首页 > 最新文献

Analytica Chimica Acta最新文献

英文 中文
A mitochondria-targeted nitric oxide probe with large Stokes shift for real-time imaging and evaluation of inflammatory bowel disease in situ 具有大斯托克斯位移的线粒体靶向一氧化氮探针,用于原位实时成像和评估炎症性肠病
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-24 DOI: 10.1016/j.aca.2024.343372
Jiatian Liu , Xueqian Chen , Andong Wang , Dongdong Su

Background

Inflammatory bowel disease (IBD) is a prevalent inflammatory disorder, and the abnormal expression of nitric oxide (NO) produced by biocatalysis of iNOS enzyme in mitochondria is directly associated with the occurrence and progression of IBD. Activatable fluorescent probes offer promising tools for early diagnosis of IBD, however, inadequate biodistribution and limited targeting properties of these probes in vivo severely impede accurate diagnosis of IBD and real-time evaluation of inflammatory levels in situ. Therefore, it is necessary to design a highly efficient fluorescent probe towards NO to overcome inadequate biodistribution and achieve accurate diagnosis and evaluation of IBD in situ.

Results

We designed a highly efficient mitochondria-targeted “turn-on” NIR fluorescent probe Cy-OMe which has excellent targeting properties and imaging ability. The response mechanism is probe Cy-OMe rapidly undergoes N-nitrosation reaction resulting in “turn-on” NIR fluorescence signal when exposed to NO. Cy-OMe exhibits high sensitivity and specificity in detecting NO content in vitro, owing to its large Stokes shift. Furthermore, the probe Cy-OMe not only efficiently targets mitochondria but also enables precise assessment of fluctuations in endogenous NO concertation across various cell types. Importantly, by virtue of large Stokes shift and excellent mitochondrial targeting ability, Cy-OMe has the capability to specifically evaluate dynamic fluctuations of NO in lipopolysaccharide (LPS)‐stimulated IBD mouse models in situ and Cy-OMe was achieved high-contrast imaging and precision diagnosis of intestinal inflammation diseases.

Significance

Cy-OMe can accurately assess fluctuations in NO levels and show high signal fidelity in the diseased intestine region, which has prospects in the non-invasive diagnosis of intestinal inflammation in vivo. At the same time, it is expected to serve as a potential diagnose platform for investigating the physiological processes underlying NO-related inflammatory diseases and promoting understanding of the pathological functions of NO across diverse inflammatory diseases.
背景炎症性肠病(IBD)是一种常见的炎症性疾病,线粒体中 iNOS 酶的生物催化产生的一氧化氮(NO)的异常表达与 IBD 的发生和发展直接相关。可激活的荧光探针为 IBD 的早期诊断提供了前景广阔的工具,然而,这些探针在体内的生物分布不足和靶向性有限,严重阻碍了 IBD 的准确诊断和原位炎症水平的实时评估。因此,有必要设计一种针对 NO 的高效荧光探针,以克服生物分布不足的问题,实现对 IBD 的原位准确诊断和评估。其反应机制是探针 Cy-OMe 在暴露于 NO 时会迅速发生 N-亚硝基化反应,从而产生开启的近红外荧光信号。由于 Cy-OMe 具有较大的斯托克斯位移,因此在体外检测 NO 含量时具有较高的灵敏度和特异性。此外,探针 Cy-OMe 不仅能有效靶向线粒体,还能精确评估不同类型细胞中内源性 NO 的协同波动。重要的是,凭借大斯托克斯位移和出色的线粒体靶向能力,Cy-OMe 能够在原位特异性评估脂多糖(LPS)刺激的 IBD 小鼠模型中 NO 的动态波动,Cy-OMe 实现了肠道炎症疾病的高对比度成像和精准诊断。意义Cy-OMe能准确评估NO水平的波动,并在病变肠道区域显示高信号保真度,在体内无创诊断肠道炎症方面具有广阔前景。同时,它有望成为一个潜在的诊断平台,用于研究 NO 相关炎症疾病的生理过程,并促进对 NO 在各种炎症疾病中的病理功能的了解。
{"title":"A mitochondria-targeted nitric oxide probe with large Stokes shift for real-time imaging and evaluation of inflammatory bowel disease in situ","authors":"Jiatian Liu ,&nbsp;Xueqian Chen ,&nbsp;Andong Wang ,&nbsp;Dongdong Su","doi":"10.1016/j.aca.2024.343372","DOIUrl":"10.1016/j.aca.2024.343372","url":null,"abstract":"<div><h3>Background</h3><div>Inflammatory bowel disease (IBD) is a prevalent inflammatory disorder, and the abnormal expression of nitric oxide (NO) produced by biocatalysis of iNOS enzyme in mitochondria is directly associated with the occurrence and progression of IBD. Activatable fluorescent probes offer promising tools for early diagnosis of IBD, however, inadequate biodistribution and limited targeting properties of these probes <em>in vivo</em> severely impede accurate diagnosis of IBD and real-time evaluation of inflammatory levels <em>in situ</em>. Therefore, it is necessary to design a highly efficient fluorescent probe towards NO to overcome inadequate biodistribution and achieve accurate diagnosis and evaluation of IBD <em>in situ</em>.</div></div><div><h3>Results</h3><div>We designed a highly efficient mitochondria-targeted “turn-on” NIR fluorescent probe <strong>Cy-OMe</strong> which has excellent targeting properties and imaging ability. The response mechanism is probe <strong>Cy-OMe</strong> rapidly undergoes N-nitrosation reaction resulting in “turn-on” NIR fluorescence signal when exposed to NO. <strong>Cy-OMe</strong> exhibits high sensitivity and specificity in detecting NO content <em>in vitro</em>, owing to its large Stokes shift. Furthermore, the probe <strong>Cy-OMe</strong> not only efficiently targets mitochondria but also enables precise assessment of fluctuations in endogenous NO concertation across various cell types. Importantly, by virtue of large Stokes shift and excellent mitochondrial targeting ability, <strong>Cy-OMe</strong> has the capability to specifically evaluate dynamic fluctuations of NO in lipopolysaccharide (LPS)‐stimulated IBD mouse models <em>in situ</em> and <strong>Cy-OMe</strong> was achieved high-contrast imaging and precision diagnosis of intestinal inflammation diseases.</div></div><div><h3>Significance</h3><div><strong>Cy-OMe</strong> can accurately assess fluctuations in NO levels and show high signal fidelity in the diseased intestine region, which has prospects in the non-invasive diagnosis of intestinal inflammation <em>in vivo</em>. At the same time, it is expected to serve as a potential diagnose platform for investigating the physiological processes underlying NO-related inflammatory diseases and promoting understanding of the pathological functions of NO across diverse inflammatory diseases.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1332 ","pages":"Article 343372"},"PeriodicalIF":5.7,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489134","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
Analysis of chemosensitivity of tumor spheroids exposed to two-dimensional gradient of combination drugs in a hydrogel-based diffusion microfluidic platform 在基于水凝胶的扩散微流控平台上分析肿瘤球体对二维梯度复合药物的化疗敏感性
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-24 DOI: 10.1016/j.aca.2024.343371
Kin Fong Lei , Yu-Ting Lin , Sai Kiran Reddy Boreddy , Ping-Ching Pai

Background

Liver cancer stands as a leading cause of cancer-related deaths globally, challenging conventional treatments due to resistance to chemotherapy and targeted therapy. Although frontline medications show initial efficacy, prolonged use often leads to resistance and harm. Current clinical strategies rely on combination therapies, but evaluating their effectiveness remains challenging.

Results

To address this, we developed a hydrogel-based diffusion microfluidic platform for assessing chemosensitivity. This platform features a hydrogel-filled diffusion layer linked to liquid wells, allowing the creation of drug gradients. Tumor spheroids, cultured on the non-adhesive hydrogel surface, were exposed to single or combination drug gradients. Analysis revealed that drug efficacy, quantified by IC50 values, could be determined from responses to single drug gradients. A novel method was introduced to assess spheroid circularity as a time-invariant index of drug efficacy. Furthermore, exposing spheroids to 2D combination drug gradients allowed intuitive visualization of their responses via a color map. This analysis identified optimal drug combinations, exhibiting superior efficacy to monotherapy.

Significance

The microfluidic platform enables assessment of synergistic effects and replicates in vivo conditions, enhancing the relevance of test results. By offering a streamlined, fast, and efficient drug screening approach, this platform aims to provide insight into tumor spheroid responses to varying drug combinations, facilitating more effective clinical applications.
背景肝癌是全球癌症相关死亡的主要原因之一,由于对化疗和靶向治疗的耐药性,传统治疗方法面临挑战。虽然一线药物显示出初步疗效,但长期使用往往会导致耐药性和伤害。为了解决这个问题,我们开发了一种基于水凝胶的扩散微流控平台,用于评估化疗敏感性。该平台的特点是将充满水凝胶的扩散层与液孔相连,从而形成药物梯度。在非粘性水凝胶表面培养的肿瘤球体暴露于单一或组合药物梯度。分析表明,通过对单一药物梯度的反应,可以确定以 IC50 值量化的药物疗效。该研究采用了一种新方法来评估球体的圆度,以此作为药物疗效的时间不变指标。此外,将球体暴露于二维组合药物梯度可通过彩色图直观地显示球体的反应。这项分析确定了最佳药物组合,其疗效优于单一疗法。意义该微流体平台可评估协同效应,并复制体内条件,提高了测试结果的相关性。通过提供简化、快速和高效的药物筛选方法,该平台旨在深入了解肿瘤球体对不同药物组合的反应,从而促进更有效的临床应用。
{"title":"Analysis of chemosensitivity of tumor spheroids exposed to two-dimensional gradient of combination drugs in a hydrogel-based diffusion microfluidic platform","authors":"Kin Fong Lei ,&nbsp;Yu-Ting Lin ,&nbsp;Sai Kiran Reddy Boreddy ,&nbsp;Ping-Ching Pai","doi":"10.1016/j.aca.2024.343371","DOIUrl":"10.1016/j.aca.2024.343371","url":null,"abstract":"<div><h3>Background</h3><div>Liver cancer stands as a leading cause of cancer-related deaths globally, challenging conventional treatments due to resistance to chemotherapy and targeted therapy. Although frontline medications show initial efficacy, prolonged use often leads to resistance and harm. Current clinical strategies rely on combination therapies, but evaluating their effectiveness remains challenging.</div></div><div><h3>Results</h3><div>To address this, we developed a hydrogel-based diffusion microfluidic platform for assessing chemosensitivity. This platform features a hydrogel-filled diffusion layer linked to liquid wells, allowing the creation of drug gradients. Tumor spheroids, cultured on the non-adhesive hydrogel surface, were exposed to single or combination drug gradients. Analysis revealed that drug efficacy, quantified by IC<sub>50</sub> values, could be determined from responses to single drug gradients. A novel method was introduced to assess spheroid circularity as a time-invariant index of drug efficacy. Furthermore, exposing spheroids to 2D combination drug gradients allowed intuitive visualization of their responses via a color map. This analysis identified optimal drug combinations, exhibiting superior efficacy to monotherapy.</div></div><div><h3>Significance</h3><div>The microfluidic platform enables assessment of synergistic effects and replicates <em>in vivo</em> conditions, enhancing the relevance of test results. By offering a streamlined, fast, and efficient drug screening approach, this platform aims to provide insight into tumor spheroid responses to varying drug combinations, facilitating more effective clinical applications.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1332 ","pages":"Article 343371"},"PeriodicalIF":5.7,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142488684","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
Comparative analysis of purity of human albumin preparations for clinical use 临床用人血白蛋白制剂纯度对比分析
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-24 DOI: 10.1016/j.aca.2024.343364
Liye Maeyama, Stefanie Fas, Jörg Schüttrumpf, Selma Henrichsen

Background

Albumin is the most prevalent plasma protein and serves numerous physiological roles, both in body fluid management and in various other capacities. In many diseases, a deficiency of albumin has been observed, and in certain conditions, albumin substitution has been demonstrated to improve outcome in comparison to plasma expansion using crystalloid or other colloid solutions. The favourable effects of using albumin in patients with liver cirrhosis are likely associated with the non-oncotic functions of albumin. Albumin for clinical use is obtained through fractionation of pooled donor plasma. The production procedures are optimized to ensure pure, chemically uncompromised and native protein.

Results

We have extensively analysed commercial preparations of human albumin for clinical use from six different providers. Parameters that must correspond to the requirements of international pharmacopoeias were assessed (aluminium, ethanol, sodium, the presence of dimers and oligomers) and found to conform in all cases. In addition, we used for the first time nuclear magnetic resonance (NMR) as an additional analytical approach for investigating in greater depth the quality of a biological remedy gained from human plasma. We applied both 1H NMR and 13C-HSQC for confirming the identity of the albumin preparations, which also conformed in all cases. Moreover, we utilized T2-filtered 1H NMR and 13C-HSQC measurements to identify the presence of small molecules in the preparations. This demonstrated similar patterns of additional substances present, but also unveiled certain differences in purity in the products of the different providers.

Significance

Our analyses confirmed that albumin preparations in clinical use conform to the requirements. We furthermore demonstrate that NMR measurements can provide further depth in identity and purity measurements of biologicals. Despite largely standardized protocols in pharmaceutical albumin production, our in-depth analyses revealed differences in purity. Some samples exhibited lower levels of components other than albumin. We discuss possible causes of these observations and their potential implications for clinical therapy.
背景白蛋白是最常见的血浆蛋白,在体液管理和其他各种功能中发挥着多种生理作用。在许多疾病中都可观察到白蛋白缺乏,在某些情况下,白蛋白替代品与使用晶体液或其他胶体溶液进行血浆扩容相比,可改善预后。肝硬化患者使用白蛋白的良好效果可能与白蛋白的非抗凝血功能有关。临床使用的白蛋白是通过对集合供体血浆进行分馏获得的。我们广泛分析了六家不同供应商提供的临床用人血白蛋白商业制剂。对必须符合国际药典要求的参数(铝、乙醇、钠、二聚体和低聚物的存在)进行了评估,发现所有参数都符合要求。此外,我们还首次将核磁共振(NMR)作为一种额外的分析方法,用于更深入地研究从人体血浆中提取的生物药剂的质量。我们同时使用 1H-NMR 和 13C-HSQC 来确认白蛋白制剂的身份,结果也全部吻合。此外,我们还利用 T2 过滤 1H-NMR 和 13C-HSQC 测量来确定制剂中是否存在小分子物质。我们的分析证实,临床使用的白蛋白制剂符合要求。我们的分析证实了临床使用的白蛋白制剂符合要求,并进一步证明了 NMR 测量可进一步深入生物制品的特性和纯度测量。尽管药用白蛋白的生产规程基本标准化,但我们的深入分析发现了纯度方面的差异。一些样品中除白蛋白以外的其他成分含量较低。我们讨论了这些观察结果的可能原因及其对临床治疗的潜在影响。
{"title":"Comparative analysis of purity of human albumin preparations for clinical use","authors":"Liye Maeyama,&nbsp;Stefanie Fas,&nbsp;Jörg Schüttrumpf,&nbsp;Selma Henrichsen","doi":"10.1016/j.aca.2024.343364","DOIUrl":"10.1016/j.aca.2024.343364","url":null,"abstract":"<div><h3>Background</h3><div>Albumin is the most prevalent plasma protein and serves numerous physiological roles, both in body fluid management and in various other capacities. In many diseases, a deficiency of albumin has been observed, and in certain conditions, albumin substitution has been demonstrated to improve outcome in comparison to plasma expansion using crystalloid or other colloid solutions. The favourable effects of using albumin in patients with liver cirrhosis are likely associated with the non-oncotic functions of albumin. Albumin for clinical use is obtained through fractionation of pooled donor plasma. The production procedures are optimized to ensure pure, chemically uncompromised and native protein.</div></div><div><h3>Results</h3><div>We have extensively analysed commercial preparations of human albumin for clinical use from six different providers. Parameters that must correspond to the requirements of international pharmacopoeias were assessed (aluminium, ethanol, sodium, the presence of dimers and oligomers) and found to conform in all cases. In addition, we used for the first time nuclear magnetic resonance (NMR) as an additional analytical approach for investigating in greater depth the quality of a biological remedy gained from human plasma. We applied both <sup>1</sup>H NMR and <sup>13</sup>C-HSQC for confirming the identity of the albumin preparations, which also conformed in all cases. Moreover, we utilized T<sub>2</sub>-filtered <sup>1</sup>H NMR and <sup>13</sup>C-HSQC measurements to identify the presence of small molecules in the preparations. This demonstrated similar patterns of additional substances present, but also unveiled certain differences in purity in the products of the different providers.</div></div><div><h3>Significance</h3><div>Our analyses confirmed that albumin preparations in clinical use conform to the requirements. We furthermore demonstrate that NMR measurements can provide further depth in identity and purity measurements of biologicals. Despite largely standardized protocols in pharmaceutical albumin production, our in-depth analyses revealed differences in purity. Some samples exhibited lower levels of components other than albumin. We discuss possible causes of these observations and their potential implications for clinical therapy.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1332 ","pages":"Article 343364"},"PeriodicalIF":5.7,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489010","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Advanced design of target-driven self-powered sensor assisted by cascade catalytic strategy 级联催化策略辅助下的目标驱动型自供电传感器的先进设计
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-23 DOI: 10.1016/j.aca.2024.343359
Zongshan Zhang , Jing Xu , Lei Zhang , Gaoli Zhang , Hui Li
In this work, a self-powered microsensor platform based on enzyme biofuel cells (EBFCs) was developed for intelligent monitoring of disease markers miRNA-451. The cascade catalysis system constructed by using the strategy of enzyme-like ZIF-8 nanocapsule incorporation with biological enzymes, which could simultaneously take into account the specificity of biological enzymes and the high activity of nano-enzymes, significantly promoted the electron transfer between glucose and the bio-anode surface, and improved the sensitivity and stability of the sensing system. Meanwhile, the target-triggered hybridization chain reaction (HCR) amplification strategy to achieve exponential signal amplification based on accurate recognition, and jointly improve the detection sensitivity. As expected, the micro-sensor platform has a wide linear range of 0.5–1.0 fmol/L with a low limit of detection (LOD) of 0.13 fmol/L (S/N = 3) and exhibits excellent selectivity, reproducibility and stability in interference assays under optimal detection conditions. The designed self-powered system is simple to construct, easy to transport and the data transmission mode is intelligent and controllable, which is expected to be used in basic biochemical research, clinical diagnosis and environmental monitoring.
本研究开发了一种基于酶生物燃料电池(EBFCs)的自供电微传感器平台,用于智能监测疾病标志物miRNA-451。利用类酶 ZIF-8 纳米胶囊与生物酶结合的策略构建的级联催化系统,兼顾了生物酶的特异性和纳米酶的高活性,显著促进了葡萄糖与生物阳极表面的电子传递,提高了传感系统的灵敏度和稳定性。同时,采用目标触发杂交链反应(HCR)放大策略,在准确识别的基础上实现指数级信号放大,共同提高了检测灵敏度。正如预期的那样,微传感器平台的线性范围宽达 0.5-1.0 fmol/L,检出限(LOD)低至 0.13 fmol/L(S/N=3),并在最佳检测条件下的干扰检测中表现出优异的选择性、重现性和稳定性。所设计的自供电系统构造简单、运输方便,数据传输模式智能可控,有望用于基础生化研究、临床诊断和环境监测。
{"title":"Advanced design of target-driven self-powered sensor assisted by cascade catalytic strategy","authors":"Zongshan Zhang ,&nbsp;Jing Xu ,&nbsp;Lei Zhang ,&nbsp;Gaoli Zhang ,&nbsp;Hui Li","doi":"10.1016/j.aca.2024.343359","DOIUrl":"10.1016/j.aca.2024.343359","url":null,"abstract":"<div><div>In this work, a self-powered microsensor platform based on enzyme biofuel cells (EBFCs) was developed for intelligent monitoring of disease markers miRNA-451. The cascade catalysis system constructed by using the strategy of enzyme-like ZIF-8 nanocapsule incorporation with biological enzymes, which could simultaneously take into account the specificity of biological enzymes and the high activity of nano-enzymes, significantly promoted the electron transfer between glucose and the bio-anode surface, and improved the sensitivity and stability of the sensing system. Meanwhile, the target-triggered hybridization chain reaction (HCR) amplification strategy to achieve exponential signal amplification based on accurate recognition, and jointly improve the detection sensitivity. As expected, the micro-sensor platform has a wide linear range of 0.5–1.0 fmol/L with a low limit of detection (LOD) of 0.13 fmol/L (S/N = 3) and exhibits excellent selectivity, reproducibility and stability in interference assays under optimal detection conditions. The designed self-powered system is simple to construct, easy to transport and the data transmission mode is intelligent and controllable, which is expected to be used in basic biochemical research, clinical diagnosis and environmental monitoring.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1332 ","pages":"Article 343359"},"PeriodicalIF":5.7,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487309","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 targeted profiling of multiple steroid classes in rodent plasma using liquid chromatography-mass spectrometry 利用液相色谱-质谱法对啮齿动物血浆中的多种类固醇进行全面的靶向分析
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-23 DOI: 10.1016/j.aca.2024.343362
Taťána Gazárková , Hana Kočová Vlčková , Kateřina Plachká , Karla Vagnerová , Dominika Dubecová , Petra Klusoňová , Jiří Pácha , Frantisek Svec , Lucie Nováková

Background

Reliable quantification of multiple steroid classes in biological fluids within a single method remains an analytical challenge despite many previously published methods. Crosstalk of positional isomers, overlap of stereoisomer fragmentation patterns, differing proton affinities, in-source fragmentation, varying stability of protonated ions in the gas phase across steroid classes, and non-existence of steroid-free matrix are the main challenges limiting the number of simultaneously profiled steroids.

Results

In this study, we focused on the development of a derivatization-free, achiral, high-throughput, and cost-effective UHPLC-MS/MS approach that allows simultaneous profiling of a spectrum of 38 steroids covering progestogens, androgens, corticosteroids, and estrogens, while properly addressing the hurdles of steroid analysis. Within a 20-min method, 16 stereoisomers and 15 positional isomers were fully resolved within a single run while separated from 7 additional non-interfering steroids and matrix interferences in rodent plasma. Protein precipitation (PP) and supported liquid extraction (SLE) methods using only 40 μL of sample were developed to achieve the lowest possible limits of quantification. Nevertheless, 5α-dihydroprogesterone and 3α,5α-THDOC could be only qualitatively assessed when using PP. In contrast, DHEA-S could not be quantified or identified when using SLE. A novel surrogate matrix-background subtraction approach, using rat plasma after the animal's adrenalectomy, has been implemented into the optimized PP-UHPLC-MS/MS workflow, successfully validated according to the unified ICH/EMA M10 guidelines, and compared to the traditional quantification strategies. Moreover, the validity of the newly adopted approach has been verified by the targeted profiling of multiple biologically active endogenous steroids in more than 500 samples of mouse plasma in total.

Significance

Underestimation of hurdles associated with steroid analysis often compromises the accurate steroid quantification. Our comprehensive, fully validated UHPLC-MS/MS method targeting a wide spectrum of endogenous steroids, mitigating steroid crosstalk and using a minimal sample volume together with a novel surrogate matrix-background subtraction approach significantly advances steroid analysis for research and clinical applications covering multiple biological scopes.
背景尽管以前发表过许多方法,但用一种方法对生物液体中的多种类固醇进行可靠的定量仍然是一项分析挑战。位置异构体的串扰、立体异构体碎片模式的重叠、质子亲和力的不同、源内碎片、不同类固醇在气相中质子化离子的稳定性不同以及不存在不含类固醇的基质是限制同时分析类固醇数量的主要挑战。结果在这项研究中,我们重点开发了一种无衍生化、非手性、高通量、高性价比的超高效液相色谱-质谱/质谱分析方法,该方法可同时分析 38 种类固醇,涵盖孕激素、雄激素、皮质类固醇和雌激素,同时还能妥善解决类固醇分析中遇到的障碍。在 20 分钟的方法中,一次运行即可完全解析 16 种立体异构体和 15 种位置异构体,同时与啮齿类动物血浆中另外 7 种非干扰类固醇和基质干扰分离。为了达到尽可能低的定量限,我们开发了仅使用 40 μL 样品的蛋白质沉淀和辅助液体萃取方法。然而,使用蛋白沉淀法只能定性评估 5α-二氢孕酮和 3α,5α-THDOC。与此相反,使用 SLE 时无法定量或识别 DHEA-S。在优化的PP-UHPLC-MS/MS工作流程中采用了一种新颖的替代基质-背景减去方法,该方法使用的是动物肾上腺切除术后的大鼠血浆,根据统一的ICH/EMA M10指南成功地进行了验证,并与传统的定量策略进行了比较。此外,在总共 500 多份小鼠血浆样本中对多种具有生物活性的内源性类固醇进行了有针对性的分析,从而验证了新方法的有效性。我们的超高效液相色谱-质谱/质谱(UHPLC-MS/MS)方法针对多种内源性类固醇,减轻了类固醇的串扰,样品量极少,并采用了新颖的替代基质-背景减去方法,极大地推动了类固醇分析在多种生物学领域的研究和临床应用。
{"title":"Comprehensive targeted profiling of multiple steroid classes in rodent plasma using liquid chromatography-mass spectrometry","authors":"Taťána Gazárková ,&nbsp;Hana Kočová Vlčková ,&nbsp;Kateřina Plachká ,&nbsp;Karla Vagnerová ,&nbsp;Dominika Dubecová ,&nbsp;Petra Klusoňová ,&nbsp;Jiří Pácha ,&nbsp;Frantisek Svec ,&nbsp;Lucie Nováková","doi":"10.1016/j.aca.2024.343362","DOIUrl":"10.1016/j.aca.2024.343362","url":null,"abstract":"<div><h3>Background</h3><div>Reliable quantification of multiple steroid classes in biological fluids within a single method remains an analytical challenge despite many previously published methods. Crosstalk of positional isomers, overlap of stereoisomer fragmentation patterns, differing proton affinities, in-source fragmentation, varying stability of protonated ions in the gas phase across steroid classes, and non-existence of steroid-free matrix are the main challenges limiting the number of simultaneously profiled steroids.</div></div><div><h3>Results</h3><div>In this study, we focused on the development of a derivatization-free, achiral, high-throughput, and cost-effective UHPLC-MS/MS approach that allows simultaneous profiling of a spectrum of 38 steroids covering progestogens, androgens, corticosteroids, and estrogens, while properly addressing the hurdles of steroid analysis. Within a 20-min method, 16 stereoisomers and 15 positional isomers were fully resolved within a single run while separated from 7 additional non-interfering steroids and matrix interferences in rodent plasma. Protein precipitation (PP) and supported liquid extraction (SLE) methods using only 40 μL of sample were developed to achieve the lowest possible limits of quantification. Nevertheless, 5α-dihydroprogesterone and 3α,5α-THDOC could be only qualitatively assessed when using PP. In contrast, DHEA-S could not be quantified or identified when using SLE. A novel surrogate matrix-background subtraction approach, using rat plasma after the animal's adrenalectomy, has been implemented into the optimized PP-UHPLC-MS/MS workflow, successfully validated according to the unified ICH/EMA M10 guidelines, and compared to the traditional quantification strategies. Moreover, the validity of the newly adopted approach has been verified by the targeted profiling of multiple biologically active endogenous steroids in more than 500 samples of mouse plasma in total.</div></div><div><h3>Significance</h3><div>Underestimation of hurdles associated with steroid analysis often compromises the accurate steroid quantification. Our comprehensive, fully validated UHPLC-MS/MS method targeting a wide spectrum of endogenous steroids, mitigating steroid crosstalk and using a minimal sample volume together with a novel surrogate matrix-background subtraction approach significantly advances steroid analysis for research and clinical applications covering multiple biological scopes.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1332 ","pages":"Article 343362"},"PeriodicalIF":5.7,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487421","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-mode sensing platform for Bisphenol A detection via bifunctional CsPbBr3@Cu-MOF assisted fluorescence and colorimetric analysis 通过双功能 Cu-MOF@CsPbBr3 辅助荧光和比色分析检测双酚 A 的双模式传感平台
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-22 DOI: 10.1016/j.aca.2024.343354
Junyi Ma , Ying-zhuo Shen , Jianxiao Gong , Seitkhan Azat , Zheng Ping Ji , Xiao-Ya Hu , Qin Xu

Background

Bisphenol A (BPA) has been identified as an endocrine disruptor with numerous detrimental effects on human health. There is an urgent need to develop fluorescence/colorimetric dual-mode sensing approaches with expanded detection linear range, increased accuracy, and enhanced application flexibility for BPA detection. The utilization of fluorescence and colorimetric signals in point-of-care applications and real-time sensitive sensing further highlights the significance of developing novel and efficient fluorescence/colorimetric dual-mode sensing platform with high-efficiency probes.

Results

Herein, a fluorescence and colorimetric dual-mode aptasensor was developed by using CsPbBr3@Cu-MOF as the aptamer immobilization matrix and signal generator. CsPbBr3 was functionalized with Cu-MOF using a simple two-step strategy. This strategy involved in-situ formation and modified ligand-assisted precipitation technique with 4,4′-bipyridine (4,4-Bpy) serving as the bifunctional linker. The resulting CsPbBr3@Cu-MOF exhibited improved stability in water and enhanced fluorescence. Additionally, it functioned as peroxidase mimetic to oxidize 3,3′,5,5′-tetramethyl benzidine (TMB), leading to a colorimetric change from colorless to blue. In the presence of BPA, aptamers were removed from CsPbBr3@Cu-MOF. Consequently, the fluorescence and peroxidase-activity of CsPbBr3@Cu-MOF were recovered, resulting in the enhanced fluorescence intensity and color change of TMB. Using this system, the proposed aptasensor demonstrated detection ranges of 1.0–80.0 nM with a LOD of 0.60 nM for the colorimetric method, and a linearity range of 0.1–100 nM with a LOD of 0.02 nM for the fluorescence method.

Significance

The obtained CsPbBr3@Cu-MOF composites showed excellent fluorescence properties, good peroxidase-like activity, and aqueous stability. Furthermore, the proposed dual-mode aptasensor demonstrated simplicity, cost-effectiveness and good anti-interference abilities. This can be extended to the construction of other dual-mode sensors by changing aptamers and provides novel insights on the potential applications of perovskites in bioanalysis.
背景双酚 A(BPA)已被确认为一种内分泌干扰物,对人体健康有诸多不利影响。目前急需开发荧光/比色双模式传感方法,以扩大双酚 A 检测的线性范围、提高准确性和应用灵活性。结果本文以 CsPbBr3@Cu-MOF 作为适配体固定基质和信号发生器,开发了一种荧光和比色双模式适配体传感器。CsPbBr3 通过简单的两步策略与 Cu-MOF 功能化。该策略包括原位形成和改进的配体辅助沉淀技术,以 4,4'-联吡啶(4,4-Bpy)作为双功能连接剂。由此产生的 CsPbBr3@Cu-MOF 在水中的稳定性更好,荧光也更强。此外,它还能作为过氧化物酶模拟物,氧化 3,3′,5,5′-四甲基联苯胺(TMB),从而使比色值从无色变为蓝色。在双酚 A 的存在下,CsPbBr3@Cu-MOF 中的适配体被去除。因此,CsPbBr3@Cu-MOF 的荧光和过氧化物酶活性得以恢复,从而增强了 TMB 的荧光强度和颜色变化。利用该系统,拟议的适配传感器在比色法中的检测范围为 1.0 至 80.0 nM,LOD 为 0.60 nM;在荧光法中的线性范围为 0.1 至 100 nM,LOD 为 0.02 nM。此外,所提出的双模灵敏度传感器具有简便、经济和良好的抗干扰能力。通过改变适配体,该研究还可扩展到其他双模传感器的构建,并为包晶石在生物分析中的潜在应用提供了新的见解。
{"title":"Dual-mode sensing platform for Bisphenol A detection via bifunctional CsPbBr3@Cu-MOF assisted fluorescence and colorimetric analysis","authors":"Junyi Ma ,&nbsp;Ying-zhuo Shen ,&nbsp;Jianxiao Gong ,&nbsp;Seitkhan Azat ,&nbsp;Zheng Ping Ji ,&nbsp;Xiao-Ya Hu ,&nbsp;Qin Xu","doi":"10.1016/j.aca.2024.343354","DOIUrl":"10.1016/j.aca.2024.343354","url":null,"abstract":"<div><h3>Background</h3><div>Bisphenol A (BPA) has been identified as an endocrine disruptor with numerous detrimental effects on human health. There is an urgent need to develop fluorescence/colorimetric dual-mode sensing approaches with expanded detection linear range, increased accuracy, and enhanced application flexibility for BPA detection. The utilization of fluorescence and colorimetric signals in point-of-care applications and real-time sensitive sensing further highlights the significance of developing novel and efficient fluorescence/colorimetric dual-mode sensing platform with high-efficiency probes.</div></div><div><h3>Results</h3><div>Herein, a fluorescence and colorimetric dual-mode aptasensor was developed by using CsPbBr<sub>3</sub>@Cu-MOF as the aptamer immobilization matrix and signal generator. CsPbBr<sub>3</sub> was functionalized with Cu-MOF using a simple two-step strategy. This strategy involved in-situ formation and modified ligand-assisted precipitation technique with 4,4′-bipyridine (4,4-Bpy) serving as the bifunctional linker. The resulting CsPbBr<sub>3</sub>@Cu-MOF exhibited improved stability in water and enhanced fluorescence. Additionally, it functioned as peroxidase mimetic to oxidize 3,3′,5,5′-tetramethyl benzidine (TMB), leading to a colorimetric change from colorless to blue. In the presence of BPA, aptamers were removed from CsPbBr<sub>3</sub>@Cu-MOF. Consequently, the fluorescence and peroxidase-activity of CsPbBr<sub>3</sub>@Cu-MOF were recovered, resulting in the enhanced fluorescence intensity and color change of TMB. Using this system, the proposed aptasensor demonstrated detection ranges of 1.0–80.0 nM with a LOD of 0.60 nM for the colorimetric method, and a linearity range of 0.1–100 nM with a LOD of 0.02 nM for the fluorescence method.</div></div><div><h3>Significance</h3><div>The obtained CsPbBr<sub>3</sub>@Cu-MOF composites showed excellent fluorescence properties, good peroxidase-like activity, and aqueous stability. Furthermore, the proposed dual-mode aptasensor demonstrated simplicity, cost-effectiveness and good anti-interference abilities. This can be extended to the construction of other dual-mode sensors by changing aptamers and provides novel insights on the potential applications of perovskites in bioanalysis.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1332 ","pages":"Article 343354"},"PeriodicalIF":5.7,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486468","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
Enhanced data point importance: Layered significance of variables in multivariate calibration 增强数据点重要性:多变量校准中变量的分层重要性
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-22 DOI: 10.1016/j.aca.2024.343357
Somaye Vali Zade , Klaus Neymeyr , Mathias Sawall , Hamid Abdollahi

Background

The Enhanced Data Point Importance (EDPI) method, a systematic approach for evaluating the importance of data points in multivariate calibration, is introduced. Factor decomposition methods allow for the evaluation of the impact of variables on maintaining the structural pattern of data in the abstract space. Essential data points play a key role in these patterns and the method of Data Point Importance (DPI) aims to evaluate the essential data points in terms of their importance. All other points are rated by zero. In this contribution, DPI is extended to include inner points to evaluate the importance of these points in the absence of the essential points. The EDPI method employs convex peeling to sort data points systematically.

Results

EDPI method was applied to near-infrared and Raman spectroscopy data sets, including corn and alcohol mixtures and simulated data, to rank and select important variables. EDPI effectively identified variables that contributed to the preservation of the data structure and highlighted key spectral regions with different degrees of selectivity. In the alcohol dataset, EDPI revealed important physicochemical insights by focusing on specific regions where non-analytes spectra overlapped. It performed in a similar way to the Variable Importance in Projection (VIP) method, but with fewer variables selected.

Significance

The experimental results obtained from calibrating near-infrared and Raman spectroscopic datasets using partial least squares highlight the effectiveness of the proposed EDPI strategy when contrasted with the conventional variable importance in projection (VIP) method for variable selection.
背景介绍增强数据点重要性(EDPI)方法是一种评估多元校准中数据点重要性的系统方法。因子分解方法可以评估变量对维持抽象空间中数据结构模式的影响。基本数据点在这些模式中起着关键作用,数据点重要性(DPI)方法旨在评估基本数据点的重要性。所有其他点的评分均为零。在本文中,DPI 扩展到包括内部点,以便在没有基本点的情况下评估这些点的重要性。结果将 EDPI 方法应用于近红外和拉曼光谱数据集,包括玉米和酒精混合物以及模拟数据,对重要变量进行排序和选择。EDPI 有效地识别了有助于保持数据结构的变量,并突出了具有不同选择性的关键光谱区域。在酒精数据集中,EDPI 通过关注非分析物光谱重叠的特定区域,揭示了重要的物理化学观点。它的性能与投影变量重要性(VIP)方法类似,但选择的变量更少。重要意义使用偏最小二乘法校准近红外和拉曼光谱数据集所获得的实验结果,与传统的投影变量重要性(VIP)变量选择方法相比,凸显了所提出的 EDPI 策略的有效性。
{"title":"Enhanced data point importance: Layered significance of variables in multivariate calibration","authors":"Somaye Vali Zade ,&nbsp;Klaus Neymeyr ,&nbsp;Mathias Sawall ,&nbsp;Hamid Abdollahi","doi":"10.1016/j.aca.2024.343357","DOIUrl":"10.1016/j.aca.2024.343357","url":null,"abstract":"<div><h3>Background</h3><div>The Enhanced Data Point Importance (EDPI) method, a systematic approach for evaluating the importance of data points in multivariate calibration, is introduced. Factor decomposition methods allow for the evaluation of the impact of variables on maintaining the structural pattern of data in the abstract space. Essential data points play a key role in these patterns and the method of Data Point Importance (DPI) aims to evaluate the essential data points in terms of their importance. All other points are rated by zero. In this contribution, DPI is extended to include inner points to evaluate the importance of these points in the absence of the essential points. The EDPI method employs convex peeling to sort data points systematically.</div></div><div><h3>Results</h3><div>EDPI method was applied to near-infrared and Raman spectroscopy data sets, including corn and alcohol mixtures and simulated data, to rank and select important variables. EDPI effectively identified variables that contributed to the preservation of the data structure and highlighted key spectral regions with different degrees of selectivity. In the alcohol dataset, EDPI revealed important physicochemical insights by focusing on specific regions where non-analytes spectra overlapped. It performed in a similar way to the Variable Importance in Projection (VIP) method, but with fewer variables selected.</div></div><div><h3>Significance</h3><div>The experimental results obtained from calibrating near-infrared and Raman spectroscopic datasets using partial least squares highlight the effectiveness of the proposed EDPI strategy when contrasted with the conventional variable importance in projection (VIP) method for variable selection.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1332 ","pages":"Article 343357"},"PeriodicalIF":5.7,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486967","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
On-The-Flight trapping, LIBS analysis and discrimination of single meteorite particles generated by laser ablation 对激光烧蚀产生的单个陨石颗粒进行飞行捕获、Libs 分析和鉴别
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-22 DOI: 10.1016/j.aca.2024.343361
C. Burgos-Palop , F.J. Fortes , P. Purohit , T. Delgado , J. Laserna

Background

Thousands of micrometeorites fall to the Earth on a daily basis. Most of these meteorites have a rocky composition, but others are mainly composed of iron and nickel. Due to their small size, often ca. 100 μm in diameter, the process of searching for, collecting, and identifying these samples is remarkably tedious. In this work, we introduce a minimally invasive methodology for evaluating the full elemental composition of micrometeorites using optical emission spectroscopy of single particles produced by laser ablation of bulk targets.

Results

Bulk meteorite samples were directly ablated within an ablation cell. From few micrograms of ablated matrix, we originated dry aerosols consisting of multielemental particles which were representative of the sample chemistry. SEM images confirmed that the generated particles exhibited spherical geometry. Particles were first optically trapped in air and, then, analyzed by laser-induced breakdown spectroscopy (LIBS). LIBS spectra evidenced compositional differences among samples. For example, Campo de Cielo meteorite featured a high iron content due to its metallic nature whereas LIBS results for Jbilet Winselwan and NWA 869 suggested that pyroxene components dominated the composition of the samples. In contrast, NWA 13739 and Vaca Muerta contained high aluminum intensity, thus indicating that the feldspathic component was dominant, as then verified by XRD. The intra-sample compositional variability were quite satisfactory, as revealed by the RSD data, below 45 %. For quantitative analysis, the percentages of FeO, SiO2, Al2O3, Na2O, MgO, TiO2, CaO, K2O, MnO, SrO, Cr2O3, and Li2O were calculated using CF-LIBS.

Significance

This work demonstrates the applicability of laser excitation of individual particles in an optical trap for the multielemental analysis of meteorites. The methodology provides a complete overview of the samples, is capable of classificating them according to their main phases and yield preliminary quantitative information about those phases. Therefore, we present a minimally destructive pathway to be used as the first step in the inspection of these delicate samples. If the particles represent nanostructures inherent to the meteorites, it would constitute a major step in the analysis of extraterrestrial material that may provide fundamental insights into the structure and composition of the original materials at the microscale, a topic that remains an active area of research worldwide.
背景每天有数以千计的微陨石坠落到地球上。这些陨石大多数都是岩石成分,但也有一些主要由铁和镍组成。由于这些陨石体积小,直径通常只有约 100 微米,因此寻找、收集和鉴定这些样本的过程非常繁琐。在这项工作中,我们介绍了一种微创方法,利用激光烧蚀大块目标产生的单个颗粒的光学发射光谱来评估微陨石的全部元素组成。我们从几微克的烧蚀基质中产生了由多元素颗粒组成的干气溶胶,这些颗粒代表了样品的化学成分。扫描电子显微镜图像证实,生成的颗粒呈球形。首先在空气中对颗粒进行光学捕获,然后用激光诱导击穿光谱(LIBS)进行分析。激光诱导击穿光谱分析结果表明,不同样品之间存在成分差异。例如,Campo de Cielo 陨石因其金属特性而具有较高的铁含量,而 Jbilet Winselwan 和 NWA 869 的激光诱导击穿光谱分析结果表明,样品成分中主要是辉石成分。相比之下,NWA 13739 和 Vaca Muerta 含有较高的铝强度,从而表明长石成分占主导地位,XRD 也验证了这一点。正如 RSD 数据所显示的,样品内部的成分变化非常令人满意,低于 45%。为了进行定量分析,使用 CF-LIBS 计算了 FeO、SiO2、Al2O3、Na2O、MgO、TiO2、CaO、K2O、MnO、SrO、Cr2O3 和 Li2O 的百分比。该方法提供了样品的完整概览,能够根据主要物相对样品进行分类,并获得有关这些物相的初步定量信息。因此,我们提出了一种破坏性最小的方法,作为检测这些微妙样本的第一步。如果这些颗粒代表了陨石固有的纳米结构,那么这将是分析地外物质的重要一步,可以从根本上了解原始材料在微观尺度上的结构和组成,而这一主题仍然是全世界研究的一个活跃领域。
{"title":"On-The-Flight trapping, LIBS analysis and discrimination of single meteorite particles generated by laser ablation","authors":"C. Burgos-Palop ,&nbsp;F.J. Fortes ,&nbsp;P. Purohit ,&nbsp;T. Delgado ,&nbsp;J. Laserna","doi":"10.1016/j.aca.2024.343361","DOIUrl":"10.1016/j.aca.2024.343361","url":null,"abstract":"<div><h3>Background</h3><div>Thousands of micrometeorites fall to the Earth on a daily basis. Most of these meteorites have a rocky composition, but others are mainly composed of iron and nickel. Due to their small size, often ca. 100 μm in diameter, the process of searching for, collecting, and identifying these samples is remarkably tedious. In this work, we introduce a minimally invasive methodology for evaluating the full elemental composition of micrometeorites using optical emission spectroscopy of single particles produced by laser ablation of bulk targets.</div></div><div><h3>Results</h3><div>Bulk meteorite samples were directly ablated within an ablation cell. From few micrograms of ablated matrix, we originated dry aerosols consisting of multielemental particles which were representative of the sample chemistry. SEM images confirmed that the generated particles exhibited spherical geometry. Particles were first optically trapped in air and, then, analyzed by laser-induced breakdown spectroscopy (LIBS). LIBS spectra evidenced compositional differences among samples. For example, <em>Campo de Cielo</em> meteorite featured a high iron content due to its metallic nature whereas LIBS results for <em>Jbilet Winselwan</em> and <em>NWA 869</em> suggested that pyroxene components dominated the composition of the samples. In contrast, <em>NWA 13739</em> and <em>Vaca Muerta</em> contained high aluminum intensity, thus indicating that the feldspathic component was dominant, as then verified by XRD. The intra-sample compositional variability were quite satisfactory, as revealed by the RSD data, below 45 %. For quantitative analysis, the percentages of FeO, SiO<sub>2</sub>, Al<sub>2</sub>O<sub>3</sub>, Na<sub>2</sub>O, MgO, TiO<sub>2</sub>, CaO, K<sub>2</sub>O, MnO, SrO, Cr<sub>2</sub>O<sub>3</sub>, and Li<sub>2</sub>O were calculated using CF-LIBS.</div></div><div><h3>Significance</h3><div>This work demonstrates the applicability of laser excitation of individual particles in an optical trap for the multielemental analysis of meteorites. The methodology provides a complete overview of the samples, is capable of classificating them according to their main phases and yield preliminary quantitative information about those phases. Therefore, we present a minimally destructive pathway to be used as the first step in the inspection of these delicate samples. If the particles represent nanostructures inherent to the meteorites, it would constitute a major step in the analysis of extraterrestrial material that may provide fundamental insights into the structure and composition of the original materials at the microscale, a topic that remains an active area of research worldwide.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1332 ","pages":"Article 343361"},"PeriodicalIF":5.7,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486968","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Mid-level data fusion strategy based on urinary nucleosides SERS spectra and blood CEA levels for enhanced preoperative detection of lymph node metastasis in colorectal cancer 基于尿核苷 SERS 光谱和血 CEA 水平的中层数据融合策略用于增强结直肠癌淋巴结转移的术前检测
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-22 DOI: 10.1016/j.aca.2024.343360
Jinyong Lin , Yuduo Wu , Zhizhong Lin , Xueliang Lin , Qiong Wu , JiaJia Lin , Yuanji Xu , Shangyuan Feng , Junxin Wu

Background

Preoperative prediction of lymph node metastasis (LNM) plays a crucial role in the treatment and prognosis of colorectal cancer (CRC). The traditional histopathological examination is invasive and time-consuming, providing pathological features only postoperatively. Preoperative serum carcinoembryonic antigen (CEA) is strongly correlated with postoperative LN status. However, the detection accuracy of LNM based on a single preoperative CEA level is low. Therefore, developing a more powerful and sensitive diagnostic tool would be of great clinical value for improving the accurate preoperative prediction of LNM in CRC patients.

Results

This study aimed to develop a mid-level fusion approach using urinary nucleosides Raman spectra and blood CEA data to enhance the preoperative discrimination of CRC patients with and without LNM. Surface-enhanced Raman scattering (SERS) spectra of urinary modified nucleosides, isolated by affinity chromatography, were first acquired from 48 patients with LNM and 49 patients without LNM. The principal component analysis (PCA) scores obtained from the SERS spectra were then combined with preoperative blood CEA values to create a fused data array. The discriminant accuracy based on either dataset alone or the fused data was evaluated using three machine learning algorithms: linear discriminant analysis, k-nearest neighbors, and support vector machine. Results showed that the fused data could discriminate between the two groups with an accuracy of up to 91 %, outperforming SERS alone (86 %) and CEA alone (69 %).

Significance

To our knowledge, this is the first report of mid-level data fusion of urinary nucleosides SERS spectra with blood CEA levels for the preoperative prediction of LNM in CRC. This work demonstrates that the mid-level data fusion strategy aided by SVM algorithm can greatly improve the preoperative prediction accuracy of LNM. This is crucial for therapeutic decision-making and prognostic assessment in CRC.
背景术前预测淋巴结转移(LNM)对结直肠癌(CRC)的治疗和预后起着至关重要的作用。传统的组织病理学检查具有创伤性且耗时,只能在术后提供病理特征。术前血清癌胚抗原(CEA)与术后 LN 状态密切相关。然而,基于单一术前 CEA 水平的 LNM 检测准确率很低。因此,开发一种更强大、更灵敏的诊断工具将对提高 CRC 患者术前 LNM 的准确预测具有重要的临床价值。结果 本研究旨在开发一种中层融合方法,利用尿液核苷拉曼光谱和血液 CEA 数据来提高有 LNM 和无 LNM 的 CRC 患者的术前分辨能力。首先从 48 名 LNM 患者和 49 名非 LNM 患者中获取了通过亲和层析法分离的尿液修饰核苷的表面增强拉曼散射(SERS)光谱。然后将从 SERS 光谱中获得的主成分分析 (PCA) 分数与术前血液 CEA 值相结合,创建一个融合数据阵列。使用三种机器学习算法(线性判别分析、k-近邻和支持向量机)评估了基于单独数据集或融合数据的判别准确性。结果表明,融合数据对两组患者的区分准确率高达 91%,优于单独使用 SERS(86%)和单独使用 CEA(69%)。这项工作表明,SVM 算法辅助下的中层数据融合策略可大大提高 LNM 的术前预测准确率。这对 CRC 的治疗决策和预后评估至关重要。
{"title":"Mid-level data fusion strategy based on urinary nucleosides SERS spectra and blood CEA levels for enhanced preoperative detection of lymph node metastasis in colorectal cancer","authors":"Jinyong Lin ,&nbsp;Yuduo Wu ,&nbsp;Zhizhong Lin ,&nbsp;Xueliang Lin ,&nbsp;Qiong Wu ,&nbsp;JiaJia Lin ,&nbsp;Yuanji Xu ,&nbsp;Shangyuan Feng ,&nbsp;Junxin Wu","doi":"10.1016/j.aca.2024.343360","DOIUrl":"10.1016/j.aca.2024.343360","url":null,"abstract":"<div><h3>Background</h3><div>Preoperative prediction of lymph node metastasis (LNM) plays a crucial role in the treatment and prognosis of colorectal cancer (CRC). The traditional histopathological examination is invasive and time-consuming, providing pathological features only postoperatively. Preoperative serum carcinoembryonic antigen (CEA) is strongly correlated with postoperative LN status. However, the detection accuracy of LNM based on a single preoperative CEA level is low. Therefore, developing a more powerful and sensitive diagnostic tool would be of great clinical value for improving the accurate preoperative prediction of LNM in CRC patients.</div></div><div><h3>Results</h3><div>This study aimed to develop a mid-level fusion approach using urinary nucleosides Raman spectra and blood CEA data to enhance the preoperative discrimination of CRC patients with and without LNM. Surface-enhanced Raman scattering (SERS) spectra of urinary modified nucleosides, isolated by affinity chromatography, were first acquired from 48 patients with LNM and 49 patients without LNM. The principal component analysis (PCA) scores obtained from the SERS spectra were then combined with preoperative blood CEA values to create a fused data array. The discriminant accuracy based on either dataset alone or the fused data was evaluated using three machine learning algorithms: linear discriminant analysis, k-nearest neighbors, and support vector machine. Results showed that the fused data could discriminate between the two groups with an accuracy of up to 91 %, outperforming SERS alone (86 %) and CEA alone (69 %).</div></div><div><h3>Significance</h3><div>To our knowledge, this is the first report of mid-level data fusion of urinary nucleosides SERS spectra with blood CEA levels for the preoperative prediction of LNM in CRC. This work demonstrates that the mid-level data fusion strategy aided by SVM algorithm can greatly improve the preoperative prediction accuracy of LNM. This is crucial for therapeutic decision-making and prognostic assessment in CRC.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1332 ","pages":"Article 343360"},"PeriodicalIF":5.7,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486751","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
Fluorescence imaging of dopamine in living cells triggered by unique coupling reactions 独特耦合反应引发的活细胞多巴胺荧光成像
IF 5.7 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2024-10-22 DOI: 10.1016/j.aca.2024.343358
Shaofei Fu , Jianwen Qiu , Biaofeng Gu , Yong Gao

Background

Dopamine (DA) is a significant neurotransmitter and catecholamine molecule in the mammalian brain. It plays a crucial role in perception, cognition, central nervous system regulation, and hormone secretion. The detection of DA levels in living systems is a vital aspect of the research and early diagnosis of neurological disorders.

Results

In this study, we achieved an effective fluorescence generation specific to DA under physiological pH conditions by coupling the DA detection reaction to the HClO oxidation reaction. This method has been used for the detection of DA in cells, as well as for the visualization of DA levels in cellular models of inflammation and depression.

Significance

This is the first time that utilizes an organic fluorescent molecular probe to detect DA in living cells.
背景多巴胺(DA)是哺乳动物大脑中一种重要的神经递质和儿茶酚胺分子。它在感知、认知、中枢神经系统调节和激素分泌中起着至关重要的作用。结果在这项研究中,我们通过将 DA 检测反应与 HClO 氧化反应耦合,在生理 pH 条件下实现了有效的 DA 特异荧光生成。该方法已被用于细胞中 DA 的检测,以及炎症和抑郁细胞模型中 DA 水平的可视化。
{"title":"Fluorescence imaging of dopamine in living cells triggered by unique coupling reactions","authors":"Shaofei Fu ,&nbsp;Jianwen Qiu ,&nbsp;Biaofeng Gu ,&nbsp;Yong Gao","doi":"10.1016/j.aca.2024.343358","DOIUrl":"10.1016/j.aca.2024.343358","url":null,"abstract":"<div><h3>Background</h3><div>Dopamine (DA) is a significant neurotransmitter and catecholamine molecule in the mammalian brain. It plays a crucial role in perception, cognition, central nervous system regulation, and hormone secretion. The detection of DA levels in living systems is a vital aspect of the research and early diagnosis of neurological disorders.</div></div><div><h3>Results</h3><div>In this study, we achieved an effective fluorescence generation specific to DA under physiological pH conditions by coupling the DA detection reaction to the HClO oxidation reaction. This method has been used for the detection of DA in cells, as well as for the visualization of DA levels in cellular models of inflammation and depression.</div></div><div><h3>Significance</h3><div>This is the first time that utilizes an organic fluorescent molecular probe to detect DA in living cells.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1332 ","pages":"Article 343358"},"PeriodicalIF":5.7,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486752","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
期刊
Analytica Chimica Acta
全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1