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Exploring the impact mechanism of ambient gas properties on laser-induced breakdown spectroscopy to guide the raw signal improvement 探索环境气体特性对激光诱导击穿光谱仪的影响机制,指导原始信号的改进
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-22 DOI: 10.1016/j.aca.2024.343464
Yuzhou Song, Zongyu Hou, Xiang Yu, Weili Yao, Zhe Wang
<h3>Background</h3>Laser-induced breakdown spectroscopy (LIBS) has long been regarded as the future superstar for chemical analysis. However, hindered by the fact that the signal source of LIBS is a spatially and temporally unstable plasma that interacts dramatically with ambient gases, LIBS has always suffered from poor signal quality, especially low signal repeatability. Although ambient gases act as one of the most direct and critical factors affecting LIBS signals, a clear understanding on how ambient gas properties impact LIBS signals is still lacking to act as guideline for the signal quality improvement.<h3>Results</h3>In this work, the impact mechanism of three main ambient gas properties, including specific heat ratio (<span><span style=""></span><span data-mathml='<math xmlns="http://www.w3.org/1998/Math/MathML" />' role="presentation" style="font-size: 90%; display: inline-block; position: relative;" tabindex="0"><svg aria-hidden="true" focusable="false" height="0.24ex" role="img" style="vertical-align: -0.12ex;" viewbox="0 -51.7 0 103.4" width="0" xmlns:xlink="http://www.w3.org/1999/xlink"><g fill="currentColor" stroke="currentColor" stroke-width="0" transform="matrix(1 0 0 -1 0 0)"></g></svg><span role="presentation"><math xmlns="http://www.w3.org/1998/Math/MathML"></math></span></span><script type="math/mml"><math></math></script></span>), molar mass (<span><span style=""></span><span data-mathml='<math xmlns="http://www.w3.org/1998/Math/MathML" />' role="presentation" style="font-size: 90%; display: inline-block; position: relative;" tabindex="0"><svg aria-hidden="true" focusable="false" height="0.24ex" role="img" style="vertical-align: -0.12ex;" viewbox="0 -51.7 0 103.4" width="0" xmlns:xlink="http://www.w3.org/1999/xlink"><g fill="currentColor" stroke="currentColor" stroke-width="0" transform="matrix(1 0 0 -1 0 0)"></g></svg><span role="presentation"><math xmlns="http://www.w3.org/1998/Math/MathML"></math></span></span><script type="math/mml"><math></math></script></span>), and ionization energy (<span><span style=""></span><span data-mathml='<math xmlns="http://www.w3.org/1998/Math/MathML" />' role="presentation" style="font-size: 90%; display: inline-block; position: relative;" tabindex="0"><svg aria-hidden="true" focusable="false" height="0.24ex" role="img" style="vertical-align: -0.12ex;" viewbox="0 -51.7 0 103.4" width="0" xmlns:xlink="http://www.w3.org/1999/xlink"><g fill="currentColor" stroke="currentColor" stroke-width="0" transform="matrix(1 0 0 -1 0 0)"></g></svg><span role="presentation"><math xmlns="http://www.w3.org/1998/Math/MathML"></math></span></span><script type="math/mml"><math></math></script></span>) was investigated by ignoring secondary properties, accurately proportioning gas mixtures, and experimental comparative study by applying various plasma diagnosis methods. The results indicate that these three properties impact signal repeatability by impacting the intensity of the back-pressing
背景激光诱导击穿光谱(LIBS)一直被视为化学分析领域的未来之星。然而,由于激光诱导击穿光谱的信号源是空间和时间上不稳定的等离子体,会与环境气体发生剧烈的相互作用,因此激光诱导击穿光谱一直存在信号质量差,特别是信号重复性低的问题。尽管环境气体是影响 LIBS 信号最直接、最关键的因素之一,但人们对环境气体特性如何影响 LIBS 信号仍缺乏清晰的认识,因此无法为改善信号质量提供指导。结果表明,这三种特性通过影响等离子体内部反压过程的强度来影响信号的可重复性,其中由 和 决定的声速起着重要作用。这些特性通过影响等离子体中的三个能量传递过程来影响信号强度,包括激光能量吸收、气体和样品之间的能量分配以及热耗散。意义首次清晰直观地揭示了环境气体主要性质对 LIBS 信号的影响机制。该影响机制不仅加深了对等离子体演化过程的理解,而且为改善 LIBS 信号质量提供了实用的指导原则,有助于 LIBS 技术的精确量化。
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引用次数: 0
Construction of Zinc-based metal-organic frameworks for visual ratiometric fluorescence detection of tetracycline 构建锌基金属有机框架,用于四环素的可视比率荧光检测
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-22 DOI: 10.1016/j.aca.2024.343461
Yating Zhong, Haocheng Gao, Jingqi Yang, Xinru Wang, Ying Yu, Yujuan Cao, Manli Guo, Bixia Lin

Background

Tetracycline (TC) is frequently utilized as additives in animal feed. The misuse can lead to the residue in food and threaten human health.

Results

A ratiometric fluorescence method for tetracycline detection is developed based on Zinc-based metal-organic framework (Zn-MOF) materials. A series of Zn-MOFs are synthesized with phthalic acid derivatives as ligand, and their luminescence properties and interaction with tetracycline are investigated. Thereinto, Zn-BDC-OH MOF synthesized with 2-hydroxyterephthalic acid (BDC-OH) as ligand exhibits sensitive fluorescence response to tetracycline. The blue fluorescence of Zn-BDC-OH at 434 nm is quenched by tetracycline due to inner filter effect (IFE), and the green fluorescence of TC at 531 nm is enhanced because of coordination with Zn2+. The fluorescence intensity ratio I531/I434 shows a linear relationship with TC concentration in the range of 0.10-40.0 μM with a limit of detection at 79 nM. The fluorescence colors of Zn-BDC-OH MOF change from blue to cyan to green accompanying with increasing TC concentration, which enables the visual and semi-quantitative detection of tetracycline by naked eyes. Moreover, combined with a smartphone, the RGB value of the fluorescence color can be further identified. The ratio (G/B) of green channel to blue channel shows a linear relationship with the TC concentration in the range of 0.25-25.0 μM with a limit of detection at 0.2 μM. Afterwards, Zn-BDC-OH MOF is successfully applied to detect tetracycline in honey, and the results are consistent with those obtained from chromatography.

Significance

The established method exhibits great potential for field visualization and rapid detection of tetracycline.
背景四环素(TC)经常被用作动物饲料添加剂。结果 以锌基金属有机框架(Zn-MOF)材料为基础,开发了一种比率荧光检测四环素的方法。以邻苯二甲酸衍生物为配体合成了一系列 Zn-MOF,并研究了它们的发光特性以及与四环素的相互作用。其中,以 2-羟基对苯二甲酸(BDC-OH)为配体合成的 Zn-BDC-OH MOF 对四环素具有敏感的荧光响应。由于内滤光片效应(IFE),Zn-BDC-OH 在 434 纳米波长处的蓝色荧光被四环素淬灭;由于与 Zn2+ 配位,TC 在 531 纳米波长处的绿色荧光增强。在 0.10-40.0 μM 范围内,荧光强度比 I531/I434 与 TC 浓度呈线性关系,检测限为 79 nM。随着 TC 浓度的增加,Zn-BDC-OH MOF 的荧光颜色由蓝色变为青色,再由青色变为绿色,从而实现了对四环素的肉眼半定量检测。此外,结合智能手机还可以进一步识别荧光颜色的 RGB 值。在 0.25-25.0 μM 的范围内,绿色通道与蓝色通道的比率(G/B)与四环素浓度呈线性关系,检测限为 0.2 μM。随后,Zn-BDC-OH MOF 被成功应用于蜂蜜中四环素的检测,结果与色谱法的结果一致。
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引用次数: 0
SINGLE CELL COMB INED WITH LASER ABLATION ICP-MS TO STUDY PLATINUM (IV) LOADED NANOPARTICLES PENETRATION PATHWAYS IN OSTEOSARCOMA SPHEROIDS. 用激光消融 ICP-MS进行单细胞组合,研究骨肉瘤球体内铂(iv)纳米粒子的渗透途径。
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-22 DOI: 10.1016/j.aca.2024.343462
L. Gutierrez-Romero, B. Gallego, E. Blanco, U. Karst, R. Rodríguez, M. Montes Bayon

Background

3D cellular structures have been considered the following step in the evaluation of drugs penetration after 2D cultures since they are more physiologically representative in cancer cell biology. Here the penetration capabilities of Pt (IV)-loaded ultrasmall iron oxide nanoparticles in 143B osteosarcoma multicellular spheroids of different sizes is conducted by a multidimensional quantitative approach. Single cell (SC) and imaging techniques (laser ablation, LA) coupled to inductively coupled plasma-mass spectrometry (ICP-MS) are used to visualize their penetration pathways and distribution in comparison to those of cisplatin.

Results

The analysis of Pt in disaggregated individual cells from spheroids shows levels of incorporation dependent on the spheroid surface to volume ratio and considerably higher than those observed for cisplatin. These results in combination with the total Pt determination in the complete spheroids reveal a preferential transcellular incorporation pathway of the Pt(IV)-loaded NPs. Elemental imaging by LA-ICP-MS shows the co—localization of Pt/Fe in hot spots at distances up to 100 μm from the spheroid surface reaching concentrations of Pt up to 200 μg·g-1 when exposed to Pt(IV)-loaded NPs. A more homogeneous distribution all along the spheroid is observed in the cisplatin-treated models.

Significance

The multidimensional ICP-MS based analytical methodology developed through this work offers a generalizable approach to quantitatively study the tissue penetration of nano-transported drugs to be applied in the design of nanoparticles with high accumulation at a target site.
背景三维细胞结构被认为是继二维培养后评估药物渗透性的又一步骤,因为它们在癌细胞生物学中更具生理代表性。在此,我们采用多维定量方法研究了铂(IV)负载超小氧化铁纳米粒子在不同大小的 143B 骨肉瘤多细胞球体内的穿透能力。单细胞(SC)和成像技术(激光烧蚀,LA)与电感耦合等离子体质谱法(ICP-MS)相结合,用于观察铂的渗透途径和分布情况,并与顺铂的渗透途径和分布情况进行比较。这些结果与完整球体内的总铂测定结果相结合,揭示了负载铂(IV)的 NPs 的优先跨细胞掺入途径。通过 LA-ICP-MS 进行的元素成像显示,铂/铁共定位在距离球体表面 100 μm 的热点上,当接触到负载铂(IV)的 NPs 时,铂的浓度可达 200 μg-g-1。本研究开发的基于 ICP-MS 的多维分析方法为定量研究纳米药物的组织穿透性提供了一种可推广的方法,可用于设计在目标部位具有高蓄积性的纳米粒子。
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引用次数: 0
Selective-excitation-based method for measurement of NMR relaxation time 基于选择性激发的核磁共振弛豫时间测量方法
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-22 DOI: 10.1016/j.aca.2024.343465
Xiaoqi Shi, Wen Zhu, Qing Zeng, Yao Luo, Zhong Chen, Yanqin Lin

Background

Relaxation time provides invaluable insights into the molecular structure, interactions, and dynamics in nuclear magnetic resonance spectroscopy. However, conventional relaxation-time measurement techniques produce inaccurate relaxation times when the spectral peaks overlap because of the narrow chemical-shift range and J-coupled splitting. While the combination of pure-shift methods can solve this issue, they are not widely used due to their inherent drawbacks such as low sensitivity and long acquisition time. There is a great need for a feasible and sensitive method to measure the relaxation time for overlapping peaks. (87)

Results

This study proposes a new method that combines selective excitation with a conventional relaxation-time measurement method, named GEM-IR/CPMG, to accurately measure the longitudinal and transverse relaxation times in the samples with overlapping peaks. The method has a similar acquisition time as the conventional method with small sensitivity loss. The feasibility and effectiveness of the method were demonstrated through experiments using three types of samples: 1-bromobutane, a mixture of butanol and butyric acid, and 17β-estradiol. The results show that the relaxation times measured by this method are in general agreement with the results of the conventional method. In addition, to demonstrate the advantages of the method for low-concentration samples, a sample of estradiol at 8 mM was measured with the results obtained matching the high concentration. (125)

Significance

The GEM-IR/CPMG method eliminates interference from overlapping peaks in proton relaxation-time measurement and preserves the crucial coupling information of the sample, thus allowing accurate measurement of the relaxation time. Moreover, it selectively excites the spin of interest in a single scan, demonstrating a minor loss of spectral sensitivity and facilitating the measurement of low-concentration samples, making it widely applicable to chemical analyses. (62)
背景在核磁共振光谱学中,弛豫时间为了解分子结构、相互作用和动力学提供了宝贵的信息。然而,传统的弛豫时间测量技术会在光谱峰重叠时产生不准确的弛豫时间,原因是化学位移范围窄和 J 耦合分裂。虽然纯移位方法的组合可以解决这一问题,但由于其固有的缺点,如灵敏度低、采集时间长等,并未得到广泛应用。因此,亟需一种可行且灵敏的方法来测量重叠峰的弛豫时间。(87)结果本研究提出了一种将选择性激发与传统弛豫时间测量方法相结合的新方法,命名为 GEM-IR/CPMG,用于精确测量具有重叠峰的样品的纵向和横向弛豫时间。该方法的采集时间与传统方法相似,灵敏度损失较小。通过使用三种样品进行实验,证明了该方法的可行性和有效性:1-溴丁烷、丁醇和丁酸的混合物以及 17β-雌二醇。结果表明,该方法测得的弛豫时间与传统方法的结果基本一致。此外,为了证明该方法在低浓度样品中的优势,还测量了 8 mM 的雌二醇样品,结果与高浓度样品一致。(125)意义GEM-IR/CPMG 方法消除了质子弛豫时间测量中重叠峰的干扰,保留了样品的关键耦合信息,从而实现了弛豫时间的精确测量。此外,它还能在一次扫描中选择性地激发感兴趣的自旋,光谱灵敏度损失小,便于测量低浓度样品,因此广泛适用于化学分析。(62)
{"title":"Selective-excitation-based method for measurement of NMR relaxation time","authors":"Xiaoqi Shi, Wen Zhu, Qing Zeng, Yao Luo, Zhong Chen, Yanqin Lin","doi":"10.1016/j.aca.2024.343465","DOIUrl":"https://doi.org/10.1016/j.aca.2024.343465","url":null,"abstract":"<h3>Background</h3>Relaxation time provides invaluable insights into the molecular structure, interactions, and dynamics in nuclear magnetic resonance spectroscopy. However, conventional relaxation-time measurement techniques produce inaccurate relaxation times when the spectral peaks overlap because of the narrow chemical-shift range and <em>J</em>-coupled splitting. While the combination of pure-shift methods can solve this issue, they are not widely used due to their inherent drawbacks such as low sensitivity and long acquisition time. There is a great need for a feasible and sensitive method to measure the relaxation time for overlapping peaks. (87)<h3>Results</h3>This study proposes a new method that combines selective excitation with a conventional relaxation-time measurement method, named GEM-IR/CPMG, to accurately measure the longitudinal and transverse relaxation times in the samples with overlapping peaks. The method has a similar acquisition time as the conventional method with small sensitivity loss. The feasibility and effectiveness of the method were demonstrated through experiments using three types of samples: 1-bromobutane, a mixture of butanol and butyric acid, and 17β-estradiol. The results show that the relaxation times measured by this method are in general agreement with the results of the conventional method. In addition, to demonstrate the advantages of the method for low-concentration samples, a sample of estradiol at 8 mM was measured with the results obtained matching the high concentration. (125)<h3>Significance</h3>The GEM-IR/CPMG method eliminates interference from overlapping peaks in proton relaxation-time measurement and preserves the crucial coupling information of the sample, thus allowing accurate measurement of the relaxation time. Moreover, it selectively excites the spin of interest in a single scan, demonstrating a minor loss of spectral sensitivity and facilitating the measurement of low-concentration samples, making it widely applicable to chemical analyses. (62)","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Dual-CRISPR/Cas12a-assisted RT-RAA visualization system for rapid on-site detection of nervous necrosis virus (NNV) 用于现场快速检测神经坏死病毒(NNV)的双 CRISPR/Cas12a 辅助 RT-RAA 可视化系统
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-22 DOI: 10.1016/j.aca.2024.343469
Jie Gao, Siyou Huang, Jing Jiang, Qijin Miao, Rui Zheng, Yiling Kang, Wanting Tang, Hongliang Zuo, Jianguo He, Junfeng Xie

Background

Nervous necrosis virus (NNV) poses a severe threat to the aquaculture industry, particularly infecting fish fry with devastating mortality rates and inflicting heavy economic losses. Traditional detection methods, such as cell culture and conventional RT-PCR, are not only time-consuming and require specialized laboratory facilities but also hard to eliminate contamination. Rapid and accurate on-site detection methods in aquaculture settings are crucial for effective control of NNV outbreaks in fish farms.

Results

This study developed a one-tube visualization system for rapid and precise identification of NNV in a pond-side setting. This system utilizes the dual-clustered regularly interspaced short palindromic repeats (CRISPR)/Cas12a-assisted reverse transcription-recombinase aided amplification (RT-RAA) detection method, employing fluorescence intensity to indicate positive results for easy interpretation by field operators. The key to this system involved the meticulous selection of RT-RAA primer sets and CRISPR RNA (crRNA) primer sets targeting two genes of NNV, the capsid protein (CP) and RNA-dependent RNA polymerase (RdRp), distributing on two particles of genomic sequences. The assay demonstrated a speed and efficiency process within 30 min and a detection limit of 0.5 copies/μL, achieving 100% accuracy when compared to qRT-PCR. The practical utility and effectiveness were validated by using 32 field samples. The results underscored the simplicity, rapidity, and reliability of the system, confirming its potential as a robust tool for NNV diagnosis in fish farms.

Significance

This study introduces the first application of a dual-CRISPR/Cas12a-assisted RT-RAA visualization system for diagnosing NNV infections. The novel approach substantially enhances on-site diagnostic capabilities, offering a rapid, reliable, and cost-effective solution for fish farm operators. This innovation not only streamlines the detection process but also ensures timely intervention, thereby mitigating the impact of NNV on aquaculture.
背景神经坏死病毒(NNV)对水产养殖业构成严重威胁,尤其是感染鱼苗后死亡率极高,造成严重的经济损失。细胞培养和传统 RT-PCR 等传统检测方法不仅耗时长,需要专门的实验室设施,而且难以消除污染。在水产养殖环境中采用快速准确的现场检测方法对于有效控制养鱼场 NNV 的爆发至关重要。该系统采用双簇有规则间隔短回文重复序列(CRISPR)/Cas12a辅助反转录-重组酶辅助扩增(RT-RAA)检测方法,利用荧光强度显示阳性结果,便于现场操作人员解读。该系统的关键在于精心选择 RT-RAA 引物组和 CRISPR RNA(crRNA)引物组,这些引物组针对 NNV 的两个基因,即囊膜蛋白(CP)和 RNA 依赖性 RNA 聚合酶(RdRp),分布在两个基因组序列颗粒上。与 qRT-PCR 相比,该检测方法的速度和效率均在 30 分钟内完成,检测限为 0.5 个拷贝/μL,准确率达到 100%。使用 32 份现场样本验证了该方法的实用性和有效性。结果强调了该系统的简便性、快速性和可靠性,证实了其作为鱼类养殖场 NNV 诊断的有力工具的潜力。这种新方法大大提高了现场诊断能力,为养鱼场经营者提供了快速、可靠和经济高效的解决方案。这一创新不仅简化了检测过程,还确保了及时干预,从而减轻了 NNV 对水产养殖的影响。
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引用次数: 0
Capillary electrophoresis separations with Betaine:Urea, a deep eutectic solvent as the separation medium 使用甜菜碱:尿素(一种深共晶溶剂)作为毛细管电泳分离介质
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-22 DOI: 10.1016/j.aca.2024.343467
Haoxiang Meng, Sihui Ding, Song Xue, Siyao Liu, Qing Wu, Qi Zhang

Background

Capillary electrophoresis (CE) is a highly versatile separation technique widely used in analytical chemistry. Traditionally, CE can be categorized as either aqueous or non-aqueous systems based on the buffer solvents employed. For decades, non-aqueous CE has been predominantly associated with the use of organic solvents, a perception deeply ingrained in the scientific community. However, growing concerns about the health and environmental impacts of these solvents, driven by the principles of green chemistry, have prompted a reevaluation of their use. In response to these concerns, our group recently introduced a deep eutectic solvent (DES), specifically Proline:Urea, as an innovative and eco-friendly separation medium for CE. This approach not only enhances the sustainability of CE separations but also offers a new perspective for the development of innovative CE separation media.

Results

Building on our previous work, here we report the use of the second DES, Betaine:Urea (BU), as a new separation medium that offers further improved performance for CE applications. The DES was systematically characterized, with key physical properties relevant to CE separations, such as thermal properties, viscosity, dielectric constant, Joule heating effect, and UV transmittance, being thoroughly examined. Using a complex sample of 10 structurally similar naphthalene derivatives, we demonstrated the efficiency of BU in capillary zone electrophoresis (CZE) for separating analytes with varying charges (including cations, neutrals, and anions) and sizes. Additionally, we established the first micellar electrokinetic chromatography (MEKC) system in this DES using sodium dodecyl sulfate (SDS) as the surfactant. This system successfully resolved 6 structurally similar neutrals that could not be separated by conventional aqueous SDS-MEKC, highlighting the versatility of this DES-type separation medium. Furthermore, BU showed several advantages over the previously reported DES, Proline:Urea, particularly in terms of stability, viscosity, and Joule heating effects.

Significance

This study holds the potential to challenge the traditional notion that “CE separation media are merely categorized into aqueous and organic solvents”. Given that DESs are “designer” solvents with highly tunable properties and environmentally friendly characteristics, the introduction of BU as a viable alternative to traditional solvents not only expands the media available for CE separations, but also offers a more efficient and potentially more sustainable option for specific analyses.
背景毛细管电泳(CE)是一种广泛应用于分析化学的多功能分离技术。传统上,根据所使用的缓冲溶剂,毛细管电泳可分为水溶液系统和非水溶液系统。几十年来,非水 CE 主要与使用有机溶剂有关,这种观念在科学界根深蒂固。然而,在绿色化学原则的推动下,人们越来越关注这些溶剂对健康和环境的影响,这促使人们重新评估这些溶剂的使用。针对这些问题,我们小组最近推出了一种深共晶溶剂 (DES),特别是脯氨酸:尿素,作为一种创新的生态友好型 CE 分离介质。这种方法不仅提高了 CE 分离的可持续性,还为开发创新型 CE 分离介质提供了新的视角。结果在之前工作的基础上,我们在此报告了第二种 DES(甜菜碱:尿素 (BU))的使用情况,作为一种新的分离介质,它能进一步提高 CE 应用的性能。我们对 DES 进行了系统表征,并对与 CE 分离相关的关键物理性质(如热性能、粘度、介电常数、焦耳热效应和紫外线透过率)进行了全面检查。利用 10 种结构相似的萘衍生物的复杂样品,我们证明了 BU 在毛细管区带电泳 (CZE) 中分离不同电荷(包括阳离子、中性离子和阴离子)和大小的分析物的效率。此外,我们还利用十二烷基硫酸钠(SDS)作为表面活性剂,在该 DES 中建立了首个胶束电动色谱(MEKC)系统。该系统成功分离了 6 种结构相似的中性物质,这些物质无法通过传统的水性 SDS-MEKC 分离出来,这凸显了这种 DES 型分离介质的多功能性。此外,BU 与之前报道过的 DES(脯氨酸:尿素)相比,尤其是在稳定性、粘度和焦耳加热效应方面,显示出了若干优势。鉴于 DES 是一种 "设计型 "溶剂,具有高度可调的特性和环境友好型特征,因此引入 BU 作为传统溶剂的可行替代品,不仅扩大了可用于 CE 分离的介质范围,而且还为特定分析提供了一种更高效、可能更具可持续性的选择。
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引用次数: 0
(001) facet-supported TiO2 facet heterojunction with abundant active sites and high-efficiency carrier separation for ultrasensitive SERS detection of antibiotic residues in foods 具有丰富活性位点和高效载流子分离功能的 (001) 面支撑 TiO2 面异质结,用于超灵敏 SERS 检测食品中的抗生素残留物
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-22 DOI: 10.1016/j.aca.2024.343470
Yimin Tang, Shuang He, Xiuwen Wang, Bing Zhao, Xin Jiang, Libin Yang

Background

Antibiotic residues in animal-derived foods are seriously threatening human health and have attracted growing public attention. It is very important and valuable to carry out a rapid ultrasensitive detection of antibiotic residues, especially accurate identification based on molecular fingerprints.

Results

Here, a (001) facet-supported TiO2 facet heterojunction with abundant active sites (SF-TiO2) was developed as a surface-enhanced Raman scattering (SERS) substrate for ultrasensitive detection of antibiotic residues in milk and honey foods. Exposure of more (001) facets in SF-TiO2 can not only provide abundant surface-active sites for efficient chemical recognition of target molecules, but also form effective facet heterojunctions to achieve high-efficient carrier separation for charge transfer between substrate and molecule, which are together responsible for ultrasensitive SERS detection of target molecules with an enhancement factor of 1.3 × 107. The detection limit of enrofloxacin, enoxacin, ciprofloxacin and chloramphenicol residues in milk or honey reaches to 10-10-10-9 M, far lower than the EU standard. And, a simultaneous identification of multi-component residues in foods can be realized. The developed substrate exhibits excellent stability, anti-interference ability, and recyclability in the actual detection.

Significance

This work not only provides a novel SERS method for ultrasensitive detection of antibiotic residues in animal-derived foods, but also provides new ideas and concepts for the development of new-type semiconductor SERS substrates and their practical application.
背景动物源性食品中的抗生素残留严重威胁人类健康,已引起越来越多的公众关注。结果本研究开发了一种具有丰富活性位点的(001)面支撑 TiO2 面异质结(SF-TiO2)作为表面增强拉曼散射(SERS)基底,用于超灵敏检测牛奶和蜂蜜食品中的抗生素残留。在 SF-TiO2 中暴露更多的 (001) 面,不仅能提供丰富的表面活性位点以有效识别目标分子,还能形成有效的面异质结以实现高效的载流子分离,从而实现基底和分子之间的电荷转移,这些共同作用使目标分子的超灵敏 SERS 检测增强因子达到 1.3 × 107。牛奶或蜂蜜中恩诺沙星、依诺沙星、环丙沙星和氯霉素残留的检测限达到 10-10-10-9 M,远低于欧盟标准。而且,还可以同时鉴定食品中的多成分残留。这项工作不仅为超灵敏检测动物源性食品中的抗生素残留提供了一种新型的 SERS 方法,而且为新型半导体 SERS 底物的开发及其实际应用提供了新的思路和理念。
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引用次数: 0
Polypeptide functionalized gold nanoprobes for SERS-fluorescence detection and imaging of caspase-9 during apoptosis 多肽功能化金纳米探针用于细胞凋亡过程中 Caspase-9 的 SERS 荧光检测和成像
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-21 DOI: 10.1016/j.aca.2024.343458
Xiaoyuan Ma, Yue Pan, Xichi Lin, Zhouping Wang

Background

Deoxynivalenol is one of the common fungal toxins in processed grain foods. It has the characteristic of high temperature resistance. Dietary intake of DON contaminated food can cause adverse symptoms. Its cytotoxicity is mainly associated with the expression of apoptosis and interfering with protein synthesis. Among which, caspase family proteases play a crucial role in different types of apoptosis signaling pathways. Thus, it is important to develop a platform for real-time and in situ monitoring of caspase in living cells.

Results

In this paper, a polypeptide functionalized gold nanoprobes was designed for real-time and in situ detection of caspase-9 in living cells during DON induced apoptosis. Highly anisotropic gold nanostars (AuNSs) with good LSPR effect were synthesized. It could either serve as the surface enhanced Raman scattering (SERS) substrate or quench fluorescence through fluorescence resonance energy transfer (FRET). Polypeptide containing the LEHD (Leu-Glu-His-Asp) sequence was connected to AuNSs through Au-S bonds. During DON induced cell apoptosis, caspase-9 was activated, which could specifically cleave the recognition site LEHD, causing the polypeptide chain modified with Rhodamine B (Rb) signal group to fall off and move away from AuNSs, ultimately reducing the SERS signal and enhancing the fluorescence signal in the system. The experimental results showed that the nanoprobe had high sensitivity, with a linear range of 5 ng/mL to 400 ng/mL and a minimum detection limit of 0.38 ng/mL.

Significance

This method achieved dual signal quantification and visualization imaging of fluorescence and SERS for caspase-9. The application of nanomaterials has been broadened and the assay was well versatile in different human cell lines. It provided a new platform in studying the relationship between food safety and cellular homeostasis mechanisms.
背景脱氧雪腐镰刀菌烯醇是加工谷物食品中常见的真菌毒素之一。它具有耐高温的特点。摄入受 DON 污染的食物会引起不良症状。其细胞毒性主要与表达细胞凋亡和干扰蛋白质合成有关。其中,caspase 家族蛋白酶在不同类型的细胞凋亡信号通路中起着至关重要的作用。结果本文设计了一种多肽功能化金纳米探针,用于在 DON 诱导细胞凋亡过程中实时原位检测活细胞中的 caspase-9。合成了具有良好 LSPR 效果的高各向异性金纳米柱(AuNSs)。它既可以作为表面增强拉曼散射(SERS)基底,也可以通过荧光共振能量转移(FRET)淬灭荧光。含有 LEHD(Leu-Glu-His-Asp)序列的多肽通过 Au-S 键与 AuNSs 连接。在 DON 诱导的细胞凋亡过程中,caspase-9 被激活,可以特异性地裂解识别位点 LEHD,使修饰有罗丹明 B(Rb)信号基团的多肽链脱落并远离 AuNSs,最终降低系统中的 SERS 信号并增强荧光信号。实验结果表明,该纳米探针灵敏度高,线性范围为 5 ng/mL 至 400 ng/mL,最低检测限为 0.38 ng/mL。该方法拓宽了纳米材料的应用范围,并在不同的人体细胞系中具有良好的通用性。它为研究食品安全与细胞平衡机制之间的关系提供了一个新的平台。
{"title":"Polypeptide functionalized gold nanoprobes for SERS-fluorescence detection and imaging of caspase-9 during apoptosis","authors":"Xiaoyuan Ma, Yue Pan, Xichi Lin, Zhouping Wang","doi":"10.1016/j.aca.2024.343458","DOIUrl":"https://doi.org/10.1016/j.aca.2024.343458","url":null,"abstract":"<h3>Background</h3>Deoxynivalenol is one of the common fungal toxins in processed grain foods. It has the characteristic of high temperature resistance. Dietary intake of DON contaminated food can cause adverse symptoms. Its cytotoxicity is mainly associated with the expression of apoptosis and interfering with protein synthesis. Among which, caspase family proteases play a crucial role in different types of apoptosis signaling pathways. Thus, it is important to develop a platform for real-time and in situ monitoring of caspase in living cells.<h3>Results</h3>In this paper, a polypeptide functionalized gold nanoprobes was designed for real-time and in situ detection of caspase-9 in living cells during DON induced apoptosis. Highly anisotropic gold nanostars (AuNSs) with good LSPR effect were synthesized. It could either serve as the surface enhanced Raman scattering (SERS) substrate or quench fluorescence through fluorescence resonance energy transfer (FRET). Polypeptide containing the LEHD (Leu-Glu-His-Asp) sequence was connected to AuNSs through Au-S bonds. During DON induced cell apoptosis, caspase-9 was activated, which could specifically cleave the recognition site LEHD, causing the polypeptide chain modified with Rhodamine B (Rb) signal group to fall off and move away from AuNSs, ultimately reducing the SERS signal and enhancing the fluorescence signal in the system. The experimental results showed that the nanoprobe had high sensitivity, with a linear range of 5 ng/mL to 400 ng/mL and a minimum detection limit of 0.38 ng/mL.<h3>Significance</h3>This method achieved dual signal quantification and visualization imaging of fluorescence and SERS for caspase-9. The application of nanomaterials has been broadened and the assay was well versatile in different human cell lines. It provided a new platform in studying the relationship between food safety and cellular homeostasis mechanisms.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678801","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Comprehensive Host Cell Proteins Profiling in Biopharmaceuticals by A Sensitivity Enhanced Mass Spectrometry Strategy Using TMT-labeling and Signal Boosting 利用 TMT 标记和信号增强技术的灵敏度增强型质谱分析策略,对生物制药中的宿主细胞蛋白质进行全面分析
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-21 DOI: 10.1016/j.aca.2024.343445
Andong Xue, Linlin Kong, Jialin Li, Yuxin Jiao, Zhishang Hu, Bin Fu, Guibin Wang, Wanjun Zhang, Jianheng Li, Weijie Qin

Background

Host Cell Proteins (HCPs) are impurities expressed in host cells during the biopharmaceutical production process, which. may compromise product quality and potentially leading to immunogenic reactions or other adverse effects. Mass spectrometry (MS)-based strategy is more and more considered as a promising method for HCPs analysis, since it is capable of simultaneously quantifying thousands of proteins in a single test. However, considering the large excess biopharmaceutical product protein present in the system and the extremely low abundance of HCPs, sensitive MS methods are urgently needed in HCPs analysis.

Results

In this work, we introduced a novel approach that leveraged host cell lysate as a boosting channel to enhance the MS signal of the residue HCPs in biopharmaceutical products using isobaric TMT labeling, thereby elevating the low-abundant HCPs to detectable and quantifiable levels of current MS without using enrichment or depletion method to avoid disturbance of the original concentration of the HCPs. Our method surpassed previous benchmarks by identifying a significantly higher number (23844 unique peptides for 3475 proteins) compared to existing records (4541 unique peptides for 848 proteins) for HCPs analysis in RM8671 NIST monoclonal antibody (mAb), demonstrating unparalleled sensitivity and robustness. Furthermore, our workflow successfully identified 44 of 48 UPS1 proteins across a concentration range of 0.32 to 4.15 ppm in monoclonal antibodies (mAbs), proving its effectiveness for in-depth HCPs analysis in biopharmaceuticals.

Significance

Present even at sub-ppm levels, HCPs may compromise the stability and safety of product proteins and alter pharmacokinetics or neutralization of therapeutic effects. Our MS signal enhancing method presented an advancement in HCP analysis, combining improved sensitivity and increased scale of HCPs with a streamlined and robust workflow. This method allowed HCPs quantification at <1 ppm level without disturbance of the original HCPs concentration, which is still rare in the field.
背景宿主细胞蛋白(HCPs)是生物制药生产过程中宿主细胞中表达的杂质,可能会影响产品质量,并可能导致免疫原性反应或其他不良反应。基于质谱法(MS)的策略越来越被认为是一种有前途的 HCPs 分析方法,因为它能够在一次检测中同时定量数千种蛋白质。然而,考虑到系统中存在大量过剩的生物制药产品蛋白质,以及 HCPs 的丰度极低,HCPs 分析迫切需要灵敏的 MS 方法。结果在这项工作中,我们引入了一种新方法,利用宿主细胞裂解液作为增强通道,使用等位 TMT 标记法增强生物制药产品中残留 HCPs 的 MS 信号,从而将低丰度 HCPs 提高到当前 MS 可检测和可量化的水平,而无需使用富集或耗竭方法来避免 HCPs 原始浓度受到干扰。在 RM8671 NIST 单克隆抗体(mAb)的 HCPs 分析中,与现有记录(848 个蛋白质的 4541 个唯一肽)相比,我们的方法识别出了更多的 HCPs(3475 个蛋白质的 23844 个唯一肽),超越了之前的基准,显示了无与伦比的灵敏度和稳健性。此外,我们的工作流程成功鉴定了单克隆抗体 (mAb) 中浓度范围为 0.32 至 4.15ppm 的 48 个 UPS1 蛋白中的 44 个,证明了其在生物制药中深入分析 HCPs 的有效性。我们的质谱信号增强方法是 HCP 分析的一大进步,它将提高灵敏度、扩大 HCP 的范围与简化、稳健的工作流程相结合。该方法可在不干扰原始 HCPs 浓度的情况下,将 HCPs 定量在百万分之 1 的水平,这在该领域仍属罕见。
{"title":"Comprehensive Host Cell Proteins Profiling in Biopharmaceuticals by A Sensitivity Enhanced Mass Spectrometry Strategy Using TMT-labeling and Signal Boosting","authors":"Andong Xue, Linlin Kong, Jialin Li, Yuxin Jiao, Zhishang Hu, Bin Fu, Guibin Wang, Wanjun Zhang, Jianheng Li, Weijie Qin","doi":"10.1016/j.aca.2024.343445","DOIUrl":"https://doi.org/10.1016/j.aca.2024.343445","url":null,"abstract":"<h3>Background</h3>Host Cell Proteins (HCPs) are impurities expressed in host cells during the biopharmaceutical production process, which. may compromise product quality and potentially leading to immunogenic reactions or other adverse effects. Mass spectrometry (MS)-based strategy is more and more considered as a promising method for HCPs analysis, since it is capable of simultaneously quantifying thousands of proteins in a single test. However, considering the large excess biopharmaceutical product protein present in the system and the extremely low abundance of HCPs, sensitive MS methods are urgently needed in HCPs analysis.<h3>Results</h3>In this work, we introduced a novel approach that leveraged host cell lysate as a boosting channel to enhance the MS signal of the residue HCPs in biopharmaceutical products using isobaric TMT labeling, thereby elevating the low-abundant HCPs to detectable and quantifiable levels of current MS without using enrichment or depletion method to avoid disturbance of the original concentration of the HCPs. Our method surpassed previous benchmarks by identifying a significantly higher number (23844 unique peptides for 3475 proteins) compared to existing records (4541 unique peptides for 848 proteins) for HCPs analysis in RM8671 NIST monoclonal antibody (mAb), demonstrating unparalleled sensitivity and robustness. Furthermore, our workflow successfully identified 44 of 48 UPS1 proteins across a concentration range of 0.32 to 4.15 ppm in monoclonal antibodies (mAbs), proving its effectiveness for in-depth HCPs analysis in biopharmaceuticals.<h3>Significance</h3>Present even at sub-ppm levels, HCPs may compromise the stability and safety of product proteins and alter pharmacokinetics or neutralization of therapeutic effects. Our MS signal enhancing method presented an advancement in HCP analysis, combining improved sensitivity and increased scale of HCPs with a streamlined and robust workflow. This method allowed HCPs quantification at &lt;1 ppm level without disturbance of the original HCPs concentration, which is still rare in the field.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"18 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678803","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Characterization of biogenic selenium nanoparticles in hypersaline media by single particle inductively coupled plasma mass spectrometry: Haloferax mediterranei case. 单颗粒电感耦合等离子体质谱法表征高盐介质中的生物硒纳米颗粒:米德兰光蜡(Haloferax mediterranei)案例。
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-11-21 DOI: 10.1016/j.aca.2024.343453
Nuria Guijarro-Ramírez, Iraide Sáez-Zamacona, Daniel Torregrosa, Guillermo Grindlay, Luis Gras, Carmen Pire, Juan Mora, Rosa María Martínez-Espinosa

Background

Single particle inductively coupled plasma mass spectrometry (spICP-MS) is extensively employed for the characterization of biogenic selenium nanoparticles (SeNPs) produced by mesophilic microorganisms. Nevertheless, because halophilic microorganisms are also well-known to produce SeNPs, further research efforts are required to investigate spICP-MS applicability for characterizing such nanomaterials in hypersaline media. The goal of this work is to develop a methodology for characterizing SeNPs in hypersaline media by spICP-MS. To this end, plasma operating conditions, non-spectral interferences and calibration strategies were investigated. The proposed method was employed to investigate the capabilities of the halophilic archaea Haloferax mediterranei to produce SeNPs.

Results

By the appropriate selection of experimental conditions, SeNPs can be accurately analyzed in hypersaline media by spICP-MS. Unlike previous works in the literature, no differences in ionic signal were observed between SeNPs and dissolved Se and, hence, there is no need to apply any empirical corrector factor for obtaining accurate particle size distributions. Non-spectral interferences are mitigated by diluting the sample at least 1:103 which allows the use of water standards. Size (30 nm) and particle (7 x 105 particles mL-1) detection limits were low enough to characterize biogenic SeNPs produced by halophilic microorganisms. The use of the optimized methodology reveals that Haloferax mediterranei can produce SeNPs when it is exposed to selenite up to 1 mM, but no formation is produced for selenate exposure. Depending on incubation parameters (selenite concentration and time), the particle median diameter ranged from 80-100 nm, whereas particle concentration varied from 0.8 to 1.9 x1013 particles mL-1.

Significance

This represents the first methodology for characterizing biogenic SeNPs in hypersaline media by spICP-MS with accuracy and precision using non-matrix matched standards. It opens the opportunity to investigate the capabilities of halophilic microorganisms (e.g., H. mediterranei) to produce Se-based nanomaterials.
背景单颗粒电感耦合等离子体质谱法(spICP-MS)被广泛用于表征中嗜酸性微生物产生的生物硒纳米颗粒(SeNPs)。然而,由于众所周知嗜卤微生物也会产生 SeNPs,因此需要进一步研究 spICP-MS 是否适用于表征超盐介质中的此类纳米材料。这项工作的目标是开发一种利用 spICP-MS 表征超碱性介质中 SeNPs 的方法。为此,研究了等离子体操作条件、非光谱干扰和校准策略。结果 通过适当选择实验条件,spICP-MS 可以准确分析超碱性介质中的 SeNPs。与之前的文献不同,SeNPs 和溶解的 Se 之间没有观察到离子信号的差异,因此无需应用任何经验校正因子来获得准确的粒度分布。通过将样品稀释至少 1:103,可以使用水标准,从而减轻非光谱干扰。粒度(30 nm)和颗粒(7 x 105 个颗粒 mL-1)的检测限很低,足以确定嗜卤微生物产生的生物源 SeNPs 的特征。使用优化方法发现,当 Haloferax mediterranei 暴露于高达 1 mM 的亚硒酸盐时,它可以产生 SeNPs,但暴露于硒酸盐时则不会产生。根据培养参数(亚硒酸盐浓度和时间)的不同,颗粒的中值直径在 80-100 nm 之间,而颗粒浓度则在 0.8-1.9 x1013 颗粒 mL-1 之间变化。它为研究嗜卤微生物(如 H. mediterranei)生产 Se 基纳米材料的能力提供了机会。
{"title":"Characterization of biogenic selenium nanoparticles in hypersaline media by single particle inductively coupled plasma mass spectrometry: Haloferax mediterranei case.","authors":"Nuria Guijarro-Ramírez, Iraide Sáez-Zamacona, Daniel Torregrosa, Guillermo Grindlay, Luis Gras, Carmen Pire, Juan Mora, Rosa María Martínez-Espinosa","doi":"10.1016/j.aca.2024.343453","DOIUrl":"https://doi.org/10.1016/j.aca.2024.343453","url":null,"abstract":"<h3>Background</h3>Single particle inductively coupled plasma mass spectrometry (spICP-MS) is extensively employed for the characterization of biogenic selenium nanoparticles (SeNPs) produced by mesophilic microorganisms. Nevertheless, because halophilic microorganisms are also well-known to produce SeNPs, further research efforts are required to investigate spICP-MS applicability for characterizing such nanomaterials in hypersaline media. The goal of this work is to develop a methodology for characterizing SeNPs in hypersaline media by spICP-MS. To this end, plasma operating conditions, non-spectral interferences and calibration strategies were investigated. The proposed method was employed to investigate the capabilities of the halophilic archaea <em>Haloferax mediterranei</em> to produce SeNPs.<h3>Results</h3>By the appropriate selection of experimental conditions, SeNPs can be accurately analyzed in hypersaline media by spICP-MS. Unlike previous works in the literature, no differences in ionic signal were observed between SeNPs and dissolved Se and, hence, there is no need to apply any empirical corrector factor for obtaining accurate particle size distributions. Non-spectral interferences are mitigated by diluting the sample at least 1:10<sup>3</sup> which allows the use of water standards. Size (30 nm) and particle (7 x 10<sup>5</sup> particles mL<sup>-1</sup>) detection limits were low enough to characterize biogenic SeNPs produced by halophilic microorganisms. The use of the optimized methodology reveals that <em>Haloferax mediterranei</em> can produce SeNPs when it is exposed to selenite up to 1 mM, but no formation is produced for selenate exposure. Depending on incubation parameters (selenite concentration and time), the particle median diameter ranged from 80-100 nm, whereas particle concentration varied from 0.8 to 1.9 x10<sup>13</sup> particles mL<sup>-1</sup>.<h3>Significance</h3>This represents the first methodology for characterizing biogenic SeNPs in hypersaline media by spICP-MS with accuracy and precision using non-matrix matched standards. It opens the opportunity to investigate the capabilities of halophilic microorganisms (e.g., <em>H. mediterranei</em>) to produce Se-based nanomaterials.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"117 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678841","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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Analytica Chimica Acta
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