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Analytica Chimica Acta最新文献

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Advancing elemental analysis by collision/reaction cell technology and micro-droplet calibration for bioimaging applications by LA-ICP-TOFMS 利用碰撞池技术和微滴校准推进元素分析,通过 LA-ICP-TOFMS 实现生物成像应用
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-19 DOI: 10.1016/j.aca.2024.343345
Sarah Theiner , Elisabeth Foels , Gunda Koellensperger

Background

Bioimaging applications by laser ablation inductively coupled plasma time-of-flight mass spectrometry (LA-ICP-TOFMS) require comprehensive elemental analysis spanning the entire mass range. Within biological systems, endogenous elements are critical for maintaining metal homeostasis in cells, a fundamental aspect in disease progression when disrupted. Additionally, elements from the higher mass range may originate from various sources such as metal-tags for immuno-mass spectrometry, nanoparticles, or metal-based anticancer drugs. This study assesses the efficacy of collision/reacton cell (CCT) mode for simultaneously analysing elements across the complete mass spectrum. Furthermore, we demonstrate the accuracy of the LA-ICP-TOFMS methodology through the analysis of serum reference material.

Results

Our findings demonstrate that the CCT mode outperforms the standard/no gas mode for LA-ICP-TOFMS measurements, particularly in quantifying endogenous elements susceptible to interferences. Through the analysis of picolitre-volume micro-droplet standards and serum reference material (deposited as micro-droplets), we observed accurate quantification of elements such as iron and selenium, with isotope ratios closely resembling natural compositions. As key advantage, the utilization of the CCT mode eliminated the need for labor-intensive post-data processing, streamlining analytical procedures. Additionally, the CCT mode also provided enhanced sensitivity (factor of 1.5–2) for elements in the higher mass range compared to the standard mode, without compromising the sensitivity for endogenous elements.

Significance

We successfully integrated Seronorm serum reference material-containing micro-droplets into LA-ICPMS bioimaging workflows for quality control, enabling validated measurements of key biological elements. The use of the CCT mode is highly recommended for bioimaging applications that address the analysis of elements across the entire mass range.
背景使用激光烧蚀电感耦合等离子体飞行时间质谱(LA-ICP-TOFMS)进行生物成像应用需要在整个质量范围内进行全面的元素分析。在生物系统中,内源元素对维持细胞中的金属平衡至关重要,一旦受到破坏,就会成为疾病发展的一个基本方面。此外,更高质 量范围的元素可能来自各种来源,如用于免疫质谱分析的金属标签、纳米粒子或基于金属的抗癌药物。本研究评估了碰撞/反应池(CCT)模式同时分析整个质谱中元素的功效。结果我们的研究结果表明,在 LA-ICP-TOFMS 测量中,CCT 模式优于标准/无气模式,尤其是在定量易受干扰的内源元素方面。通过分析皮升体积的微滴标准物质和血清参考物质(沉积为微滴),我们观察到了铁和硒等元素的精确定量,其同位素比值与天然成分非常接近。CCT 模式的主要优点是无需进行劳动密集型的后数据处理,从而简化了分析程序。此外,与标准模式相比,CCT 模式还提高了对高质范围元素的灵敏度(系数为 1.5 到 2),同时不影响对内源性元素的灵敏度。我们强烈建议在分析整个质量范围内元素的生物成像应用中使用 CCT 模式。
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引用次数: 0
Selectivity in Nontargeted Qualitative Analysis 非目标定性分析的选择性
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-19 DOI: 10.1016/j.aca.2024.343352
A.L. Pomerantsev, O.Ye. Rodionova

Background

The concept of selectivity is used extensively in analytical chemistry in both quantitative and qualitative analyses. While in the first case, the definition and use of selectivity have been somehow regulated, in the second case it remains a vague concept.

Results

In this paper we propose a new definition of selectivity in qualitative analysis as well as the way to estimate it numerically.

Significance

It is shown how selectivity can be used practically to compare analytical objects, measurement techniques, and data modeling methods.
背景选择性的概念在分析化学的定量和定性分析中被广泛使用。在前者中,选择性的定义和使用已经有了一定的规范,而在后者中,它仍然是一个模糊的概念。(40)结果在本文中,我们提出了定性分析中选择性的新定义以及用数字估算选择性的方法。(23)意义本文展示了如何实际利用选择性来比较分析对象、测量技术和数据建模方法。(19)
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引用次数: 0
Synthesis of a novel β-cyclodextrin chiral stationary phase and its application to the evaluation of the enantioselective bioaccumulation and elimination behavior of tebuconazole in Rana nigromaculata tadpoles 新型 β-环糊精手性固定相的合成及其在评估戊唑醇在黑鳃蛙蝌蚪中的对映体选择性生物累积和消除行为中的应用
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-18 DOI: 10.1016/j.aca.2024.343344
Linbin Zheng , Meng Li , Zhouyu Jiang , Junyan Fan , Zengbo Fang , Jihuai Zheng , Yan Cui

Background

The increased production and use of chiral pesticides will enhance their exposure in the environment. Chiral pesticides typically exhibit varied biological effects among these enantiomers. Therefore, it is very essential to develop and validate chiral analytical methods to investigate their potential ecological risks from a stereoselective perspective. Current separation of pesticides enantiomers relies extensively on chiral stationary phases (CSPs), while the development of β-Cyclodextrin derivatives CSPs become the research focus due to their great modifiability and excellent chiral recognition capabilities.

Results

A novel chiral stationary phase, 3,5-dichlorophenylaminomethyl-6-phenylenediamine-β-cyclodextrin chemically bonded silica gel (MPDCDA), was successfully prepared. Based on that, a stereoselective HPLC-MS/MS method was developed and validated for the determination of tebuconazole enantiomers in Rana nigromaculata tadpoles. After extraction by QuEChERS, the tebuconazole enantiomers were completely separated with the resolutions of 1.63 using the mobile phase of methanol-water (70/30, v/v). Good linearity (r > 0.9990) for both enantiomers over a concentration range of 0.20–500.0 ng/mL was obtained with the accuracy ranged from 6.7 % to 9.3 % and the intra-day and inter-day precisions below 6.2 % at three quality control levels. The proposed method was successfully applied in evaluating the enantioselective bioaccumulation and elimination profiles of tebuconazole in tadpoles. At the tested conditions, there was no significantly enantioselective difference in the bioaccumulation process for S- tebuconazole and R-tebuconazole. However, the elimination process of tebuconazole enantiomers was enantioselective with R-tebuconazole preferentially degraded.

Significance

This work provided an accurate risk assessment of chiral pesticides to non-target aquatic organisms from a stereoselective perspective. These findings would deepen our understanding of the potential ecological risks of chiral pesticides on aquatic organisms and provide scientific support for the protection of aquatic organisms and their ecological environments, as well as sustainable development.
背景手性农药生产和使用的增加会增加其在环境中的暴露量。手性农药的对映体通常具有不同的生物效应。因此,开发和验证手性分析方法以从立体选择性角度研究其潜在的生态风险非常重要。目前农药对映体的分离广泛依赖于手性固定相(CSPs),而β-环糊精衍生物 CSPs 因其极佳的可调控性和优异的手性识别能力而成为研究的重点。在此基础上,建立并验证了一种立体选择性 HPLC-MS/MS 方法,用于测定黑线蛙蝌蚪中戊唑醇对映体的含量。经QuEChERS萃取后,以甲醇-水(70/30,v/v)为流动相,戊唑醇对映体完全分离,分辨率为1.63。在0.20-500.0 ng/mL浓度范围内,两种对映体的线性关系良好(r > 0.9990),在3个质控水平下,准确度为6.7%-9.3%,日内和日间精密度低于6.2%。该方法成功地应用于评价戊唑醇在蝌蚪体内的对映体选择性生物累积和消除谱图。在测试条件下,S-戊唑醇和 R-戊唑醇的生物累积过程没有明显的对映体选择性差异。不过,戊唑醇对映体的消除过程具有对映选择性,R- 戊唑醇优先降解。这些发现将加深我们对手性农药对水生生物潜在生态风险的认识,为水生生物及其生态环境的保护和可持续发展提供科学支持。
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引用次数: 0
A novel near-infrared fluorescent probe for butyrylcholinesterase: Research for screening of natural anti-AD inhibitors 丁酰胆碱酯酶的新型近红外荧光探针:天然抗丁酰胆碱酯酶抑制剂的筛选研究
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-18 DOI: 10.1016/j.aca.2024.343348
Xiaoyi Yin , Gaoning Zhang , Guangxu Song , Xiaoru Li , Xinming Liu , Lufan Wang , Hai Zhang , Zhixin Tang
Elevated levels of butyrylcholinesterase (BuChE) have the potential to be predictive in the timely detection and diagnosis of Alzheimer's disease (AD). By inhibiting of BuChE activity can raise acetylcholine levels and intervene AD processes. Therefore, BuChE as an important factor in treatment AD has been given more and more attention in clinical studies. Given the facts above, in this study, for precise monitoring of BuChE level changes and screening for possible butyrylcholinesterase inhibitor (BuChEI) for AD diagnosis and therapy, a near-infrared (NIR) fluorescence probe (NFP-BuChE) was created. The probe exhibits excellent sensitivity and selectivity for BuChE. NFP-BuChE has been successfully applied to the detection of endogenous BuChE levels in live cells, and we successfully constructed a screening system for BuChEI on cells and a novel natural efficient BuChEI (matrine) was discovered and identified, which significantly reduced BuChE activity and thus alleviated AD symptoms. Most importantly, for the first time, we measured the changes of BuChE levels in zebrafish (0–4 days) after fertilization, various organs of zebrafish, and AD zebrafish modeled by different concentrations of AlCl3 by NFP-BuChE, and at the same time, we also validated the inhibitory effect of matrine on BuChE by NFP-BuChE in zebrafish. In addition, NFP-BuChE has also been successfully used to measure the changes of BuChE levels in the brains of AD mice. These findings imply that NFP-BuChE is a potentially useful molecular tool for screening possible natural BuChEI quickly and for monitoring changes in BuChE activity, and it is expected that more value will be explored in mice. In addition, matrine and its derivatives are promising options for future Alzheimer's disease treatments.
丁酰胆碱酯酶(BuChE)水平的升高有可能预测阿尔茨海默病(AD)的及时检测和诊断。通过抑制 BuChE 的活性可以提高乙酰胆碱的水平,从而干预阿尔茨海默病的进程。因此,BuChE作为治疗AD的重要因素在临床研究中越来越受到重视。鉴于以上事实,为了精确监测 BuChE 水平的变化并筛选可能的丁酰胆碱酯酶抑制剂(BuChEI)用于 AD 的诊断和治疗,本研究创建了一种近红外(NIR)荧光探针(NFP-BuChE)。该探针对 BuChE 具有出色的灵敏度和选择性。NFP-BuChE 已成功应用于活细胞中内源性 BuChE 水平的检测,我们还成功构建了细胞中 BuChEI 的筛选系统,发现并鉴定了一种新型天然高效 BuChEI(matrine),它能显著降低 BuChE 活性,从而缓解 AD 症状。最重要的是,我们首次用NFP-BuChE测定了受精后(0-4天)斑马鱼、斑马鱼各器官和不同浓度AlCl3模拟的AD斑马鱼体内BuChE水平的变化,同时还验证了NFP-BuChE在斑马鱼体内对matrine的BuChE抑制作用。此外,NFP-BuChE还被成功用于测量AD小鼠大脑中BuChE水平的变化。这些发现意味着,NFP-BuChE 是一种潜在的有用分子工具,可用于快速筛选可能的天然 BuChEI 和监测 BuChE 活性的变化,有望在小鼠身上挖掘出更多价值。此外,马钱子碱及其衍生物是未来治疗阿尔茨海默病的有望选择。
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引用次数: 0
Radical-directed dissociation mass spectrometry for differentiation and relative quantitation of isomeric ether-linked phosphatidylcholines 用于区分和相对定量异构醚键磷脂酰胆碱的 Radical-Directed Dissociation Mass Spectrometry 方法
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-18 DOI: 10.1016/j.aca.2024.343337
Xiaohui Zhang , Qinhua Chen , Lun Wu , Wenpeng Zhang , Xue Zhao

Background

Ether-linked phosphatidylcholines (PCs) include both plasmanyl and plasmenyl PCs, which contain an ether or a vinyl ether bond at the sn-1 linkage position, respectively. Profiling and quantifying ether PCs with accurate structural information is challenging because of the common presence of isomeric and isobaric species in a lipidome.

Results

In the present study, radical directed dissociation (RDD) from collision-induced dissociation (CID) of the bicarbonate anion adduct of ether PCs has been investigated to differentiate and relatively quantify ether PCs. Alkyl- and alkenyl- PCs give diagnostic characteristic fragment patterns that enable their confident identification and isomer differentiation. Additionally, the sn-position specific product ions have proven effective for relative quantitation among isomers in ether PCs and their isobaric PC species. Using this methodology, we successfully identified a total of 30 PC-O species, 21 PC-P species at the chain composition level, and 22 species of isobaric PC at the sn-position level in the human plasma lipid extract. The quantitative analysis revealed that ether PCs with a 20:4 fatty acyl chain are relatively more abundant in human plasma. Finally, the profile of ether PCs in type 2 diabetic (T2D) groups compared to normal control groups revealed a significant decrease in PC-O 18:1/20:5. We also found it is the PC species containing a 17-carbon fatty acyl chain, rather than their isobaric ether PCs, that shows a decreasing trend in the T2D groups.

Significance

ether-linked PCs are firstly investigated by RDD mass spectrometry.
背景醚键磷脂酰胆碱(PCs)包括plasmanyl和plasmmenyl PCs,它们分别在sn-1连接位上含有一个醚键或一个乙烯基醚键。由于脂质体中通常存在异构体和同分异构体,因此利用准确的结构信息来分析和定量醚类 PC 具有挑战性。研究结果本研究研究了醚类 PC 的碳酸氢盐阴离子加合物碰撞诱导解离(CID)产生的自由基定向解离(RDD),以区分和相对定量醚类 PC。烷基和烯基多氯联苯具有诊断性的特征碎片模式,可以对其进行可靠的识别和异构体区分。此外,Sn 位特异性产物离子已被证明可有效地对醚多氯化萘及其异构体多氯化萘进行相对定量。利用这种方法,我们成功地在人体血浆脂质提取物中鉴定出了 30 种 PC-O、21 种 PC-P(链组成水平)和 22 种异构 PC(sn-位置水平)。定量分析结果显示,人血浆中脂肪酰基链为 20:4 的醚型多氯联苯含量相对较高。最后,与正常对照组相比,2 型糖尿病(T2D)组中的醚型多氯化萘的分布显示 PC-O 18:1/20:5 显著减少。我们还发现,在 T2D 组别中呈下降趋势的是含有 17 碳脂肪酰基链的 PC 种类,而不是它们的异位醚 PC。
{"title":"Radical-directed dissociation mass spectrometry for differentiation and relative quantitation of isomeric ether-linked phosphatidylcholines","authors":"Xiaohui Zhang ,&nbsp;Qinhua Chen ,&nbsp;Lun Wu ,&nbsp;Wenpeng Zhang ,&nbsp;Xue Zhao","doi":"10.1016/j.aca.2024.343337","DOIUrl":"10.1016/j.aca.2024.343337","url":null,"abstract":"<div><h3>Background</h3><div>Ether-linked phosphatidylcholines (PCs) include both plasmanyl and plasmenyl PCs, which contain an ether or a vinyl ether bond at the <em>sn</em>-1 linkage position, respectively. Profiling and quantifying ether PCs with accurate structural information is challenging because of the common presence of isomeric and isobaric species in a lipidome.</div></div><div><h3>Results</h3><div>In the present study, radical directed dissociation (RDD) from collision-induced dissociation (CID) of the bicarbonate anion adduct of ether PCs has been investigated to differentiate and relatively quantify ether PCs. Alkyl- and alkenyl- PCs give diagnostic characteristic fragment patterns that enable their confident identification and isomer differentiation. Additionally, the <em>sn</em>-position specific product ions have proven effective for relative quantitation among isomers in ether PCs and their isobaric PC species. Using this methodology, we successfully identified a total of 30 PC-O species, 21 PC-P species at the chain composition level, and 22 species of isobaric PC at the <em>sn</em>-position level in the human plasma lipid extract. The quantitative analysis revealed that ether PCs with a 20:4 fatty acyl chain are relatively more abundant in human plasma. Finally, the profile of ether PCs in type 2 diabetic (T2D) groups compared to normal control groups revealed a significant decrease in PC-O 18:1/20:5. We also found it is the PC species containing a 17-carbon fatty acyl chain, rather than their isobaric ether PCs, that shows a decreasing trend in the T2D groups.</div></div><div><h3>Significance</h3><div>ether-linked PCs are firstly investigated by RDD mass spectrometry.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1331 ","pages":"Article 343337"},"PeriodicalIF":5.7,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449711","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
Optimising the acquisition conditions of high information quality low-field NMR signals based on a cutting-edge approach applying information theory and Taguchi's experimental designs – Virgin olive oil as an application example 基于应用信息论和田口试验设计的前沿方法优化高信息质量低场核磁共振信号的采集条件--以初榨橄榄油为例
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-18 DOI: 10.1016/j.aca.2024.343350
Alejandra Arroyo-Cerezo , Ana M. Jiménez-Carvelo , Rosalía López-Ruíz , María Tello-Liébana , Luis Cuadros-Rodríguez

Background

Developing a new spectrometric analytical method based on a fingerprinting approach requires optimisation of the experimental stage, particularly with novel instruments like benchtop low-field NMR spectrometers. To ensure high-quality LF-NMR spectra before developing the multivariate model, an experimental design to optimise instrument conditions is essential. However, difficult-to-control factors may be critical for optimisation. Taguchi methodology addresses these factors to obtain a system robust to variation. This study uses the Taguchi methodology to optimise instrument settings for acquiring high-quality 1H and 13C LF-NMR signals in a short time from virgin olive oil (VOO).

Results

Two experimental trials (for 1H and 13C signals, respectively) were carried out and analysed to find an optimal and robust combination of instrument settings against changes in two difficult-to-control factors: ambient temperature and small deviations of the NMR tube volume (700 ± 50 μL). The responses to be optimised, run time and spectral information quality, were analysed separately and jointly, as some factors showed opposite behaviour in the effect on the responses. Multiple response analysis based on suitable desirability functions yielded a combination of factors resulting in desirability values above 0.8 for 1H LF-NMR signals and almost 1.0 for 13C LF-NMR signals.
In addition, a novel approach to assess the information quality of an analytical signal was proposed, addressing a major challenge in analytical chemistry. By applying information theory and calculating information entropy, this approach demonstrated its potential for selecting the highest quality (i.e. most informative) analytical signals.

Significance

The acquisition instrument conditions of LF-NMR were successfully optimised using Taguchi methodology to acquire highly informative 1H and 13C spectra in a minimum run time. The importance lies in the future development of non-targeted analytical applications for VOO quality control. In addition, the innovative use of information entropy to a priori assess the signal quality represents a significant advance and proposes a solution to a long-standing challenge in analytical chemistry.
背景开发基于指纹识别方法的新光谱分析方法需要优化实验阶段,尤其是台式低场 NMR 光谱仪等新型仪器。为了在建立多元模型之前确保高质量的低场 NMR 图谱,优化仪器条件的实验设计至关重要。然而,难以控制的因素可能是优化的关键。田口方法可解决这些因素,从而获得一个对变化具有鲁棒性的系统。本研究使用田口方法优化仪器设置,以便在短时间内从初榨橄榄油 (VOO) 中获取高质量的 1H 和 13C LF-NMR 信号。结果进行了两次实验(分别针对 1H 和 13C 信号),并对实验结果进行了分析,以找到针对两个难以控制的因素(环境温度和 NMR 管容积的微小偏差(700 ± 50 μL))变化的仪器设置的最佳稳健组合。需要优化的响应、运行时间和光谱信息质量分别和联合进行了分析,因为某些因素对响应的影响表现出相反的行为。根据适当的可取性函数进行多重响应分析,得出了各种因素的组合,结果是 1H LF-NMR 信号的可取值高于 0.8,13C LF-NMR 信号的可取值接近 1.0。通过应用信息论和计算信息熵,该方法证明了其在选择最高质量(即信息量最大)分析信号方面的潜力。这对未来开发用于 VOO 质量控制的非目标分析应用具有重要意义。此外,创新性地使用信息熵来先验评估信号质量是一项重大进步,并为分析化学中的一个长期挑战提出了解决方案。
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引用次数: 0
Microwave-assisted extraction of polysaccharides from Micromelum minutum leaves using citric acid monohydrate-glycerol based deep eutectic solvents and evaluation of biological activities 使用一水柠檬酸-甘油深共晶溶剂微波辅助提取小叶藻叶多糖及其生物活性评价
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-18 DOI: 10.1016/j.aca.2024.343351
Muhammad Hasnun Md Yusoff, Muhammad Hakimin Shafie

Background

The extraction of polysaccharides using an acidic extraction media has been extensively reported, highlighting its effectiveness in yielding high-quality polysaccharides. A higher concentration of acidic solution could hydrolyze the structure of polysaccharide, while a low concentration reduces the extraction efficiency. Despite this challenges, deep eutectic solvents (DES) were introduced as an alternative extraction medium due to additional interactions such as inter and intra-molecular interactions, Van de Waals, hydrogen bond, and electrostatic interactions, which could improve the polysaccharide extraction efficiency and biological activities. Furthermore, the extraction conditions such as extraction medium and extraction parameters could affect the properties of polysaccharides as well as influence their structure-activity relationship for biological activities.

Results

The result showed that the microwave-assisted extraction of Micromelum minutum leaf polysaccharide (MMLP) using DES as an extraction media (MMLP-DES) gave a higher yield (improvement of 101.20 %) than citric acid monohydrate (CAM) (MMLP-CAM) and required a lower percentage of microwave power (19.83 % less) and time (0.78 min less). The properties of MMLPs significantly differ based on their pH, molecular weight, viscosity, degree of esterification and monosaccharide molar ratio which influenced the biological activities. Compared to MMLP-CAM, MMLP-DES had a more branched and less linear structure. The bioactivities study revealed that MMLP-DES exhibited higher antioxidant and anti-α-amylase activities (i.e., DPPH: 74.52 %, FRAP: 2.87 mM FeSO4 and α-amylase inhibition: 86.23 %) compared to MMLP-CAM (i.e., DPPH: 49.33 %, FRAP: 1.49 mM FeSO4, and α-amylase inhibition: 81.76 %). The mechanism and structure-activity relationship of MMLPs on bioactivities were also hypothesized.

Significance

Based on our previous study, the citric acid monohydrate-glycerol based DES as an extraction medium has enhanced the extraction yield of polysaccharides from M. minutum. This study highlights the DES combined with microwave-assisted extraction to improve the yield of MMLP and evaluate the biological activities compared to CAM as a classical solvent. In conclusion, the DES showed the advantages for extraction of polysaccharides with desired biological activities.
背景使用酸性萃取介质萃取多糖的研究已被广泛报道,突出了其在获得高质量多糖方面的有效性。高浓度的酸性溶液会水解多糖的结构,而低浓度的酸性溶液则会降低提取效率。尽管存在这些挑战,但由于深共晶溶剂(DES)具有分子间和分子内相互作用、范德华作用、氢键作用和静电作用等额外的相互作用,可提高多糖的提取效率和生物活性,因此被引入作为替代提取介质。此外,萃取介质和萃取参数等萃取条件也会影响多糖的性质,并影响其生物活性的结构-活性关系。结果表明,以DES为提取介质的微波辅助提取小麦叶多糖(MMLP)(MMLP-DES)比一水柠檬酸(CAM)(MMLP-CAM)的得率高(提高了101.20%),所需的微波功率(减少19.83%)和时间(减少0.78分钟)也更低。MMLPs 的 pH 值、分子量、粘度、酯化程度和单糖摩尔比对生物活性有显著影响。与 MMLP-CAM 相比,MMLP-DES 的支链结构较多,线性结构较少。生物活性研究表明,与 MMLP-CAM 相比,MMLP-DES 具有更高的抗氧化和抗α-淀粉酶活性(即 DPPH:74.52%,FRAP:2.87 mM FeSO4,α-淀粉酶抑制率:86.23%)(即 DPPH:49.33%,FRAP:1.49 mM FeSO4,α-淀粉酶抑制率:81.76%)。意义根据我们之前的研究,以一水柠檬酸-甘油为基础的 DES 作为提取介质提高了 M. minutum 多糖的提取率。与传统溶剂 CAM 相比,本研究强调 DES 与微波辅助萃取相结合可提高 MMLP 的得率并评估其生物活性。总之,DES在提取具有所需生物活性的多糖方面显示出了优势。
{"title":"Microwave-assisted extraction of polysaccharides from Micromelum minutum leaves using citric acid monohydrate-glycerol based deep eutectic solvents and evaluation of biological activities","authors":"Muhammad Hasnun Md Yusoff,&nbsp;Muhammad Hakimin Shafie","doi":"10.1016/j.aca.2024.343351","DOIUrl":"10.1016/j.aca.2024.343351","url":null,"abstract":"<div><h3>Background</h3><div>The extraction of polysaccharides using an acidic extraction media has been extensively reported, highlighting its effectiveness in yielding high-quality polysaccharides. A higher concentration of acidic solution could hydrolyze the structure of polysaccharide, while a low concentration reduces the extraction efficiency. Despite this challenges, deep eutectic solvents (DES) were introduced as an alternative extraction medium due to additional interactions such as inter and intra-molecular interactions, Van de Waals, hydrogen bond, and electrostatic interactions, which could improve the polysaccharide extraction efficiency and biological activities. Furthermore, the extraction conditions such as extraction medium and extraction parameters could affect the properties of polysaccharides as well as influence their structure-activity relationship for biological activities.</div></div><div><h3>Results</h3><div>The result showed that the microwave-assisted extraction of <em>Micromelum minutum</em> leaf polysaccharide (MMLP) using DES as an extraction media (MMLP-DES) gave a higher yield (improvement of 101.20 %) than citric acid monohydrate (CAM) (MMLP-CAM) and required a lower percentage of microwave power (19.83 % less) and time (0.78 min less). The properties of MMLPs significantly differ based on their pH, molecular weight, viscosity, degree of esterification and monosaccharide molar ratio which influenced the biological activities. Compared to MMLP-CAM, MMLP-DES had a more branched and less linear structure. The bioactivities study revealed that MMLP-DES exhibited higher antioxidant and anti-α-amylase activities (i.e., DPPH: 74.52 %, FRAP: 2.87 mM FeSO<sub>4</sub> and α-amylase inhibition: 86.23 %) compared to MMLP-CAM (i.e., DPPH: 49.33 %, FRAP: 1.49 mM FeSO<sub>4</sub>, and α-amylase inhibition: 81.76 %). The mechanism and structure-activity relationship of MMLPs on bioactivities were also hypothesized.</div></div><div><h3>Significance</h3><div>Based on our previous study, the citric acid monohydrate-glycerol based DES as an extraction medium has enhanced the extraction yield of polysaccharides from <em>M. minutum</em>. This study highlights the DES combined with microwave-assisted extraction to improve the yield of MMLP and evaluate the biological activities compared to CAM as a classical solvent. In conclusion, the DES showed the advantages for extraction of polysaccharides with desired biological activities.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1331 ","pages":"Article 343351"},"PeriodicalIF":5.7,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449713","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
Sensitive detection of Hg(II) on MoS2/NiS2 based on interfacial engineering to accelerate the Ni2+/Ni3+ cycle: Identification the role of atomic-level heterojunction-induced electron transfer in electroanalysis 基于加速 Ni2+/Ni3+ 循环的界面工程在 MoS2/NiS2 上灵敏检测 Hg(II):鉴定原子级异质结诱导的电子转移在电分析中的作用
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-17 DOI: 10.1016/j.aca.2024.343339
Huan Xu, Hao-Ran Li, Jing-Yi Li, Jian-Jun Qu, Shan-Shan Li
The valence change of transition metal ions in nanomaterials can highly enhance the electrochemical detection performance toward heavy metal ions (HMIs), and how to further promote the valence change calls enormous concerns in electroanalysis. In this work, an interfacial engineering that combing the MoS2 and NiS2 together to form the MoS2/NiS2 complex is proposed. The density functional theory (DFT) results reveals that the novel atomic-level heterojunction between MoS2 and NiS2 will build an internal electric field (IEF), which leads to an enhanced conductivity and valence change behavior of Ni atoms in MoS2/NiS2 complex, resulting in a superior detection performance. In detail, the formation of atomic-level heterojunctions in the MoS2/NiS2 complex accelerates electron transfer due to the valence changes associated with Ni2+/Ni3+ cycling. The active Mo4+ species on MoS2 act as electron donors, facilitating the reduction of Ni3+ to Ni2+ on NiS2, thereby promoting Ni2+/Ni3+ cycling. As anticipated, the MoS2/NiS2 complex exhibits exceptional detection performance for Hg(II), with a sensitivity of 459.13 μA μM−1 cm−2, surpassing even that of other composite materials. In general, these findings are expected to significantly advance the application of electron transfer acceleration in electroanalysis based on the construction of heterojunction.
纳米材料中过渡金属离子的价态变化可以极大地提高对重金属离子(HMIs)的电化学检测性能,而如何进一步促进价态变化则是电分析领域的一个重大课题。本研究提出了一种将 MoS2 和 NiS2 结合在一起形成 MoS2/NiS2 复合物的界面工程学方法。密度泛函理论(DFT)结果表明,MoS2 和 NiS2 之间的新型原子级异质结将形成内电场(IEF),从而增强 MoS2/NiS2 复合物中 Ni 原子的电导率和价态变化行为,进而实现优异的检测性能。具体来说,由于 Ni2+/Ni3+ 循环相关的价态变化,MoS2/NiS2 复合物中原子级异质结的形成加速了电子转移。MoS2 上的活性 Mo4+ 物种充当电子供体,促进 NiS2 上的 Ni3+ 还原成 Ni2+,从而促进 Ni2+/Ni3+ 循环。正如预期的那样,MoS2/NiS2 复合物对 Hg(II)的检测性能优异,灵敏度达到 459.13 μA μM-1 cm-2,甚至超过了其他复合材料。总之,这些发现有望在构建异质结的基础上大大推进电子转移加速在电分析中的应用。
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引用次数: 0
Zwitterionic covalent organic nanosheets for selective analysis of domoic acid in marine environment 用于选择性分析海洋环境中多摩酸的共价键离子有机纳米片
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-17 DOI: 10.1016/j.aca.2024.343343
Jinhua Xu , Zhenli Yu , Wenmin Zhang , Shiye Xie , Baodi Liao , Lan Zhang

Background

Domoic acid (DA) is a neurotoxic compound causing amnesic shellfish poisoning, secreted by red algae and diatoms. As a glutamate analogue, DA accumulates in filter-feeding marine organisms, posing significant health risks to humans upon consumption. Detecting DA in marine environments remains challenging due to its low concentration and interference from complex matrices. Effective detection and removal require materials with high efficiency and selectivity, which traditional inorganic ionic materials lack due to their limited adsorption capacity and selectivity. Ionic covalent organic frameworks (iCOFs) expected to become highly efficient DA adsorbents due to tunable ionic sites.

Results

Thus, a zwitterionic covalent organic nanosheet (TGDB-iCONs) was synthesized to selectively capture DA. TGDB-iCONs was prepared by one-step Schiff-base reaction of the charged monomer triaminoguanidine hydrochloride. It uniformly distributed positively charged guanidinium and negatively charged chloride ions on the surface, forming zwitterionic binding sites. The self-peeling of TGDB-iCONs facilitated the exposure of active sites and improved the adsorption efficiency. Several binding forces were generated between TGDB-iCONs and DA, including complementary electrostatic hydrophilic interactions, which were verified by density functional theory (DFT) calculation. TGDB-iCONs exhibited ultra-fast adsorption kinetics (7 min) and relatively high adsorption capacity (66.48 mg/g) for DA. Furthermore, TGDB-iCONs exhibit strong salt resistance, which is attributed to the charge “shielding” effect of the zwitterionic ions present in TGDB-iCONs. TGDB-iCONs could highly selectively enrich DA and detect trace DA from marine environment including seawater, algae and marine organisms and the limit of detection as low as 0.3 ng/kg.

Significance and novelty

This comprehensive study not only sheds light on the vast potential of ionic covalent organic frameworks nanosheets (iCONs) in supporting early warning, control, and traceability of DA, but also lays a solid foundation for future research endeavors aimed at designing and harnessing the unique properties of iCONs.
背景多摩酸(DA)是一种神经毒性化合物,可导致失忆性贝类中毒,由红藻和硅藻分泌。作为谷氨酸类似物,DA 会在滤食性海洋生物体内积累,食用后会对人类健康造成严重危害。由于 DA 的浓度较低,且受到复杂基质的干扰,因此检测海洋环境中的 DA 仍然具有挑战性。有效的检测和去除需要具有高效率和高选择性的材料,而传统的无机离子材料由于吸附能力和选择性有限,缺乏这种能力。由于离子位点可调,离子共价有机框架(iCOFs)有望成为高效的 DA 吸附剂。TGDB-iCONs 是通过带电单体盐酸三氨基胍的一步席夫碱反应制备的。它在表面均匀分布着带正电荷的胍离子和带负电荷的氯离子,形成了齐聚离子结合位点。TGDB-iCON 的自剥离促进了活性位点的暴露,提高了吸附效率。TGDB-iCONs 与 DA 之间产生了多种结合力,包括互补的静电亲水相互作用,密度泛函理论(DFT)计算验证了这一点。TGDB-iCONs 对 DA 具有超快的吸附动力学(7 分钟)和相对较高的吸附容量(66.48 毫克/克)。此外,TGDB-iCONs 还具有很强的耐盐性,这归因于 TGDB-iCONs 中存在的齐聚离子的电荷 "屏蔽 "效应。这项综合研究不仅揭示了离子共价有机框架纳米片(iCONs)在支持 DA 早期预警、控制和溯源方面的巨大潜力,而且为今后旨在设计和利用 iCONs 独特性能的研究工作奠定了坚实的基础。
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引用次数: 0
In-situ electrochemically synthesized “artificial” Gly m TI antibody for soybean allergen quantification in complex foods 用于复杂食品中大豆过敏原定量的原位电化学合成 "人工 "Gly m TI 抗体
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-16 DOI: 10.1016/j.aca.2024.343340
Catarina Dias , Daniela Fernandes , Joana Costa , Caterina Villa , Patrícia Moreira , Ana T.S.C. Brandão , Isabel Mafra , A.Fernando Silva , Carlos M. Pereira , Renata Costa
Biosensors, especially those designed for detecting food allergens like Gly m TI in soybean, play a crucial role in safeguarding individuals who suffer from adverse food allergies, extending to both individual well-being and broader public health considerations. Furthermore, their integration into food production and monitoring processes aids in compliance with regulatory standards, reducing the incidence of allergen-related recalls and protecting vulnerable populations. Technological advancements in biosensor development, such as increased portability, real-time monitoring capabilities, and user-friendly interfaces, have expanded their practical applications, making them indispensable in various settings, including manufacturing plants, food service establishments, and even at-home use by consumers.
For the first time, a biosensor targeting the Gly m TI allergen based on molecularly imprinted polymer (MIP) technology was developed to detect/quantify soybean in complex food matrices and effectively address the detection challenges of complex and processed foods. The Gly m TI-MIP underwent a thorough validation process using anti-Gly m TI IgG raised as a polyclonal response to the trypsin inhibitor. Gly m TI-MIP was successfully tested across a range of food matrices, including tree nuts (e.g., peanuts, walnuts, and hazelnuts) and legumes (e.g., lentils, beans, and lupine), presenting minimal cross-reactivity with lupine and walnut. The innovative approach provided a linear response in the 1 ag mL−1 - 10 μg mL−1 range, with a LOD<1 ag mL−1. Applying the Gly m TI-MIP sensor to complex model foods allowed to detect 0.1 mg kg−1 (0.00001 %) of soybean protein isolate in biscuits, ham, and sausages before and after the respective thermal treatments. The innovative biosensor can significantly improve food safety protocols by addressing the complexities of tracing allergens in processed and unprocessed food products. By ensuring rigorous allergen control, these biosensors may support global food trade compliance with international safety standards, boost consumer confidence, and promote transparency in food labeling, ultimately contributing to a safer food supply chain.
生物传感器,尤其是用于检测大豆中的 Gly m TI 等食物过敏原的生物传感器,在保护食物过敏患者方面发挥着至关重要的作用,不仅关系到个人健康,还关系到更广泛的公共卫生问题。此外,将它们集成到食品生产和监测流程中有助于遵守监管标准,减少与过敏原有关的召回事件,保护弱势群体。生物传感器开发技术的进步,例如便携性的提高、实时监测能力的增强以及用户友好的界面,扩大了生物传感器的实际应用范围,使其在各种环境中都不可或缺,包括制造工厂、食品服务机构,甚至消费者在家中使用。Gly m TI-MIP 经过了全面的验证过程,使用的是对胰蛋白酶抑制剂产生多克隆反应的抗 Gly m TI IgG。Gly m TI-MIP 成功地在一系列食品基质中进行了测试,包括树坚果(如花生、核桃和榛子)和豆类(如扁豆、豆类和羽扇豆),与羽扇豆和核桃的交叉反应极小。该创新方法在 1 ag mL-1 - 10 μg mL-1 范围内提供线性响应,LOD<1 ag mL-1。将 Gly m TI-MIP 传感器应用到复杂的模型食品中,可以检测出饼干、火腿和香肠在各自热处理前后的大豆分离蛋白含量为 0.1 mg kg-1(0.00001%)。这种创新型生物传感器可以解决加工食品和未加工食品中过敏原追踪的复杂问题,从而大大改善食品安全协议。通过确保严格的过敏原控制,这些生物传感器可以支持全球食品贸易遵守国际安全标准,增强消费者信心,提高食品标签的透明度,最终促进食品供应链的安全。
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引用次数: 0
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Analytica Chimica Acta
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