Analytica Chimica Acta最新文献_第3页

Unlocking the complexity of macromolecular protein heterogeneity of glycoprotein IgE via an optimized online digestion middle-down proteomics approach 通过优化的在线消化中下蛋白质组学方法揭示糖蛋白IgE大分子蛋白异质性的复杂性

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2026-04-01 Epub Date: 2026-01-30 DOI: 10.1016/j.aca.2026.345161

Ruijie Liu , Zixin Liang , Shujun Xia , Yuxiang Luo , Huilin Li

Background

Proteoform-level analysis of large, highly modified proteins (≥50 kDa) such as immunoglobulin E (IgE) remains challenging due to their size and molecular heterogeneity. While traditional bottom-up proteomics fails to retain proteoform-level information, top-down approaches often lack the resolution required for effective proteoform discrimination. Middle-down proteomics (MDP) overcomes these limitations by generating highly redundant peptides in the 3–15 kDa range, which retain critical combinatorial modification patterns, thereby enabling more comprehensive characterization of complex proteoforms.

Results

To advance heterogeneity analysis of large proteins, we developed an online, tunable pepsin digestion platform that facilitates rapid and in-depth middle-down analysis of large proteins. When applied to IgE—a key allergy-related antibody with a large molecular weight (170–190 kDa) and bearing seven potential N-glycosylation sites—this platform produces high-redundancy peptides, enabling de novo sequencing of the variable region, which is critical for antigen recognition. Furthermore, analysis of middle-sized peptides allowed us to detect combined glycosylation patterns on the constant region 3 of the epsilon heavy chain (Cε3), revealing 39 Cε3 domain proteoforms. These proteoforms are important for Fcε receptor I interaction, therapeutic antibody binding, and downstream signaling. The platform also provided comprehensive glycosylation insights, including composition, occupancy, and microheterogeneity, thereby supporting detailed annotation of intact IgE proteoforms with varying glycan numbers.

Significance

By integrating sequence and glycosylation information, our approach offers a holistic perspective of IgE heterogeneity, which is essential for elucidating their roles in allergic diseases and for guiding diagnostic and therapeutic development. This study demonstrates that MDP analysis is highly valuable for large, diverse proteins like IgE. Our workflows enhance methodological versatility by minimizing dependence on specific proteases for particular proteins, thereby broadening the potential applications of MDP.

大的、高度修饰的蛋白（≥50 kDa），如免疫球蛋白E (IgE)，由于其大小和分子异质性，在蛋白形态水平上的分析仍然具有挑战性。传统的自底向上的蛋白质组学无法保留蛋白质水平的信息，而自顶向下的方法往往缺乏有效区分蛋白质所需的分辨率。中下蛋白质组学（mid -down proteomics， MDP）通过生成3-15 kDa范围内的高度冗余肽来克服这些限制，这些肽保留了关键的组合修饰模式，从而能够更全面地表征复杂的蛋白质形态。结果为了推进大蛋白的异质性分析，我们开发了一个在线、可调的胃蛋白酶消化平台，促进了对大蛋白的快速、深入的中向下分析。当应用于ige（一种关键的过敏相关抗体，分子量大（170-190 kDa），含有7个潜在的n -糖基化位点）时，该平台产生高冗余肽，使可变区域的重新测序成为可能，这对抗原识别至关重要。此外，对中等大小多肽的分析使我们能够检测到epsilon重链恒定区3 （Cε3）上的组合糖基化模式，揭示了39种Cε3结构域蛋白形式。这些蛋白形式对于fce1受体相互作用、治疗性抗体结合和下游信号传导都很重要。该平台还提供了全面的糖基化见解，包括组成、占用和微异质性，从而支持对具有不同聚糖数的完整IgE蛋白形式的详细注释。通过整合序列和糖基化信息，我们的方法提供了IgE异质性的整体视角，这对于阐明它们在过敏性疾病中的作用以及指导诊断和治疗发展至关重要。这项研究表明，MDP分析对于像IgE这样的大而多样的蛋白质非常有价值。我们的工作流程通过最大限度地减少对特定蛋白质的特定蛋白酶的依赖来增强方法的通用性，从而扩大了MDP的潜在应用。

{"title":"Unlocking the complexity of macromolecular protein heterogeneity of glycoprotein IgE via an optimized online digestion middle-down proteomics approach","authors":"Ruijie Liu , Zixin Liang , Shujun Xia , Yuxiang Luo , Huilin Li","doi":"10.1016/j.aca.2026.345161","DOIUrl":"10.1016/j.aca.2026.345161","url":null,"abstract":"<div><h3>Background</h3><div>Proteoform-level analysis of large, highly modified proteins (≥50 kDa) such as immunoglobulin E (IgE) remains challenging due to their size and molecular heterogeneity. While traditional bottom-up proteomics fails to retain proteoform-level information, top-down approaches often lack the resolution required for effective proteoform discrimination. Middle-down proteomics (MDP) overcomes these limitations by generating highly redundant peptides in the 3–15 kDa range, which retain critical combinatorial modification patterns, thereby enabling more comprehensive characterization of complex proteoforms.</div></div><div><h3>Results</h3><div>To advance heterogeneity analysis of large proteins, we developed an online, tunable pepsin digestion platform that facilitates rapid and in-depth middle-down analysis of large proteins. When applied to IgE—a key allergy-related antibody with a large molecular weight (170–190 kDa) and bearing seven potential N-glycosylation sites—this platform produces high-redundancy peptides, enabling <em>de novo</em> sequencing of the variable region, which is critical for antigen recognition. Furthermore, analysis of middle-sized peptides allowed us to detect combined glycosylation patterns on the constant region 3 of the epsilon heavy chain (Cε3), revealing 39 Cε3 domain proteoforms. These proteoforms are important for Fcε receptor I interaction, therapeutic antibody binding, and downstream signaling. The platform also provided comprehensive glycosylation insights, including composition, occupancy, and microheterogeneity, thereby supporting detailed annotation of intact IgE proteoforms with varying glycan numbers.</div></div><div><h3>Significance</h3><div>By integrating sequence and glycosylation information, our approach offers a holistic perspective of IgE heterogeneity, which is essential for elucidating their roles in allergic diseases and for guiding diagnostic and therapeutic development. This study demonstrates that MDP analysis is highly valuable for large, diverse proteins like IgE. Our workflows enhance methodological versatility by minimizing dependence on specific proteases for particular proteins, thereby broadening the potential applications of MDP.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1393 ","pages":"Article 345161"},"PeriodicalIF":6.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089768","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

Label-free electrochemical levodopa detection via dummy imprinted polymers for advanced disease monitoring 基于假体印迹聚合物的无标记左旋多巴电化学检测用于晚期疾病监测

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2026-04-01 Epub Date: 2026-01-30 DOI: 10.1016/j.aca.2026.345174

O. Jamieson , A. Dann , X. Liu , T. Oliveira Abib , K. Novakovic , J. McClements , S. Seyedin , J. Gruber , R.D. Crapnell , H. Snyder , C.E. Banks , J.A. Dawson , M. Peeters

Current estimates see 25.2 million people living with from Parkinson's disease (PD) worldwide by 2050, with no cure close to being available. With therapeutic LDp (LDp) use being the mainstay treatment for a vast proportion of individuals with PD, an effective protocol for managing medication in real-time, is not only essential but long overdue. Presented hereafter is a highly reproducible polymeric electrochemical detection platform with an economically viable production process that can specifically and selectively detect LDp at the relevant physiological range. Computational modelling of target-monomer interactions is employed to direct monomer selection and polymer synthesis. Testing the sensor platform within a dynamic range (5–50 μM) of LDp and its metabolite Dp (Dp) in a range of different sample media affords a 42% higher response of current change upon binding to LDp compared to Dp despite high structural similarity between the compounds. Furthermore, the sensor shows no significant difference when tested in different sample media, allowing this electrochemical sensor to operate across a range of different sample sources, further enhancing its adaptability and applicability in an ever-changing landscape of medical technology.

目前估计，到2050年，全世界将有2520万人患有帕金森病（PD），目前尚无治愈方法。随着治疗性LDp （LDp）的使用成为大部分PD患者的主要治疗方法，一种有效的实时用药管理方案不仅必不可少，而且早就应该出现了。本文提出了一种高重复性的聚合物电化学检测平台，具有经济可行的生产工艺，可以特异性和选择性地检测相关生理范围内的LDp。目标-单体相互作用的计算模型用于指导单体选择和聚合物合成。在不同的样品介质中，在LDp及其代谢物Dp （Dp）的动态范围（5-50 μM）内测试传感器平台，与Dp相比，尽管化合物之间的结构高度相似，但与LDp结合时电流变化的响应要高42%。此外，该传感器在不同的样品介质中测试时没有显着差异，这使得该电化学传感器可以在一系列不同的样品源中工作，进一步增强了其在不断变化的医疗技术领域的适应性和适用性。

{"title":"Label-free electrochemical levodopa detection via dummy imprinted polymers for advanced disease monitoring","authors":"O. Jamieson , A. Dann , X. Liu , T. Oliveira Abib , K. Novakovic , J. McClements , S. Seyedin , J. Gruber , R.D. Crapnell , H. Snyder , C.E. Banks , J.A. Dawson , M. Peeters","doi":"10.1016/j.aca.2026.345174","DOIUrl":"10.1016/j.aca.2026.345174","url":null,"abstract":"<div><div>Current estimates see 25.2 million people living with from Parkinson's disease (PD) worldwide by 2050, with no cure close to being available. With therapeutic LDp (LDp) use being the mainstay treatment for a vast proportion of individuals with PD, an effective protocol for managing medication in <em>real-time</em>, is not only essential but long overdue. Presented hereafter is a highly reproducible polymeric electrochemical detection platform with an economically viable production process that can specifically and selectively detect LDp at the relevant physiological range. Computational modelling of target-monomer interactions is employed to direct monomer selection and polymer synthesis. Testing the sensor platform within a dynamic range (5–50 μM) of LDp and its metabolite Dp (Dp) in a range of different sample media affords a 42% higher response of current change upon binding to LDp compared to Dp despite high structural similarity between the compounds. Furthermore, the sensor shows no significant difference when tested in different sample media, allowing this electrochemical sensor to operate across a range of different sample sources, further enhancing its adaptability and applicability in an ever-changing landscape of medical technology.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1393 ","pages":"Article 345174"},"PeriodicalIF":6.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089622","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

Classification of DNA secondary structures by combining multiple spectral techniques with machine learning 结合多光谱技术与机器学习的DNA二级结构分类

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2026-04-01 Epub Date: 2026-02-05 DOI: 10.1016/j.aca.2026.345195

Hong Luo , Guantong Xu , Yujing Zhang , Xiaoxuan Xiang , Hao Wang , Xinhua Guo

Background

The identification of structural features is an essential prerequisite for the determination of DNA secondary structures and investigating structural formation mechanisms. Circular dichroism (CD) spectroscopy, fluorescence (FL) spectroscopy, and thermal difference spectra (TDS) have already been used to monitor the DNA secondary structures due to their advantages in operational simplicity, detection speed and lower cost. However, each individual spectroscopic method has limitations in providing comprehensive structural information. Therefore, we propose that integrating these three spectroscopic techniques could improve the classification accuracy of DNA secondary structures—though, to date, no related studies have been reported.

Results

In this assay, a combination method of CD, FL, and TDS was proposed through machine learning (ML). Principal component analysis (PCA) was firstly used to reduce the dimensionality and facilitate data analysis, and then, three machine learning methods, including linear discriminant analysis (LDA), K-nearest neighbor (KNN), and support vector machine (SVM), were employed to deeply excavate more structure-related information of CD, FL, and TDS spectra. Combined with a two-step ML strategy, 79 out of 85 DNA sequences, that fall into G4, iM and DS category respectively, were correctly classified (classification accuracy of 0.95). Thus, we achieved the goal of predicting unknown DNA secondary structures by combining CD, FL, and TDS spectra, and demonstrated the superiority of the combination of three spectra in DNA structure identification.

Significance

The method is significantly superior to the single spectroscopic technique. Thus, a simple, fast, and cost-efficient spectroscopic platform for the direct and comprehensive identification of DNA secondary structures has been established. By building a multispectral database and using ML methods, the accurate and comprehensive identification of unknown DNA secondary structures will finally be realized.

结构特征的识别是确定DNA二级结构和研究结构形成机制的必要前提。圆二色光谱（CD）、荧光光谱（FL）和热差光谱（TDS）由于其操作简单、检测速度快、成本低等优点，已被广泛用于DNA二级结构的检测。然而，每种单独的光谱方法在提供全面的结构信息方面都有局限性。因此，我们建议整合这三种光谱技术可以提高DNA二级结构的分类准确性，尽管迄今为止尚未有相关的研究报道。结果通过机器学习（ML）建立了CD、FL和TDS的联合检测方法。首先利用主成分分析（PCA）降维，方便数据分析，然后利用线性判别分析（LDA）、k近邻分析（KNN）和支持向量机（SVM）三种机器学习方法深入挖掘CD、FL和TDS光谱的更多结构相关信息。结合两步ML策略，85个分别属于G4、iM和DS类的DNA序列中有79个被正确分类（分类精度为0.95）。因此，我们通过结合CD、FL和TDS光谱达到了预测未知DNA二级结构的目的，并证明了三种光谱结合在DNA结构鉴定中的优势。意义该方法明显优于单光谱技术。因此，建立了一个简单、快速、经济的直接、全面鉴定DNA二级结构的光谱平台。通过建立多光谱数据库，利用ML方法，最终实现对未知DNA二级结构的准确、全面的鉴定。

{"title":"Classification of DNA secondary structures by combining multiple spectral techniques with machine learning","authors":"Hong Luo , Guantong Xu , Yujing Zhang , Xiaoxuan Xiang , Hao Wang , Xinhua Guo","doi":"10.1016/j.aca.2026.345195","DOIUrl":"10.1016/j.aca.2026.345195","url":null,"abstract":"<div><h3>Background</h3><div>The identification of structural features is an essential prerequisite for the determination of DNA secondary structures and investigating structural formation mechanisms. Circular dichroism (CD) spectroscopy, fluorescence (FL) spectroscopy, and thermal difference spectra (TDS) have already been used to monitor the DNA secondary structures due to their advantages in operational simplicity, detection speed and lower cost. However, each individual spectroscopic method has limitations in providing comprehensive structural information. Therefore, we propose that integrating these three spectroscopic techniques could improve the classification accuracy of DNA secondary structures—though, to date, no related studies have been reported.</div></div><div><h3>Results</h3><div>In this assay, a combination method of CD, FL, and TDS was proposed through machine learning (ML). Principal component analysis (PCA) was firstly used to reduce the dimensionality and facilitate data analysis, and then, three machine learning methods, including linear discriminant analysis (LDA), K-nearest neighbor (KNN), and support vector machine (SVM), were employed to deeply excavate more structure-related information of CD, FL, and TDS spectra. Combined with a two-step ML strategy, 79 out of 85 DNA sequences, that fall into G4, iM and DS category respectively, were correctly classified (classification accuracy of 0.95). Thus, we achieved the goal of predicting unknown DNA secondary structures by combining CD, FL, and TDS spectra, and demonstrated the superiority of the combination of three spectra in DNA structure identification.</div></div><div><h3>Significance</h3><div>The method is significantly superior to the single spectroscopic technique. Thus, a simple, fast, and cost-efficient spectroscopic platform for the direct and comprehensive identification of DNA secondary structures has been established. By building a multispectral database and using ML methods, the accurate and comprehensive identification of unknown DNA secondary structures will finally be realized.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1393 ","pages":"Article 345195"},"PeriodicalIF":6.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129535","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

Novel diffusion gradient in thin-films based on antibiofouling Ag/polydopamine membranes for measurement of antibiotics in natural waters 基于抗生素掺杂银/聚多巴胺膜的新型薄膜扩散梯度测定天然水体中抗生素

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2026-04-01 Epub Date: 2026-01-30 DOI: 10.1016/j.aca.2026.345157

Jiaxing Xie , Fan Ge , Xinyi Yan , Suyu Ren , Yan Wang , Feng Tan

Background

The diffusion gradient in thin-films (DGT) device is widely used for in situ measurement of pollutants in aquatic environments, offering high enrichment efficiency and robustness to environmental variations such as temperature and hydrodynamics. These characteristics make DGT particularly suitable for monitoring a diverse array of trace organic contaminants in waters. However, long-term deployment is often compromised by biofilm formation on the sampling outer membrane, which can obstruct analyte diffusion and lead to underestimation of analyte concentrations. This study addresses the need for a biofouling-resistant DGT device that maintains accuracy during extended field applications.

Results

A novel DGT device incorporating an antifouling Ag/polydopamine-modified polyethersulfone (Ag/PDA-PES) membrane was developed. The modified membrane demonstrated dual functional improvements: a 40 % reduction in water contact angle, indicating enhanced hydrophilicity, and strong antimicrobial efficacy, evidenced by an inhibition zone of 1165 μm ± 110 μm against Escherichia coli, while maintaining diffusion characteristics comparable to the original PES membrane. In extended deployment in both simulated and natural waters, the Ag/PDA-PES membrane effectively inhibited biofilm formation and maintained stable analyte diffusion coefficients over time compared to the unmodified membrane. The DGT devices showed constant sampling performance across varying pH (5.0–9.0), ionic strength (0–200 mM NaCl), and dissolved organic matter levels (0–20 mg/L). Field validation confirmed the device reliability, with measured total antibiotic concentrations (692–1062 ng/L) consistent with grab sampling.

Significance

This work signifies a step forward in DGT passive sampling technology by integrating antifouling properties directly into the membrane, thereby enabling accurate long-term monitoring of pollutants in biofilm-prone waters. Moreover, this study provides a promising strategy for improving the reliability of long-term DGT sampling, with meaningful implications for the precise monitoring and ecological risk assessment of other emerging pollutants.

薄膜扩散梯度（diffusion gradient in thin-films， DGT）装置广泛用于水生环境中污染物的原位测量，具有富集效率高、对温度和水动力等环境变化具有鲁棒性等优点。这些特点使DGT特别适合监测水中各种微量有机污染物。然而，长期部署通常会受到采样外膜上形成的生物膜的影响，这可能会阻碍分析物的扩散并导致分析物浓度的低估。本研究解决了在扩展的现场应用中保持精度的抗生物污垢DGT设备的需求。结果制备了一种新型的Ag/聚多巴胺改性聚醚砜（Ag/PDA-PES）防污膜DGT装置。改性后的膜显示出双重功能的改善：水接触角降低40%，表明亲水性增强；抗菌效果强，对大肠杆菌的抑制范围为1165 μm±110 μm，同时保持了与原始PES膜相当的扩散特性。Ag/PDA-PES膜在模拟水体和自然水体中均能有效抑制生物膜的形成，与未经修饰的膜相比，随着时间的推移，Ag/PDA-PES膜保持稳定的分析物扩散系数。DGT器件在不同的pH值（5.0-9.0）、离子强度（0-200 mM NaCl）和溶解有机物水平（0-20 mg/L）下均具有恒定的采样性能。现场验证证实了设备的可靠性，测量的抗生素总浓度（692-1062 ng/L）与抓取取样一致。这项工作标志着DGT被动采样技术向前迈进了一步，通过将防污特性直接集成到膜中，从而能够在易被生物膜覆盖的水域中对污染物进行准确的长期监测。此外，该研究为提高长期DGT采样的可靠性提供了一种有希望的策略，对其他新兴污染物的精确监测和生态风险评估具有重要意义。

{"title":"Novel diffusion gradient in thin-films based on antibiofouling Ag/polydopamine membranes for measurement of antibiotics in natural waters","authors":"Jiaxing Xie , Fan Ge , Xinyi Yan , Suyu Ren , Yan Wang , Feng Tan","doi":"10.1016/j.aca.2026.345157","DOIUrl":"10.1016/j.aca.2026.345157","url":null,"abstract":"<div><h3>Background</h3><div>The diffusion gradient in thin-films (DGT) device is widely used for in situ measurement of pollutants in aquatic environments, offering high enrichment efficiency and robustness to environmental variations such as temperature and hydrodynamics. These characteristics make DGT particularly suitable for monitoring a diverse array of trace organic contaminants in waters. However, long-term deployment is often compromised by biofilm formation on the sampling outer membrane, which can obstruct analyte diffusion and lead to underestimation of analyte concentrations. This study addresses the need for a biofouling-resistant DGT device that maintains accuracy during extended field applications.</div></div><div><h3>Results</h3><div>A novel DGT device incorporating an antifouling Ag/polydopamine-modified polyethersulfone (Ag/PDA-PES) membrane was developed. The modified membrane demonstrated dual functional improvements: a 40 % reduction in water contact angle, indicating enhanced hydrophilicity, and strong antimicrobial efficacy, evidenced by an inhibition zone of 1165 μm ± 110 μm against <em>Escherichia coli</em>, while maintaining diffusion characteristics comparable to the original PES membrane. In extended deployment in both simulated and natural waters, the Ag/PDA-PES membrane effectively inhibited biofilm formation and maintained stable analyte diffusion coefficients over time compared to the unmodified membrane. The DGT devices showed constant sampling performance across varying pH (5.0–9.0), ionic strength (0–200 mM NaCl), and dissolved organic matter levels (0–20 mg/L). Field validation confirmed the device reliability, with measured total antibiotic concentrations (692–1062 ng/L) consistent with grab sampling.</div></div><div><h3>Significance</h3><div>This work signifies a step forward in DGT passive sampling technology by integrating antifouling properties directly into the membrane, thereby enabling accurate long-term monitoring of pollutants in biofilm-prone waters. Moreover, this study provides a promising strategy for improving the reliability of long-term DGT sampling, with meaningful implications for the precise monitoring and ecological risk assessment of other emerging pollutants.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1393 ","pages":"Article 345157"},"PeriodicalIF":6.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089623","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

A deprotection-oxidation cascade-regulated dual-responsive near-infrared fluorescent probe for individual and sequential detection of H2S/HClO with applications in food safety monitoring 一种脱保护-氧化级联调节双响应近红外荧光探针，用于单独和顺序检测H2S/HClO在食品安全监测中的应用

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2026-04-01 Epub Date: 2026-02-03 DOI: 10.1016/j.aca.2026.345191

Jie Yang , Chao Fu , Yicong Zhou , Hua Zhang , Xiangzhi Song , Dandan Li , Chuanxiang Liu

Background

Hydrogen sulfide (H₂S) and hypochlorous acid (HClO), as critical reactive sulfur (RSS) and oxygen (ROS) species, respectively play dual roles in physiological regulation and food safety. While numerous fluorescent probes exist for individual detection of H₂S or HClO, dual-functional probes remain rare despite their significant potential in food safety, environmental monitoring, and biomedicine.

Results

A novel A-π-A (acceptor-π-bridge-acceptor) type near-infrared fluorescent probe, DCIQ-DNBS, was developed for the first time, featuring dual-response mechanisms for individual and sequential detection of H₂S and HClO via H₂S-triggered thiolysis of the 2,4-dinitrobenzenesulfonyl (DNBS) and HClO mediated DNBS-deprotection-oxidation of electron-deficient CC bond cascade oxidation. The probe DCIQ-DNBS demonstrates exceptional selectivity and rapid response times, and offers dual-channel fluorescence signaling with non-overlapping emissions: a near-infrared response at 740 nm for H₂S (LOD, 49 nM) and a short-wavelength yellow emission at 562 nm for HClO (LOD, 40 nM). Practical applications were demonstrated through DCIQ-DNBS loaded portable test strips, which successfully enabled visual monitoring of gaseous H₂S in food spoilage samples and quantitative tracing of HClO in foods. Furthermore, cellular studies revealed the probe's capability to detect elevated levels of both H₂S and HClO in HeLa cells.

Significance and novelty

This novel single-probe system enables the individual and sequential detection of two distinct analytes in a single assay. By generating unique emission signals for each target, it eliminates the need for separate tests or complex separation steps, thereby revolutionizing efficiency in fields like food safety monitoring.

硫化氢（H2S）和次氯酸（HClO）作为关键的活性硫（RSS）和活性氧（ROS）物质，分别在生理调节和食品安全中发挥着双重作用。虽然目前存在大量用于单独检测H2S或HClO的荧光探针，但双功能探针在食品安全、环境监测和生物医学方面具有巨大的潜力，但仍然很少。结果首次研制了一种新型的A-π-A（受体-π-桥接-受体）型近红外荧光探针DCIQ-DNBS，该探针具有双响应机制，可通过H2S触发2,4-二硝基苯磺酰（DNBS）的硫解和HClO介导的DNBS-脱保护-缺电子C=C键级联氧化对H2S和HClO进行单次和顺序检测。DCIQ-DNBS探针表现出卓越的选择性和快速的响应时间，并提供双通道荧光信号，无重叠发射：对H2S （LOD, 49 nm）有740 nm的近红外响应，对HClO （LOD, 40 nm）有562 nm的短波长黄色发射。通过装载DCIQ-DNBS的便携式试纸条演示了实际应用，成功实现了食品腐败样品中气态H2S的可视化监测和食品中HClO的定量溯源。此外，细胞研究表明，探针能够检测HeLa细胞中H2S和HClO水平的升高。意义和新颖性这种新颖的单探针系统能够在一次分析中对两种不同的分析物进行单独和顺序的检测。通过为每个目标产生独特的发射信号，它消除了单独测试或复杂分离步骤的需要，从而彻底提高了食品安全监测等领域的效率。

{"title":"A deprotection-oxidation cascade-regulated dual-responsive near-infrared fluorescent probe for individual and sequential detection of H2S/HClO with applications in food safety monitoring","authors":"Jie Yang , Chao Fu , Yicong Zhou , Hua Zhang , Xiangzhi Song , Dandan Li , Chuanxiang Liu","doi":"10.1016/j.aca.2026.345191","DOIUrl":"10.1016/j.aca.2026.345191","url":null,"abstract":"<div><h3>Background</h3><div>Hydrogen sulfide (H<sub>2</sub>S) and hypochlorous acid (HClO), as critical reactive sulfur (RSS) and oxygen (ROS) species, respectively play dual roles in physiological regulation and food safety. While numerous fluorescent probes exist for individual detection of H<sub>2</sub>S or HClO, dual-functional probes remain rare despite their significant potential in food safety, environmental monitoring, and biomedicine.</div></div><div><h3>Results</h3><div>A novel A-π-A (acceptor-π-bridge-acceptor) type near-infrared fluorescent probe, <strong>DCIQ-DNBS</strong>, was developed for the first time, featuring dual-response mechanisms for individual and sequential detection of H<sub>2</sub>S and HClO via H<sub>2</sub>S-triggered thiolysis of the 2,4-dinitrobenzenesulfonyl (DNBS) and HClO mediated DNBS<strong>-</strong>deprotection-oxidation of electron-deficient C<img>C bond cascade oxidation. The probe <strong>DCIQ-DNBS</strong> demonstrates exceptional selectivity and rapid response times, and offers dual-channel fluorescence signaling with non-overlapping emissions: a near-infrared response at 740 nm for H<sub>2</sub>S (LOD, 49 nM) and a short-wavelength yellow emission at 562 nm for HClO (LOD, 40 nM). Practical applications were demonstrated through <strong>DCIQ-DNBS</strong> loaded portable test strips, which successfully enabled visual monitoring of gaseous H<sub>2</sub>S in food spoilage samples and quantitative tracing of HClO in foods. Furthermore, cellular studies revealed the probe's capability to detect elevated levels of both H<sub>2</sub>S and HClO in HeLa cells.</div></div><div><h3>Significance and novelty</h3><div>This novel single-probe system enables the individual and sequential detection of two distinct analytes in a single assay. By generating unique emission signals for each target, it eliminates the need for separate tests or complex separation steps, thereby revolutionizing efficiency in fields like food safety monitoring.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1393 ","pages":"Article 345191"},"PeriodicalIF":6.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111015","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

Exploring lactoferrin as an innovative covalently immobilized chiral selector for the selective separation of pharmaceutical enantiomers using HPLC 乳铁蛋白作为新型共价固定化手性选择剂用于药物对映体的高效液相色谱选择性分离

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2026-04-01 Epub Date: 2026-02-05 DOI: 10.1016/j.aca.2026.345205

Adel Ehab Ibrahim , Samy G. Alamir , Ghanem Al-Thani , Sami El Deeb , Ahmed Al-Harrasi

Background

Molecular chirality has a profound impact on pharmaceutical drugs' efficacy and safety. Thus, chiral recognition plays a vital role in drug development throughout all process stages. LF is a globular glycoprotein composed of approximately 700 amino acids, that's capable of providing multiple interactions through its amino acid residues.

Results

In the proposed research, lactoferrin (LF) was covalently immobilized for the first time using a monolithic epoxy stationary phase via a Schiff's base formation as chiral selector (CS). LF-CS was evaluated for the enantioselective HPLC separation of 18 racemic pharmaceutical drugs. The chromatographic conditions were optimized for optimum enantio-separation. LF-CS proved its potential as a CS enabling the enantioseparation of 10 drug racemates: cetirizine, omeprazole, lansoprazole, dapoxetine, doxazosin, nebivolol, atenolol, bisoprolol, chlorthalidone and ofloxacin. Moreover, in-silico molecular docking studies were conducted to help understand the separation modes. LF as a CS reported hydrogen bonding, hydrophobic interactions, π bonding, van der Waals forces, and electrostatic interactions. Finally, the novel LF-CS was applied to determine the enantiomeric purity of marketed single-enantiomer pharmaceutical products, demonstrating its ability to verify their composition and identify impurities.

Significance

HPLC remains the primary choice for all pharmaceutical research, as it offers higher sensitivity, reliability, and reproducibility. This work introduces LF as a novel, multifunctional CS for HPLC, covalently immobilized for the first time, expanding the toolbox of protein-based chiral stationary phases. Moreover, the study also offers a critical insight into the limitations of relying solely on computational predictions, empirically demonstrating that solvent effects can override binding affinities, a phenomenon not captured by standard docking simulations.

分子手性对药物的疗效和安全性有着深远的影响。因此，手性识别在药物开发的所有过程阶段起着至关重要的作用。LF是一种由大约700个氨基酸组成的球状糖蛋白，能够通过其氨基酸残基提供多种相互作用。结果在本研究中，乳铁蛋白（LF）首次通过席夫碱形成的单片环氧固定相作为手性选择剂（CS）被共价固定。采用高效液相色谱法对18种外消旋药物的对映选择性分离进行了评价。优化了对映体分离的最佳色谱条件。LF-CS证明了其作为CS的潜力，可以对10种药物外消旋物进行对映体分离：西替利嗪、奥美拉唑、兰索拉唑、达泊西汀、多沙唑嗪、奈比洛尔、阿替洛尔、比索洛尔、氯噻酮和氧氟沙星。此外，进行了硅分子对接研究，以帮助了解分离模式。作为CS的LF报道了氢键、疏水相互作用、π键、范德华力和静电相互作用。最后，将新型LF-CS应用于已上市的单对映体药品的对映体纯度测定，证明了其验证成分和杂质鉴定的能力。高效液相色谱法仍然是所有药物研究的首选，因为它具有更高的灵敏度、可靠性和重复性。本文首次介绍了LF作为一种新型的多功能高效液相色谱，共价固定，扩大了基于蛋白质的手性固定相的工具箱。此外，该研究还对仅依靠计算预测的局限性提供了重要的见解，经验证明溶剂效应可以覆盖结合亲和力，这是标准对接模拟无法捕获的现象。

{"title":"Exploring lactoferrin as an innovative covalently immobilized chiral selector for the selective separation of pharmaceutical enantiomers using HPLC","authors":"Adel Ehab Ibrahim , Samy G. Alamir , Ghanem Al-Thani , Sami El Deeb , Ahmed Al-Harrasi","doi":"10.1016/j.aca.2026.345205","DOIUrl":"10.1016/j.aca.2026.345205","url":null,"abstract":"<div><h3>Background</h3><div>Molecular chirality has a profound impact on pharmaceutical drugs' efficacy and safety. Thus, chiral recognition plays a vital role in drug development throughout all process stages. LF is a globular glycoprotein composed of approximately 700 amino acids, that's capable of providing multiple interactions through its amino acid residues.</div></div><div><h3>Results</h3><div>In the proposed research, lactoferrin (LF) was covalently immobilized for the first time using a monolithic epoxy stationary phase via a Schiff's base formation as chiral selector (CS). LF-CS was evaluated for the enantioselective HPLC separation of 18 racemic pharmaceutical drugs. The chromatographic conditions were optimized for optimum enantio-separation. LF-CS proved its potential as a CS enabling the enantioseparation of 10 drug racemates: cetirizine, omeprazole, lansoprazole, dapoxetine, doxazosin, nebivolol, atenolol, bisoprolol, chlorthalidone and ofloxacin. Moreover, <em>in-silico</em> molecular docking studies were conducted to help understand the separation modes. LF as a CS reported hydrogen bonding, hydrophobic interactions, π bonding, van der Waals forces, and electrostatic interactions. Finally, the novel LF-CS was applied to determine the enantiomeric purity of marketed single-enantiomer pharmaceutical products, demonstrating its ability to verify their composition and identify impurities.</div></div><div><h3>Significance</h3><div>HPLC remains the primary choice for all pharmaceutical research, as it offers higher sensitivity, reliability, and reproducibility. This work introduces LF as a novel, multifunctional CS for HPLC, covalently immobilized for the first time, expanding the toolbox of protein-based chiral stationary phases. Moreover, the study also offers a critical insight into the limitations of relying solely on computational predictions, empirically demonstrating that solvent effects can override binding affinities, a phenomenon not captured by standard docking simulations.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1393 ","pages":"Article 345205"},"PeriodicalIF":6.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135331","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

·ATP-enhanced PB@MIL-100(Fe) nanozyme enables dual-mode ratiometric colorimetric and smartphone-based hydrogel detection of nitrite in food samples ·atp增强PB@MIL-100（Fe）纳米酶可实现食品样品中亚硝酸盐的双模式比例比色法和基于智能手机的水凝胶检测

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2026-04-01 Epub Date: 2026-02-02 DOI: 10.1016/j.aca.2026.345192

Biyao Dai , Quanyong Dong , Taiqi Hao , Shenghui Zhang , Dong Xu , Ying Xiong , Wang Li , Qian Wen , Zhimei Huang , Jiali Ren

Background

Nitrite residues pose significant threats to food safety, as excessive consumption of this may cause serious health risks to human. Conventional techniques such as Griess reagent and chromatographic methods can successfully quantify nitrite levels, but these approaches often suffer from complex sample preparation, poor selectivity, expensive instrumentation, necessitate professional operators and time-consuming procedures. These limitations restrict their practical application for detection nitrites in point-of-care testing (POCT). Therefore, developing sensitive and portable nitrite detection methods remains critically important for food safety monitoring.

Results

Herein, we developed a novel dual-mode sensing platform based on composite nanozymes PB@MIL-100(Fe)@ATP for sensitive, selective and portable nitrite detection. This platform integrates Prussian Blue with MIL-100(Fe) metal-organic framework and exploits adenosine triphosphate (ATP) as an enhancer. The resulting PB@MIL-100(Fe)@ATP demonstrated excellent peroxidase-like (POD-like) catalytic activity, which catalyzes the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) to form blue-colored oxidized TMB (TMBox) with a characteristic absorption peak at 652 nm. In the presence of nitrites, TMBox specifically undergoes diazotization under acidic conditions to produce yellow diazotized TMB, exhibiting increased absorbance at 450 nm while decreasing at 652 nm. The ratiometric colorimetric assay achieved a detection limit of 0.17 μM within 20 min through absorbance ratio analysis at 652/450 nm. Furthermore, a smartphone-assisted hydrogel sensing method with detection limit of 1.68 μM was developed for point-of-care nitrites monitoring through image capture and color analysis, providing equipment-free operation.

Significance

The ATP-enhanced PB@MIL-100(Fe) nanozyme was successfully applied to detect nitrites with high recovery rates in real pickled vegetables, sauerkraut, and sausage samples. This dual-mode platform demonstrated excellent selectivity, high quantitative accuracy, and practical applicability in complex food matrices, providing a simple, rapid and versatile tool for on-site food safety monitoring.

亚硝酸盐残留对食品安全构成重大威胁，过量食用会对人体健康造成严重危害。Griess试剂和色谱法等传统技术可以成功地定量亚硝酸盐水平，但这些方法通常存在样品制备复杂、选择性差、仪器昂贵、需要专业操作人员和耗时的过程等问题。这些局限性限制了它们在即时检测（POCT）中检测亚硝酸盐的实际应用。因此，开发灵敏、便携的亚硝酸盐检测方法对食品安全监测至关重要。结果建立了一种基于复合纳米酶PB@MIL-100(Fe)@ATP的新型双模传感平台，用于亚硝酸盐的灵敏、选择性和便携式检测。该平台将普鲁士蓝与MIL-100（Fe）金属有机框架相结合，利用三磷酸腺苷（ATP）作为增强剂。得到的PB@MIL-100(Fe)@ATP具有优异的过氧化物酶样（pod样）催化活性，催化3,3',5,5'-四甲基联苯胺（TMB）氧化生成蓝色氧化TMB (TMBox)，其特征吸收峰在652nm处。在亚硝酸盐的存在下，TMBox在酸性条件下特异性重氮化，生成黄色重氮化的TMB，在450nm处吸光度增加，在652nm处吸光度下降。通过652/450 nm吸光度分析，比值比色法在20分钟内检出限为0.17 μM。此外，开发了一种检测限为1.68 μM的智能手机辅助水凝胶传感方法，通过图像采集和颜色分析进行即时亚硝酸盐监测，无需设备操作。意义atp增强PB@MIL-100（Fe）纳米酶可用于实际腌菜、酸菜和香肠样品中亚硝酸盐的检测，回收率高。该双模平台在复杂的食品基质中表现出优异的选择性、高的定量准确性和实用性，为现场食品安全监测提供了一种简单、快速、通用的工具。

{"title":"·ATP-enhanced PB@MIL-100(Fe) nanozyme enables dual-mode ratiometric colorimetric and smartphone-based hydrogel detection of nitrite in food samples","authors":"Biyao Dai , Quanyong Dong , Taiqi Hao , Shenghui Zhang , Dong Xu , Ying Xiong , Wang Li , Qian Wen , Zhimei Huang , Jiali Ren","doi":"10.1016/j.aca.2026.345192","DOIUrl":"10.1016/j.aca.2026.345192","url":null,"abstract":"<div><h3>Background</h3><div>Nitrite residues pose significant threats to food safety, as excessive consumption of this may cause serious health risks to human. Conventional techniques such as Griess reagent and chromatographic methods can successfully quantify nitrite levels, but these approaches often suffer from complex sample preparation, poor selectivity, expensive instrumentation, necessitate professional operators and time-consuming procedures. These limitations restrict their practical application for detection nitrites in point-of-care testing (POCT). Therefore, developing sensitive and portable nitrite detection methods remains critically important for food safety monitoring.</div></div><div><h3>Results</h3><div>Herein, we developed a novel dual-mode sensing platform based on composite nanozymes PB@MIL-100(Fe)@ATP for sensitive, selective and portable nitrite detection. This platform integrates Prussian Blue with MIL-100(Fe) metal-organic framework and exploits adenosine triphosphate (ATP) as an enhancer. The resulting PB@MIL-100(Fe)@ATP demonstrated excellent peroxidase-like (POD-like) catalytic activity, which catalyzes the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) to form blue-colored oxidized TMB (TMBox) with a characteristic absorption peak at 652 nm. In the presence of nitrites, TMBox specifically undergoes diazotization under acidic conditions to produce yellow diazotized TMB, exhibiting increased absorbance at 450 nm while decreasing at 652 nm. The ratiometric colorimetric assay achieved a detection limit of 0.17 μM within 20 min through absorbance ratio analysis at 652/450 nm. Furthermore, a smartphone-assisted hydrogel sensing method with detection limit of 1.68 μM was developed for point-of-care nitrites monitoring through image capture and color analysis, providing equipment-free operation.</div></div><div><h3>Significance</h3><div>The ATP-enhanced PB@MIL-100(Fe) nanozyme was successfully applied to detect nitrites with high recovery rates in real pickled vegetables, sauerkraut, and sausage samples. This dual-mode platform demonstrated excellent selectivity, high quantitative accuracy, and practical applicability in complex food matrices, providing a simple, rapid and versatile tool for on-site food safety monitoring.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1393 ","pages":"Article 345192"},"PeriodicalIF":6.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116200","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

Combining laser-induced breakdown spectroscopy (LIBS) and time-gated Raman spectroscopy for underwater ores identification 结合激光诱导击穿光谱（LIBS）和时间门控拉曼光谱技术进行水下矿石识别

IF 6 2区化学 Q1 CHEMISTRY, ANALYTICAL

Analytica Chimica Acta

Pub Date : 2026-04-01 Epub Date: 2026-02-06 DOI: 10.1016/j.aca.2026.345204

Jiaojian Song , Ye Tian , Yuanyuan Xue , Qingxi Liu , Pingsai Chu , Jinjia Guo , Yuan Lu , Ronger Zheng

Background

As the land-based mineral deposits are depleting fast, deep-sea metal mineral resources have been proven to have a great mining value. Traditional deep-sea mineral detection techniques require ore samples to be brought back to the laboratory by geological sampling methods for chemical analysis. This approach suffers from substantial time delays and cannot provide real-time, large-scale and rapid feedback during the mining process. Therefore, there is a critical demand for the rapid and in-situ technique of underwater ores identification without requiring the ore samples to be brought back to the laboratory.

Results

We combined LIBS and time-gated Raman spectroscopy for the rapid identification of underwater ores. An integrated LIBS-Raman setup was built based on a same laser and a same spectrometer, to acquire both the elemental and molecular information of ore samples immersed in deionized water. PLS-DA was used to establish the classification model based on the LIBS and Raman spectra. Two data fusion strategies including data-level fusion and feature-level fusion were used for the combination of LIBS and Raman data. The data fusion strategies offer a significant improvement in ores classification compared to using the individual LIBS or Raman data. The data-level fusion model provides the best classification accuracy of 99.11%, while the feature-level fusion model has a slightly lower accuracy of 98.44% but with a much reduced computation time. The feature selection by successive projections algorithm (SPA) involved in the feature-level fusion improves the computing efficiency and the interpretability of the model.

Significance

The present results demonstrated the capability of LIBS and Raman techniques for the rapid identification of underwater ores. The integrated setup that combining LIBS with time-gated Raman spectroscopy based on a same laser source and a same spectrometer could be beneficial for developing down-sizing and low-power consumed underwater devices for the future deep-sea mining applications.

随着陆基矿产资源的快速枯竭，深海金属矿产资源已被证明具有巨大的开采价值。传统的深海矿物探测技术需要通过地质取样方法将矿石样品带回实验室进行化学分析。这种方法存在较大的时间延迟，无法在挖掘过程中提供实时、大规模和快速的反馈。因此，不需要将矿石样品带回实验室的快速原位水下矿石识别技术是一个迫切的需求。结果将LIBS与时间门控拉曼光谱相结合，实现了水下矿石的快速鉴别。基于同一激光器和同一光谱仪，建立了一个集成的LIBS-Raman装置，以获取浸在去离子水中的矿石样品的元素和分子信息。利用PLS-DA建立了基于LIBS和拉曼光谱的分类模型。采用数据级融合和特征级融合两种数据融合策略对LIBS和Raman数据进行融合。与使用单独的LIBS或Raman数据相比，数据融合策略在矿石分类方面提供了显著的改进。数据级融合模型的分类准确率最高，为99.11%，而特征级融合模型的分类准确率略低，为98.44%，但计算时间大大减少。特征级融合中采用逐次投影算法进行特征选择，提高了模型的计算效率和可解释性。意义本研究结果证明了LIBS和拉曼技术在水下矿石快速识别中的能力。将LIBS与基于同一激光源和同一光谱仪的时间门控拉曼光谱相结合的集成装置，可以为未来深海采矿应用开发小型化和低功耗的水下设备。

{"title":"Combining laser-induced breakdown spectroscopy (LIBS) and time-gated Raman spectroscopy for underwater ores identification","authors":"Jiaojian Song , Ye Tian , Yuanyuan Xue , Qingxi Liu , Pingsai Chu , Jinjia Guo , Yuan Lu , Ronger Zheng","doi":"10.1016/j.aca.2026.345204","DOIUrl":"10.1016/j.aca.2026.345204","url":null,"abstract":"<div><h3>Background</h3><div>As the land-based mineral deposits are depleting fast, deep-sea metal mineral resources have been proven to have a great mining value. Traditional deep-sea mineral detection techniques require ore samples to be brought back to the laboratory by geological sampling methods for chemical analysis. This approach suffers from substantial time delays and cannot provide real-time, large-scale and rapid feedback during the mining process. Therefore, there is a critical demand for the rapid and in-situ technique of underwater ores identification without requiring the ore samples to be brought back to the laboratory.</div></div><div><h3>Results</h3><div>We combined LIBS and time-gated Raman spectroscopy for the rapid identification of underwater ores. An integrated LIBS-Raman setup was built based on a same laser and a same spectrometer, to acquire both the elemental and molecular information of ore samples immersed in deionized water. PLS-DA was used to establish the classification model based on the LIBS and Raman spectra. Two data fusion strategies including data-level fusion and feature-level fusion were used for the combination of LIBS and Raman data. The data fusion strategies offer a significant improvement in ores classification compared to using the individual LIBS or Raman data. The data-level fusion model provides the best classification accuracy of 99.11%, while the feature-level fusion model has a slightly lower accuracy of 98.44% but with a much reduced computation time. The feature selection by successive projections algorithm (SPA) involved in the feature-level fusion improves the computing efficiency and the interpretability of the model.</div></div><div><h3>Significance</h3><div>The present results demonstrated the capability of LIBS and Raman techniques for the rapid identification of underwater ores. The integrated setup that combining LIBS with time-gated Raman spectroscopy based on a same laser source and a same spectrometer could be beneficial for developing down-sizing and low-power consumed underwater devices for the future deep-sea mining applications.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1393 ","pages":"Article 345204"},"PeriodicalIF":6.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129703","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

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

Analytica Chimica Acta

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。

{"title":"SP3-PELSA: A Rapid and Sensitive Approach for Studying Protein-Ligand Interaction with Small-Amount Samples","authors":"Jiaqin Chen, Guangxu Hu, Jie Song, Lin Huang, Xumin Zhang","doi":"10.1016/j.aca.2026.345436","DOIUrl":"https://doi.org/10.1016/j.aca.2026.345436","url":null,"abstract":"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.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"86 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506959","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

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

Analytica Chimica Acta

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。

{"title":"Unified Primer Enabled Detection (UPED) system for Magnaporthe oryzae infecting rice: A comparative study from conventional PCR to CRISPR Cas12a based detection systems.","authors":"R. Karan, M.K. Prasannakumar, Harvinder Kour Khera, J. Harish, Swathi.S. Patil, Pramesh Devanna, C. Manjunatha, Rakesh Kumar Mishra","doi":"10.1016/j.aca.2026.345418","DOIUrl":"https://doi.org/10.1016/j.aca.2026.345418","url":null,"abstract":"<h3>Background</h3>Rice blast, caused by <em>Magnaporthe oryzae</em>, 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 <em>M. oryzae</em> detection.<h3>Results</h3>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 <em>Pot2</em> transposon in <em>M. oryzae</em>. Sensitivity assays using 10-fold genomic DNA dilutions (10<sup>9</sup> to 10<sup>-1</sup> copies/reaction) revealed that LAMP-CRISPR and RPA-CRISPR were most sensitive, detecting down to 1 copy/reaction. LAMP and qPCR detected down to 10<sup>2</sup> and 10<sup>3</sup> copies/reaction, while RPA and PCR were limited to 10<sup>5</sup> and 10<sup>6</sup> 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 <em>M. oryzae</em>.<h3>Significance</h3>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 <em>M. oryzae</em> 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.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"93 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506966","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