDBD)与 ETH-5294 结合在一起,发挥了发色离子载体的作用。这种强效成分与四苯基硼酸钠(NaTPB)和邻苯二甲酸二辛酯(DOP)相融合,和谐地包裹在聚氯乙烯(PVC)基质中。研究并优化了各种参数对光阳极制备和 Pb2+ 测定的影响。显而易见的是,该光电二极管具有广阔的线性动态范围,从 6.0 × 10-9 到 8 × 10-5 M。光电二极管的响应时间为 4.0 分钟。该光电二极管的多功能性使其可以通过 0.2 M HNO3 溶液进行多轮服务,从而使其焕发青春。实验说明了潜在干扰离子对 Pb2+ 测定的影响。结果表明,所制备的光极板对铅离子具有很强的选择性,因此对 Mg2+、Mn2+、Cd2+、Ni2+、Fe2+、Fe3+、Hg2+、Cu2+ 和 Co2+ 等常见离子没有明显反应。该光电二极管被成功地应用于食品、生物和环境样品中 Pb2+ 的测定,其结果与原子吸收光谱法相当。
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引用次数: 0
MOFs with 2,6-naphthalene dicarboxylic acid as organic ligand for solid phase microextraction of aldehyde biomarkers in the exhalation of lung cancer patients 以 2,6-萘二羧酸为有机配体的 MOFs 用于固相微萃取肺癌患者呼气中的醛类生物标记物
Q3 Chemistry Pub Date : 2023-12-28 DOI: 10.1016/j.talo.2023.100286
Xiao-Ye Shi , Shu-Jun Liu , Li-Qing Yu , Lan-Fen Li , Yun-Kai Lv

In this work, four metal-organic frameworks (MOFs) including DUT-4, DUT-8, IRMOF-8, and MIL-140B were synthesized using 2,6-naphthalene dicarboxylic acid as organic ligand and Al3+, Co2+, Zn2+, and Zr4+as metal centers, then coated on stainless steel wires as solid-phase microextraction (SPME) fiber coatings. Five aldehyde biomarkers (hexanal, heptanal, octanal, decanal, and nonanal) in exhaled breath of lung cancer patients were used as the target analytes, and extracted using four MOFs fiber coatings, followed by thermal desorption and quantitative analysis using GC–MS. The DUT-4 was found to be the most appropriate sorbent. The developed SPME-GC–MS method has large enrichment factors (877–1711), wide linear ranges (0.5–1000 μg L−1), and low detection limits (0.056–0.138 μg L−1). The relative standard deviation for six replicate cycles using one DUT-4 coated fiber were 2.0–7.7 % (intra-day) and 2.2–4.6 % (inter-day), respectively. The fiber-to-fiber reproducibility for three parallel prepared fibers was in the range of 3.7–13.7 % (RSD). The fabricated DUT-4 coated fiber can withstand at least 100 cycles of extraction/desorption/conditioning without significant loss of extraction efficiency and precision. The high enrichment factors of the DUT-4 coatings are attributed to the high specific surface area, unique porous structure, and abundant aluminum coordinated unsaturated metal sites of the DUT-4 material. Moreover, the 2,6-naphthalene dicarboxylic acid has two benzene rings with a 180° orientation, which not only increases the hydrophobicity of the MOFs material to avoid water molecules occupying adsorption sites and helps to form a rigid skeleton structure with a large number of functional adsorption sites on the surface, thereby improving the enrichment factor of target analytes. Ultimately, the developed DUT-4 coated SPME fibers was sucessfully used for the analysis of exhaled breath samples, and the recoveries for the spiked analytes were in the range of 89–105 %.

本研究以2,6-萘二羧酸为有机配体,Al3+、Co2+、Zn2+和Zr4+为金属中心,合成了包括DUT-4、DUT-8、IRMOF-8和MIL-140B在内的四种金属有机框架(MOFs),并将其包覆在不锈钢丝上作为固相微萃取(SPME)纤维涂层。以肺癌患者呼出气体中的五种醛类生物标志物(己醛、庚醛、辛醛、癸醛和壬醛)为目标分析物,使用四种 MOFs 纤维涂层进行提取,然后进行热解吸附和 GC-MS 定量分析。结果发现,DUT-4 是最合适的吸附剂。所开发的 SPME-GC-MS 方法富集因子大(877-1711),线性范围宽(0.5-1000 μg L-1),检出限低(0.056-0.138 μg L-1)。使用一根 DUT-4 涂层纤维进行六个重复周期的相对标准偏差分别为 2.0-7.7%(日内)和 2.2-4.6%(日间)。三根平行制备的纤维之间的重现性为 3.7-13.7%(RSD)。所制备的 DUT-4 涂层纤维可承受至少 100 次的萃取/解吸/调节循环,而不会明显降低萃取效率和精度。DUT-4 涂层的高富集系数归功于 DUT-4 材料的高比表面积、独特的多孔结构和丰富的铝配位不饱和金属位点。此外,2,6-萘二羧酸具有两个取向为 180°的苯环,这不仅增加了 MOFs 材料的疏水性,避免水分子占据吸附位点,而且有助于在表面形成具有大量功能吸附位点的刚性骨架结构,从而提高目标分析物的富集因子。最终,开发的 DUT-4 涂层 SPME 纤维被成功用于呼出气体样品的分析,加标分析物的回收率在 89-105% 之间。
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引用次数: 0
Fluorescence-based self-diagnosis of hyperbranched polyethyleneimine oxidation 基于荧光的超支化聚乙烯亚胺氧化自我诊断
Q3 Chemistry Pub Date : 2023-12-25 DOI: 10.1016/j.talo.2023.100284
He Zhou , Qingxin Yang , Fengniu Lu , Jiaojiao Zheng , Zhiqin Yuan , Chao Lu

Polymer oxidation affects the molecular structure and decides the performances, making its rapid and sensitive diagnosis important for evaluating the state of polymer materials and predicting its service life. In this study, fluorometric analysis of the oxidation of hyperbranched polyethyleneimine is realized by Schiff-base reaction. The sensing mechanism is due to the oxidation-mediated generation of oxygen-containing groups, which react with residual primary amine and produce fluorescent Schiff-base compounds. Four hPEIs with different molecular weight possess similar fluorescence variation during oxidation, demonstrating the universality of the proposed technique. Moreover, the successful quality assessment of hPEI verifies the practical application of the proposed fluorescence-based self-diagnosis technique.

聚合物氧化会影响其分子结构并决定其性能,因此其快速、灵敏的诊断对于评估聚合物材料的状态和预测其使用寿命非常重要。本研究通过希夫碱反应实现了对超支化聚乙烯亚胺氧化过程的荧光分析。其传感机制是由于氧化介导生成含氧基团,含氧基团与残留伯胺反应生成荧光希夫碱化合物。四种不同分子量的 hPEIs 在氧化过程中具有相似的荧光变化,证明了所提议技术的通用性。此外,对 hPEI 的成功质量评估也验证了所提出的基于荧光的自诊断技术的实际应用。
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引用次数: 0
Analysis of elemental impurities in cannabis following vaporization 大麻蒸发后的元素杂质分析
Q3 Chemistry Pub Date : 2023-12-08 DOI: 10.1016/j.talo.2023.100281
Qiang Wang , Berk Oktem , Charles G. Wu , Nathan C. Twaddle , Cassandra L. Taylor

The use of vaporizers to inhale cannabis is a technique that has risen in popularity among the American public. There is a general perception that vaporizers are “safer” when compared to more traditional cannabis smoking via combustion (i.e., cigarettes). The inherent use of heated air in vaporizers might reduce the respiratory toxicants or protein toxins by heating cannabis to a temperature where active compounds form in vapor phase. Yet this temperature is below the point of combustion where smoke and associated toxicants are produced. The elemental impurities are a general concern in all botanical products including cannabis and cannabis-derived products (CCDPs). This study aimed to investigate the potential transfer of those metallic elements from cannabis material to cannabis vapor through the vaporization process. A Volcano Digit Vaporizer (Storz & Bickel) was used as the heating device to perform the vaporization. Three cannabis plant materials were evaluated with varying contents of cannabinoids, including a cannabis placebo (<0.01 % Tetrahydrocannabinol (THC), Cannabidiol (CBD) & Cannabinol (CBN)), cannabis with low potency (2.0 % THC/ 0.02 % CBD/ 0.47 % CBN) and high potency (6.7 % THC/ non detectable CBD/ 0.49 % CBN). Baseline elemental impurity levels were evaluated for all cannabis plant materials. Four different types of heat treatment, namely no heat, 30 seconds (s), and 70 s heat treatment, and finally 70 s heat treatment with air flow, were developed for the three cannabis materials and the experimental samples after vaporization were analyzed by an inductively coupled plasma-mass spectrometry (ICP-MS) system. The results showed that sixteen elemental impurities were detected, and all have similar concentration, between 10 ng/g and 8 × 106 ng/g, in the three types of cannabis materials, where Mg was measured with the highest content. Within the four heating treatments evaluated no significant changes of these metallic elements (elemental impurities) were found when compared to the plant materials. This preliminary experimental study evaluated a single vaporizer and three cannabis plant materials suggesting a transfer of metallic elements from cannabis material to cannabis vapor may not occur during the vaporization process under these study conditions.

使用蒸发器吸食大麻是一种在美国公众中日益流行的技术。人们普遍认为,与更传统的通过燃烧吸食大麻(即香烟)相比,蒸发器 "更安全"。蒸发器中固有的加热空气可以将大麻加热到活性化合物形成气相的温度,从而减少呼吸道毒物或蛋白质毒素。但这一温度低于产生烟雾和相关毒物的燃烧点。元素杂质是包括大麻和大麻衍生产品(CCDPs)在内的所有植物产品普遍关注的问题。本研究旨在调查这些金属元素通过汽化过程从大麻材料转移到大麻蒸汽中的可能性。使用 Volcano Digit Vaporizer(Storz & Bickel)作为加热装置进行蒸发。对三种大麻素含量不同的大麻植物材料进行了评估,包括大麻安慰剂(0.01% 四氢大麻酚(THC)、大麻二酚(CBD)和大麻酚(CBN))、低效力大麻(2.0% THC/ 0.02% CBD/ 0.47% CBN)和高效力大麻(6.7% THC/ 检测不到 CBD/ 0.49% CBN)。对所有大麻植物材料的基准元素杂质含量进行了评估。对三种大麻材料进行了四种不同的热处理,即不加热、30 秒(秒)和 70 秒(秒)热处理,最后是 70 秒(秒)气流热处理,蒸发后的实验样品由电感耦合等离子体质谱仪(ICP-MS)系统进行分析。结果表明,在三种大麻材料中检测到了 16 种元素杂质,它们的浓度都差不多,介于 10 纳克/克和 8 × 106 纳克/克之间,其中镁的含量最高。在所评估的四种加热处理中,与植物材料相比,这些金属元素(元素杂质)没有发现明显的变化。这项初步实验研究评估了一个蒸发器和三种大麻植物材料,表明在这些研究条件下,金属元素可能不会在蒸发过程中从大麻材料转移到大麻蒸气中。
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引用次数: 0
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