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SP3-PELSA: A Rapid and Sensitive Approach for Studying Protein-Ligand Interaction with Small-Amount Samples SP3-PELSA:一种快速、灵敏的小样本蛋白质-配体相互作用研究方法
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-03-24 DOI: 10.1016/j.aca.2026.345436
Jiaqin Chen, Guangxu Hu, Jie Song, Lin Huang, Xumin Zhang
Deciphering protein-ligand binding events is essential for unraveling biological pathways and advancing drug development. The recently developed peptide-centric local stability assay (PELSA) has demonstrated superior performance compared to other mainstream approaches. However, the conventional PELSA approach relies on filter-based peptide recovery, which results in prolonged processing times and relatively low yields, particularly when operating with limited starting material. To address these limitations, we present an optimized PELSA approach termed SP3-PELSA, which leverages the simple and efficient peptide recovery of the Single-Pot, Solid-Phase-enhanced Sample Preparation (SP3) method. Through a systematic evaluation of protein precipitation and trypsin inactivation conditions, we identified 1% formic acid and 80% acetonitrile as the optimal parameters. A comparative analysis of SP3-PELSA with conventional PELSA revealed that SP3-PELSA reduces the processing time by fivefold and significantly increases the peptide recovery rate, especially for hydrophobic peptides. Consequently, SP3-PELSA outperformed other mainstream approaches in the identification of established drug targets. Owing to its high recovery efficiency and potential for automation, SP3-PELSA holds great promise for large-scale drug target discovery, especially in the context of scarce clinical samples. Furthermore, its exceptional recovery of hydrophobic peptides positions this approach as a powerful tool for analyzing highly hydrophobic proteins in drug target screening.
破译蛋白质-配体结合事件对于揭示生物途径和推进药物开发至关重要。最近开发的肽中心局部稳定性测定(PELSA)与其他主流方法相比表现出优越的性能。然而,传统的PELSA方法依赖于基于过滤器的肽回收,这导致处理时间延长,产量相对较低,特别是在原料有限的情况下。为了解决这些限制,我们提出了一种优化的PELSA方法,称为SP3-PELSA,它利用了单锅固相增强样品制备(SP3)方法的简单有效的肽回收。通过对蛋白沉淀和胰蛋白酶失活条件的系统评价,确定了1%甲酸和80%乙腈为最佳工艺参数。对比分析SP3-PELSA与传统的PELSA,发现SP3-PELSA的处理时间缩短了5倍,并显著提高了肽的回收率,特别是对疏水肽。因此,SP3-PELSA在确定既定药物靶点方面优于其他主流方法。由于其高回收率和自动化潜力,SP3-PELSA在大规模药物靶点发现方面具有很大的前景,特别是在临床样品稀缺的情况下。此外,它的特殊的恢复疏水肽定位这种方法作为一个强大的工具,分析高度疏水蛋白在药物靶标筛选。
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引用次数: 0
Unified Primer Enabled Detection (UPED) system for Magnaporthe oryzae infecting rice: A comparative study from conventional PCR to CRISPR Cas12a based detection systems. 水稻稻瘟病菌统一引物激活检测系统:传统PCR与基于CRISPR Cas12a检测系统的比较研究
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-03-24 DOI: 10.1016/j.aca.2026.345418
R. Karan, M.K. Prasannakumar, Harvinder Kour Khera, J. Harish, Swathi.S. Patil, Pramesh Devanna, C. Manjunatha, Rakesh Kumar Mishra

Background

Rice blast, caused by Magnaporthe oryzae, is one of the most devastating fungal pathogens of rice. Early, rapid and accurate detection is critical for effective disease management and the prevention of outbreaks. Conventional and isothermal molecular methods vary widely in sensitivity and field applicability, making it difficult to understand the reliable detection. This study aimed to perform the first unified, side-by-side comparison of six molecular detection techniques using a common primer set to identify the most sensitive, specific and field deployable approach for M. oryzae detection.

Results

In this study, we have evaluated six diagnostic methods such as PCR, qPCR, LAMP, RPA, and CRISPR-Cas12a integrated with LAMP or RPA targeting the multi copy Pot2 transposon in M. oryzae. Sensitivity assays using 10-fold genomic DNA dilutions (109 to 10-1 copies/reaction) revealed that LAMP-CRISPR and RPA-CRISPR were most sensitive, detecting down to 1 copy/reaction. LAMP and qPCR detected down to 102 and 103 copies/reaction, while RPA and PCR were limited to 105 and 106 copies/reaction, respectively. All assays showed high specificity with no cross-reactivity to 10 non-target rice fungal pathogens. Field validation on 17 symptomatic samples confirmed that CRISPR-based methods outperformed traditional techniques, detecting positives missed by other platforms. This is the first systematic comparison applying the same primer set across multiple diagnostic methods for M. oryzae.

Significance

Our findings demonstrate that CRISPR-Cas12a-based platforms combined with isothermal amplification offers high sensitivity and specificity. CRISPR based detection allows strong field applicability for M. oryzae detection. The use of a unified primer set allowed for a direct performance comparison. These results highlight the potential of CRISPR-based diagnostics to enhance early pathogen detection, enabling rapid interventions and improved management of rice blast disease.
稻瘟病由稻瘟病菌(Magnaporthe oryzae)引起,是水稻最具破坏性的真菌病原体之一。早期、快速和准确的检测对于有效的疾病管理和预防疫情至关重要。常规分子方法和等温分子方法在灵敏度和现场适用性方面差异很大,难以实现可靠的检测。本研究旨在使用一组共同的引物对六种分子检测技术进行首次统一的并排比较,以确定最敏感、最特异性和最适合野外部署的米曲菌检测方法。结果本研究评价了PCR、qPCR、LAMP、RPA以及与LAMP或RPA结合的CRISPR-Cas12a对米曲菌多拷贝Pot2转座子的诊断方法。使用10倍基因组DNA稀释(109至10-1拷贝/反应)进行敏感性试验显示,LAMP-CRISPR和RPA-CRISPR最敏感,检测到低至1拷贝/反应。LAMP和qPCR分别检测到102和103拷贝/反应,RPA和PCR分别检测到105和106拷贝/反应。所有检测结果对10种非目标水稻真菌病原菌均具有高特异性,无交叉反应性。对17个有症状样本的现场验证证实,基于crispr的方法优于传统技术,可以检测到其他平台遗漏的阳性病例。这是首次采用同一引物集在多种诊断方法中对米曲菌进行系统比较。我们的研究结果表明,基于crispr - cas12的平台结合等温扩增具有高灵敏度和特异性。基于CRISPR的检测使得m.o ryzae的检测具有很强的现场适用性。使用统一的底漆集可以进行直接的性能比较。这些结果突出了基于crispr的诊断方法在加强早期病原体检测、实现快速干预和改进稻瘟病管理方面的潜力。
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引用次数: 0
Permanganate Assisted Oxidative-Chlorination Digestion for Trace Determination of Gold in Geological Samples by GF AAS 高锰酸盐辅助氧化-氯化消解法测定地质样品中的痕量金
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-03-23 DOI: 10.1016/j.aca.2026.345424
Gourab Rana, Abheek Sarkar
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引用次数: 0
Intelligent POCT for Ovarian Cancer: Dual-Biomarker Detection Combined with ROMA Risk Assessment Using Selenium Nanoparticle 智能POCT卵巢癌:双生物标志物检测结合使用硒纳米颗粒ROMA风险评估
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-03-23 DOI: 10.1016/j.aca.2026.345434
Weiqi Xie, Jinbo Wu, Xiaoyi Xie, Mengli Wu, Menghan Zhang, Mengyao Zhang, Xiaoquan Li, Li Wang, Lanju Wang, Zhigang Liu, Zhizeng Wang, Chunxia Chen
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引用次数: 0
A near-infrared ratiometric fluorescent probe for visual sensing of H2S and monitoring its fluctuation in plant roots under drought and flooding stresses 干旱和洪涝胁迫下植物根系中H2S的近红外比例荧光探针视觉感知及监测
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-03-22 Epub Date: 2026-01-29 DOI: 10.1016/j.aca.2026.345144
Ruxuan Mo , Chao Kang , Jianping Yuan , Carl Redshaw , Ying Huang , Qilong Zhang , Xiufang Yan

Background

Hydrogen sulfide (H2S) is a key endogenous gasotransmitter involved in plant physiological regulation and stress responses. Monitoring its dynamic changes in plants is essential for understanding related signaling mechanisms. However, due to its chemical instability and the complexity of plant tissues, developing a reliable method for accurate quantification and real-time visualization of H2S in living plants remains challenging. Although fluorescent probes have been developed for H2S imaging, most still face critical limitations, such as emission in the visible region being susceptible to background fluorescence interference, and insufficient quantitative reliability of single-wavelength-based signal output modes in complex samples. Therefore, developing novel probes with near-infrared emission and rationetric response characteristics is of great significance.

Results

We constructed a near-infrared rationetric fluorescent probe, NIR-Cou-H2S, for H2S detection. The probe itself emits at 716 nm, and after specific reaction with H2S, a new emission peak appears at 552 nm, resulting in a distinct dual-emission rationetric response (716 nm/552 nm) accompanied by a visible color change. Using chemometrics-based fluorescence analysis, the probe successfully enabled direct quantitative detection of H2S in river and lake water samples. Its near-infrared emission effectively reduced interference from plant autofluorescence, thereby achieving high-contrast dual-channel fluorescence imaging. The probe was successfully applied for high-quality in situ visualization of H2S in living cells and tobacco seedling roots. More importantly, using NIR-Cou-H2S, we observed and recorded in real time the dynamic upregulation trend of endogenous H2S levels in tobacco roots under both drought and flooding stress conditions.

Significance

As a novel near-infrared rationetric probe, NIR-Cou-H2S provides a powerful tool for monitoring endogenous H2S dynamics in plants. Its characteristics significantly improve the reliability of imaging and quantification in complex plant samples, offering a key methodological approach for further elucidating the regulatory mechanisms of H2S in plant stress resistance.
硫化氢(H2S)是一种参与植物生理调节和逆境反应的重要内源气体传递素。监测其在植物体内的动态变化是了解相关信号机制的必要条件。然而,由于其化学不稳定性和植物组织的复杂性,开发一种可靠的方法来准确定量和实时可视化活植物中的H2S仍然是一个挑战。虽然已经开发出用于H2S成像的荧光探针,但大多数仍然面临着关键的局限性,例如可见光区域的发射容易受到背景荧光干扰,以及复杂样品中基于单波长的信号输出模式的定量可靠性不足。因此,开发具有近红外发射和定量响应特性的新型探针具有重要意义。结果构建了一种近红外定量荧光探针nir - cu -H2S,用于检测H2S。探针本身在716 nm处发射,与H2S特异反应后,在552 nm处出现新的发射峰,产生明显的双发射理性响应(716 nm/552 nm),并伴有可见的颜色变化。利用化学计量学为基础的荧光分析,探针成功地实现了对河流和湖泊水样中H2S的直接定量检测。其近红外发射有效降低了植物自身荧光的干扰,实现了高对比度双通道荧光成像。该探针已成功应用于活细胞和烟草幼苗根中H2S的高质量原位可视化。更重要的是,利用nir - cu -H2S,我们实时观察并记录了干旱和洪涝胁迫条件下烟草根系内源H2S水平的动态上调趋势。作为一种新型的近红外定量探针,nir - cu -H2S为监测植物内源H2S动态提供了强有力的工具。其特性显著提高了复杂植物样品成像和定量的可靠性,为进一步阐明H2S在植物抗逆性中的调控机制提供了关键的方法学途径。
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引用次数: 0
A protease-resistant and anti-fouling electrochemical biosensing interface constructed with dl-serine modified Y-shaped peptides for reliable analysis of aminopeptidase N in human serum 用dl -丝氨酸修饰的y型多肽构建抗蛋白酶抗污垢电化学生物传感界面,可靠分析人血清中氨基肽酶N
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-03-22 Epub Date: 2026-01-31 DOI: 10.1016/j.aca.2026.345185
Yudong Wang, Yanxin Li, Yinan Zhan, Jie Yang, Yuxin Zhang, Lei Wang, Xiliang Luo
Electrochemical sensing techniques are still facing the challenges of biofouling and insufficient probe stability in complex biological matrices. To address this issue, we have designed a dl-serine Y-shaped peptide (YPEP) integrating the antifouling properties and recognition efficiency. Application demonstration was performed with detecting aminopeptidase N (APN) in human serum. The peptide-modified sensing interface exhibits effective antifouling performance, and enhanced resistance to enzymatic degradation. When detecting APN, the developed sensor showed a sensitive response within the linear range of 1.0 ng mL−1 to 10 μg mL−1 and a detection limit of 0.24 ng mL−1. Comparison studies were performed with the clinical human serum samples, and results obtained with the developed sensor and standard ELISA methods are in close agreement. This work provides a feasible strategy to developing robust antifouling peptide-based biosensing platforms for clinical applications in complex biological matrices.
电化学传感技术仍然面临着生物污染和探针在复杂生物基质中的稳定性不足的挑战。为了解决这一问题,我们设计了一种集防污性能和识别效率于一体的dl-丝氨酸y形肽(YPEP)。对检测人血清中氨肽酶N (APN)进行了应用演示。肽修饰的传感界面具有有效的防污性能,并增强了酶降解的抵抗力。该传感器在1.0 ~ 10 μg mL−1的线性范围内具有较高的灵敏度,检测限为0.24 ng mL−1。与临床人血清样本进行了比较研究,开发的传感器和标准ELISA方法获得的结果非常一致。这项工作为开发基于多肽的抗污染生物传感平台提供了一种可行的策略,可用于复杂生物基质的临床应用。
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引用次数: 0
Histology-guided spatial lipidomics and proteomics of the trisynaptic circuit in the human hippocampus 人类海马体三突触回路的组织学引导的空间脂质组学和蛋白质组学
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-03-22 Epub Date: 2026-01-22 DOI: 10.1016/j.aca.2026.345110
Caitlin M. Tressler , Lauren DeVine , Rahul Bharadwaj , Dalton R. Brown , Daniel Weinberger , Kristine Glunde , Robert N. Cole
The human hippocampal trisynaptic circuit activity is essential for learning and memory. This canonical circuit has spatially distinct populations of neurons, but their unique contributions to neurodevelopment, as well as to dysfunction in neurodegenerative disorders, are missed when analyzing bulk tissue homogenates. Using matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) to guide laser capture microdissection (LCMD) of regions of interest for spatial multimodal analyses is a relatively new approach to study topographically distinct neuronal cell populations in heterogenous tissues. However, MALDI-MSI may not identify region-defining molecular mass-to-charge ions. Here, we apply a multimodal approach of MALDI-MSI-LCMD-lipidomic and proteomic analysis to the trisynaptic circuit. Our MALDI-MSI of the hippocampus revealed that the of mass-to-charge ions of the cornu ammonis 1 (CA1) and cornu ammonis 3 (CA3) did not segment from the surrounding tissue. Thus, we developed a novel histology-guided MALDI-MS imaging-LCMD-spatial lipidomic/proteomic pipeline with four steps which does not rely on segmentation analysis to determine and co-register regions of interest in tissue sections. Our pipeline allows MALDI imaging, LCMD, lipidomic and proteomic analysis from the same tissue section and does not require co-registration across serial sections. In addition, poly-l-lysine coating for improving tissue/cell adherence on indium-tin-oxide microscopy slides did not impact MALDI-MSI or spatial proteomics. We show that the human trisynaptic circuit proteomes of CA1 and CA3 pyramidal neurons are more similar to each other than those of the dentate gyrus (DG), which is consistent with previously reported transcriptomics studies. The spatial distributions of several phospholipids and proteins, however, were significantly different in cell bodies from the CA1, CA3 and DG regions, and these lipids correlated with some lipid metabolizing enzymes in those regions. As little is known about lipid metabolism in the hippocampus, our pipeline provides an initial step in studying the combined and differential spatial regulation of the lipids and proteins within the trisynaptic circuit that will provide insights into the development and disease-related molecular changes in these important hippocampal regions.
人类海马体三突触回路的活动对学习和记忆至关重要。这种典型的回路在空间上具有不同的神经元群,但它们对神经发育以及神经退行性疾病功能障碍的独特贡献在分析大块组织匀浆时被忽略了。利用基质辅助激光解吸/电离(MALDI)质谱成像(MSI)引导激光捕获显微解剖(LCMD)对感兴趣的区域进行空间多模态分析,是研究异质组织中不同地形的神经细胞群的一种相对较新的方法。然而,MALDI-MSI可能无法识别区域定义的分子质量电荷比离子。在这里,我们将maldi - msi - lcmd -脂质组学和蛋白质组学分析的多模态方法应用于三突触电路。我们的海马MALDI-MSI显示鹿角氨1 (CA1)和鹿角氨3 (CA3)的质量电荷比离子没有从周围组织中分离出来。因此,我们开发了一种新的组织学引导MALDI-MS成像- lcmd -空间脂质组学/蛋白质组学管道,该管道有四个步骤,不依赖于分割分析来确定和共同注册组织切片中的感兴趣区域。我们的产品线允许在同一组织切片上进行MALDI成像、LCMD、脂质组学和蛋白质组学分析,并且不需要在连续切片上进行共同注册。此外,用于改善铟锡氧化物显微镜载玻片上组织/细胞粘附性的聚赖氨酸涂层不会影响MALDI-MSI或空间蛋白质组学。我们发现CA1和CA3锥体神经元的三突触回路蛋白质组比齿状回(DG)的蛋白质组更相似,这与先前报道的转录组学研究一致。然而,在CA1、CA3和DG区域的细胞体中,几种磷脂和蛋白质的空间分布有显著差异,这些脂质与这些区域的一些脂质代谢酶相关。由于对海马体中的脂质代谢知之甚少,我们的管道为研究三突触回路中脂质和蛋白质的联合和差异空间调节提供了初步的步骤,这将为这些重要海马体区域的发育和疾病相关的分子变化提供见解。
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引用次数: 0
Nicking-controlled biosensor: Integrating DNA Walker-RCA circuit with trimetallic nanozyme for aflatoxin B1 detection 镍控生物传感器:集成DNA Walker-RCA电路与三金属纳米酶用于黄曲霉毒素B1检测
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-03-22 Epub Date: 2026-02-02 DOI: 10.1016/j.aca.2026.345193
Longsheng Jin , YuJing Liu , Wenqing Xia , Meiling Zhou , Ziying Xiao , Jingyu Ge , Xiao Yuan , Qinqiang Zhu , Meisheng Wu

Background

Aflatoxin B1 (AFB1) is a highly toxic mycotoxin that poses serious threats to global food safety and public health. The ingestion of these contaminated products causes substantial risks to both food safety systems and public health. Despite the availability of various detection techniques, the requirement for highly sensitive analysis of AFB1 contamination in agricultural products continues to drive demand for improved methodologies.

Results

In this work, a novel electrochemiluminescence (ECL) biosensor was developed for the sensitive detection of aflatoxin B1 (AFB1) by integrating a galvanic replacement–synthesized Au@Ag–Pt nanozyme with a DNA walker–controlled rolling circle amplification (RCA) circuit. The core–shell Au@Ag–Pt nanozyme exhibits superior conductivity, enhanced peroxidase activity, and electrocatalytic performance, leading to a 17.67–fold amplification of ECL. A target-responsive “signal–off” mechanism was established based on AFB1-induced DNA structural switching and enzymatic cleavage, which effectively suppresses the RCA process and reduces the immobilization of nanozyme labels. The biosensor achieved a wide linear range from 5 × 10−11 to 5 × 10−5 mg/mL with a detection limit of 2.72 × 10−11 mg/mL. It shows high specificity against common interfering mycotoxins, good reproducibility, and satisfactory recoveries ranging from 82.7% to 110.5%.

Significance

This work not only provides a reliable platform for mycotoxin monitoring but also advances nanozyme engineering in biosensing, offering significant promise for food safety and environmental applications.
黄曲霉毒素B1 (AFB1)是一种剧毒真菌毒素,对全球食品安全和公众健康构成严重威胁。摄入这些受污染的产品会对食品安全系统和公众健康造成重大风险。尽管有各种检测技术,但对农产品中AFB1污染的高灵敏度分析的需求继续推动对改进方法的需求。结果将电替代合成的Au@Ag -Pt纳米酶与DNA步进控制的滚动圈扩增(RCA)电路集成,建立了一种新型的电化学发光(ECL)生物传感器,用于黄曲霉毒素B1 (AFB1)的灵敏检测。Au@Ag -Pt纳米酶具有优异的导电性,增强的过氧化物酶活性和电催化性能,使ECL扩增17.67倍。基于afb1诱导的DNA结构转换和酶促裂解,建立了一种靶向性的“信号关闭”机制,有效抑制了RCA过程,减少了纳米酶标签的固定化。该传感器在5 × 10−11 ~ 5 × 10−5 mg/mL范围内具有较宽的线性范围,检出限为2.72 × 10−11 mg/mL。该方法对常见的干扰性真菌毒素具有较高的特异性,重现性好,回收率为82.7% ~ 110.5%。这项工作不仅为真菌毒素监测提供了可靠的平台,而且推动了纳米酶工程在生物传感方面的发展,为食品安全和环境应用提供了重要的前景。
{"title":"Nicking-controlled biosensor: Integrating DNA Walker-RCA circuit with trimetallic nanozyme for aflatoxin B1 detection","authors":"Longsheng Jin ,&nbsp;YuJing Liu ,&nbsp;Wenqing Xia ,&nbsp;Meiling Zhou ,&nbsp;Ziying Xiao ,&nbsp;Jingyu Ge ,&nbsp;Xiao Yuan ,&nbsp;Qinqiang Zhu ,&nbsp;Meisheng Wu","doi":"10.1016/j.aca.2026.345193","DOIUrl":"10.1016/j.aca.2026.345193","url":null,"abstract":"<div><h3>Background</h3><div>Aflatoxin B<sub>1</sub> (AFB<sub>1</sub>) is a highly toxic mycotoxin that poses serious threats to global food safety and public health. The ingestion of these contaminated products causes substantial risks to both food safety systems and public health. Despite the availability of various detection techniques, the requirement for highly sensitive analysis of AFB<sub>1</sub> contamination in agricultural products continues to drive demand for improved methodologies.</div></div><div><h3>Results</h3><div>In this work, a novel electrochemiluminescence (ECL) biosensor was developed for the sensitive detection of aflatoxin B<sub>1</sub> (AFB<sub>1</sub>) by integrating a galvanic replacement–synthesized Au@Ag–Pt nanozyme with a DNA walker–controlled rolling circle amplification (RCA) circuit. The core–shell Au@Ag–Pt nanozyme exhibits superior conductivity, enhanced peroxidase activity, and electrocatalytic performance, leading to a 17.67–fold amplification of ECL. A target-responsive “signal–off” mechanism was established based on AFB<sub>1</sub>-induced DNA structural switching and enzymatic cleavage, which effectively suppresses the RCA process and reduces the immobilization of nanozyme labels. The biosensor achieved a wide linear range from 5 × 10<sup>−11</sup> to 5 × 10<sup>−5</sup> mg/mL with a detection limit of 2.72 × 10<sup>−11</sup> mg/mL. It shows high specificity against common interfering mycotoxins, good reproducibility, and satisfactory recoveries ranging from 82.7% to 110.5%.</div></div><div><h3>Significance</h3><div>This work not only provides a reliable platform for mycotoxin monitoring but also advances nanozyme engineering in biosensing, offering significant promise for food safety and environmental applications.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1392 ","pages":"Article 345193"},"PeriodicalIF":6.0,"publicationDate":"2026-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186097","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
Detailed impurity profiling of graphene oxide fractions by robust inductively coupled plasma optical emission spectrometry monitoring 用电感耦合等离子体发射光谱法监测氧化石墨烯组分的详细杂质谱图
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-03-22 Epub Date: 2026-01-29 DOI: 10.1016/j.aca.2026.345140
Iuliia A. Poimenova , Elizaveta Yu. Zhukova , Svetlana T. Ovseenko , Nikita S. Saratovsky , Ivan K. Kiryukhin , Daria-Mariia V. Ratova , Dmitrii M. Filatov , Anastasia M. Alekseeva , Svetlana V. Smirnova , Mikhail A. Proskurnin , Ivan V. Mikheev

Background

Graphene oxide (GO) is widely used in biomedicine and biotechnology due to its aqueous dispersibility and potential nanozyme activity. However, it remains analytically challenging because of structural heterogeneity and metallic inclusions, which affect its functional performance. GO therefore requires precise trace metal analysis, as even minor compositional variations can be critical. Modern multi-element analysis demands results that are both reliable and accurate, yet sound laboratory practice is not always followed. Although ICP-OES offers high sensitivity and precision, metrological rigor is often lacking. This work addresses the need for validated and robust elemental analysis of GO bulk material and particle-size fractions.

Results

ICP-OES was employed to quantify metals in bulk GO and to characterize Mn and Ti distribution in GO fractions. A fast algorithm was developed to identify robust plasma conditions by mapping the Mermet coefficient (Mg II/Mg I intensity ratio) across a range of flow rates and RF power levels. Concentrations for selected elements in the bulk material ranged from 10−1 to 103 mg kg−1; in aqueous dispersions, values reached up to 103 mg L−1. Validation parameters for Mn, Ti, and Fe included recoveries of 85–115 %, detection limits of 0.1–0.3 ng kg−1 (for used weight ca. 50 mg), and intra-/inter-day RSDs not exceeding 7 %. The Mermet coefficient exhibited an RSD of ∼0.6 %, indicating minimal matrix interference. Fraction analysis revealed a monotonic decrease in Mn toward fractions with smaller lateral-size cut-offs. ATR-FTIR spectra were obtained for stirred, purified, and ultrasound-treated GO fractions to assess whether purification altered the surface functional groups.

Significance

This study provides a validated approach for trace metal analysis in GO, combining sensitivity, robustness, and reproducibility across both bulk solid and aqueous dispersion forms. By experimentally examining the influence of plasma conditions on analytical performance, it offers the first systematic assessment of GO-specific ICP-OES parameter optimization. The results support more reliable characterization of GO materials and enable improved quality control in applications where elemental composition critically affects functionality.
氧化石墨烯(GO)由于其水溶性和潜在的纳米酶活性而广泛应用于生物医学和生物技术。然而,由于结构非均质性和金属夹杂物影响了其功能性能,因此在分析上仍然具有挑战性。因此氧化石墨烯需要精确的痕量金属分析,因为即使是微小的成分变化也可能是至关重要的。现代多元素分析要求结果既可靠又准确,但并不总是遵循良好的实验室实践。虽然ICP-OES具有较高的灵敏度和精度,但通常缺乏计量严谨性。这项工作解决了氧化石墨烯散装材料和粒度分数的验证和稳健元素分析的需要。结果icp - oes测定了大块氧化石墨烯中的金属,并表征了氧化石墨烯馏分中Mn和Ti的分布。通过绘制Mermet系数(Mg II/Mg I强度比)在流量和射频功率水平范围内的映射,开发了一种快速算法来识别稳健的等离子体条件。散装材料中选定元素的浓度范围为10 - 1至103 mg kg - 1;在水相分散体中,该值可达103 mg L−1。Mn、Ti和Fe的验证参数回收率为85 - 115%,检出限为0.1-0.3 ng kg - 1(使用重量约为50 mg),日内/日间rsd不超过7%。Mermet系数的RSD为~ 0.6%,表明基质干扰最小。分数分析显示,Mn的单调下降趋向于横向截距较小的分数。获得搅拌、纯化和超声处理氧化石墨烯馏分的ATR-FTIR光谱,以评估纯化是否改变了表面官能团。本研究为氧化石墨烯中痕量金属的分析提供了一种有效的方法,结合了敏感性、稳健性和可重复性,可以跨越大块固体和水分散形式。通过实验研究等离子体条件对分析性能的影响,首次对go特异性ICP-OES参数优化进行了系统评估。研究结果支持更可靠的氧化石墨烯材料表征,并在元素组成严重影响功能的应用中提高质量控制。
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引用次数: 0
Post-esterification preparation of carboxyl groups enriched magnetic microporous organic network for the efficient enrichment and determination of quaternary ammonium alkaloids 酯化后制备羧基富集磁微孔有机网络用于季铵盐生物碱的高效富集和测定
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-03-22 Epub Date: 2026-01-29 DOI: 10.1016/j.aca.2026.345173
Jian-Ming Liu , Jian Liu , Tian-Tian Ma , Cheng-Xiong Yang

Background

Microporous organic networks (MONs) are an emerging class of porous materials characterized by extremely large surface area, tunable topology, and superior stabilities, which have received increasing attention in sample pretreatment. However, their superhydrophobic nature has largely limited their application scope. The synthesis of functionalized MONs has proved to be a feasible strategy to broaden their utility. Nevertheless, this approach remains constrained by the limited variety and availability of functionalized monomers. Therefore, developing novel post-synthetic modification strategies is crucial for expanding the functionality and applications of MONs, particularly in trace analyte enrichment.

Results

Herein, we present a novel post-esterification strategy to synthesize a new carboxyl groups enriched magnetic MON (MMON-2COOH) for the highly efficient magnetic solid-phase extraction (MSPE) of four quaternary ammonium alkaloids (QAAs) from complex urine samples. The resulting MMON-2COOH not only retains the porous structure, excellent solvent and thermal stability, and rapid magnetic responsiveness of its precursor (hydroxyl-functionalized magnetic MON) but also incorporates conjugated networks and abundant carboxyl groups. This enables efficient extraction of QAAs through multiple interactions, including π-π stacking, hydrogen bonding, and electrostatic attraction. After optimization of extraction factors, an analytical method integrating MMON-2COOH-based extraction with HPLC-UV detection was established, achieving sensitive and selective determination of QAAs with low limits of detection of 0.05–0.5 μg L−1 and limits of quantification of 0.5–1.0 μg L−1, wide linear range of 0.5–1000 μg L−1, negligible matrix effect of 0.88–1.09, rapid extraction of 2 min, and less adsorbent consumption of 2 mg.

Significance

This is the first example of post-esterification preparation of carboxyl groups functionalized MON. The results demonstrate that MMON-2COOH is a highly effective adsorbent, and the developed method is suitable for accurate determination of QAAs in biological samples. This work highlights the significant potential of post-esterification as a versatile approach for designing high-performance adsorbents in sample pretreatment.
微孔有机网络(MONs)是一类新兴的多孔材料,具有极大的表面积,可调的拓扑结构和优异的稳定性,在样品预处理中受到越来越多的关注。然而,它们的超疏水性很大程度上限制了它们的应用范围。研究表明,合成功能化MONs是扩大其应用范围的一种可行策略。然而,这种方法仍然受到有限的品种和可用的官能化单体的限制。因此,开发新的合成后修饰策略对于扩展MONs的功能和应用至关重要,特别是在痕量分析物富集方面。结果本文提出了一种新的酯化后富集羧基的磁性MON (MMON-2COOH),用于复杂尿液样品中四种季铵盐生物碱的高效磁固相萃取(MSPE)。所得的MMON-2COOH不仅保留了其前驱体(羟基功能化磁性MON)的多孔结构、优异的溶剂稳定性和热稳定性以及快速的磁响应性,而且含有共轭网络和丰富的羧基。这使得通过多种相互作用(包括π-π堆叠、氢键和静电吸引)有效地提取QAAs成为可能。通过对提取因素的优化,建立了基于mmon - 2cooh的提取与HPLC-UV检测相结合的分析方法,实现了对QAAs的灵敏选择性测定,检测限为0.05 ~ 0.5 μg L−1,定量限为0.5 ~ 1.0 μg L−1,线性范围为0.5 ~ 1000 μg L−1,基质效应可忽略0.88 ~ 1.09,快速提取2 min,吸附剂消耗2 mg。本研究首次采用酯化后法制备羧基官能化聚氨基甲酚,结果表明,聚氨基甲酚- 2cooh是一种高效的吸附剂,该方法适用于生物样品中QAAs的精确测定。这项工作强调了后酯化作为一种设计样品预处理中高性能吸附剂的通用方法的重大潜力。
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Analytica Chimica Acta
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