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Dendritic mixed-mode stationary phases prepared by thiol-epoxy click reaction for the determination of bisphenols in a variety of complex samples 用巯基-环氧树脂咔嗒反应制备树枝状混合模式固定相,用于测定各种配合物样品中的双酚类
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-07 DOI: 10.1016/j.aca.2026.345216
Wuji Shuoti, Ruihan Peng, Xuemei Wang, Qiuxia Liu, Yixin Huang, Lishuo Liu, Yanyu Jiang, Jie Wen, Lian Zhong, Lujun Wang

Background

Bisphenols are widely used in thermal paper, inks, coatings, and other fields. Among them, abnormal concentrations of bisphenol A (BPA) can disrupt the human endocrine system, making it essential to closely monitor BPA levels in environmental and daily life samples. Owing to its strong separation and analytical capabilities, high performance liquid chromatography (HPLC) enables accurate analysis of compounds in complex real-world samples. Among various HPLC stationary phases, dendritic stationary phase materials have attracted significant attention due to their unique branched spatial structure. Therefore, it is of great research importance to continuously investigate dendritic HPLC stationary phases, expand their variety, and broaden their applications.

Results

The novel dendrimer based stationary phase named as Sil-G1-BDDE-TTCA was synthesized by modifying 1,4-butanediol diglycidyl ether and trithiocyanuric acid onto silica surfaces via thiol-epoxy click reaction. Through three repeated grafting, the third-generation stationary phase named as Sil-G3-BDDE-TTCA was prepared. The C18 modified dendrimer based stationary phase named as Sil-G3-BDDE-TTCA-C18 was finally prepared using 1-octadecene as a capping functional monomer. These dendritic stationary phases were characterized by Elemental analysis, Thermogravimetric analysis, Scanning electron microscope and X-ray photoelectron spectroscopy. To evaluate the hydrophobic, hydrophilic, and π-π interactions of the prepared dendritic stationary phases, test mixtures including alkylbenzenes, positional isomers, polycyclic aromatic hydrocarbons, nucleosides, and flavonoids were analyzed. The Tanaka test was employed to compare the chromatographic performance of different stationary phases. Thermodynamic parameters for the retention of alkylbenzenes and positional isomers on these stationary phases were calculated to investigate the effect of temperature on chromatographic behavior. The reproducibility of these prepared dendritic columns was investigated, yielding satisfactory results.

Significance

For the first time, a dendritic mixed-mode stationary phase was fabricated via thiol-epoxy click reaction for detecting bisphenols in actual samples. This strategy overcomes the time-consuming and inefficient synthesis of traditional dendritic phases, offering a novel route for dendritic materials and extending their environmental applications.
双酚类物质广泛应用于热敏纸、油墨、涂料等领域。其中,双酚A (BPA)浓度异常会扰乱人体内分泌系统,因此密切监测环境和日常生活样本中的BPA水平至关重要。由于其强大的分离和分析能力,高效液相色谱(HPLC)能够准确分析复杂样品中的化合物。在各种HPLC固定相中,树枝状固定相材料因其独特的分支空间结构而备受关注。因此,不断研究枝状高效液相色谱固定相,扩大其种类,拓宽其应用领域具有重要的研究意义。结果将1,4-丁二醇二缩水甘油醚和三硫氰尿酸通过巯基-环氧树脂的咔嗒反应修饰在二氧化硅表面,合成了新型树状聚合物固定相Sil-G1-BDDE-TTCA。通过三次重复接枝,制备了第三代固定相Sil-G3-BDDE-TTCA。最后以1-十八烯为封盖单体,制备了C18修饰的枝状大分子固定相Sil-G3-BDDE-TTCA-C18。采用元素分析、热重分析、扫描电镜和x射线光电子能谱等手段对这些枝晶固定相进行了表征。为了评价所制备的树突固定相的疏水、亲水性和π-π相互作用,分析了包括烷基苯、位置异构体、多环芳烃、核苷和黄酮类化合物在内的测试混合物。采用Tanaka法比较不同固定相的色谱性能。计算了烷基苯和位置异构体在这些固定相上保留的热力学参数,以研究温度对色谱行为的影响。对所制备的树突柱的重现性进行了研究,得到了满意的结果。意义首次利用巯基-环氧树脂咔嗒反应制备了树枝状混合模式固定相,用于检测实际样品中的双酚类物质。该策略克服了传统枝晶相合成的耗时和低效,为枝晶材料提供了一条新的途径,并扩展了其在环境中的应用。
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引用次数: 0
SERS Fingerprinting of β2-Agonists for Anti-Doping Based on Au-COF Substrate 基于Au-COF底物的β2抗掺杂激动剂的SERS指纹图谱研究
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-06 DOI: 10.1016/j.aca.2026.345206
Siqing Liu, Liping Chen, Xingju Li, Ruxi Lin, Yunxin Zhang, Xiaojun Luo

Background

β2−agonists, also known as β2−adrenoceptor agonists, are secreted by the adrenal medulla of the animal body and have a characteristic catecholamine structure. When inhaled, the drug rapidly relaxes the smooth muscles of the airways in asthma patients, improves ventilation, and temporarily increases alertness during exercise and helps relieve fatigue. However, the use of β2−agonists to improve physical performance in a short period of time can lead to extreme dependence and irritation, and there are still many unknown hazards. They are now on the World Anti−Doping Organization (WADA) prohibited list.

Results

Surface−enhanced Raman spectroscopy (SERS) can directly detect the characteristic peaks associated with β2−agonist compounds in a fast and sensitive manner. This study is the first to utilize a direct Raman detection technique, achieving successful acquisition of the fingerprint spectra of three target analytes (vilanterol, fenoterol, bambuterol) as well as the establishment of a corresponding fingerprint spectral analysis method. To further improve its performance, in this study, gold nanoparticles were synthesized via redox methods and integrated with covalent organic framework (COF) to construct a novel highly sensitive detection platform for β2−agonists. The Au−COF composite exhibits high adsorption performance and can significantly enhance the SERS signal of the target, thereby achieving low detection limits, including 9.25 × 10−6 g·mL−1 for bambuterol, 9.76 × 10−6 g·mL−1 for vilanterol, and 7.54 × 10−6 g·mL−1 for fenoterol, which makes it promising for improving the overall sensitivity of β2−agonist detection.

Significance

This study develops a novel analytical method utilizing Au−COF composites for highly sensitive SERS detection. It pioneers the application of this strategy in the qualitative and quantitative analysis of trace β2-agonists. The research not only significantly expands the scope of Au−COF composites but also provides a technologically promising approach with substantial practical value for ensuring medical safety through clinical medication monitoring and for detecting banned substances in sports.
β2 -激动剂,也称为β2 -肾上腺素受体激动剂,由动物体内肾上腺髓质分泌,具有特征性的儿茶酚胺结构。吸入后,该药物能迅速放松哮喘患者的气道平滑肌,改善通气,并在运动时暂时提高警觉性,有助于缓解疲劳。然而,使用β2−激动剂在短时间内提高身体机能会导致极度依赖和刺激,并且仍有许多未知的危害。他们现在被列入世界反兴奋剂组织(WADA)的禁止名单。结果表面增强拉曼光谱(SERS)可以快速、灵敏地直接检测到β2−激动剂化合物相关的特征峰。本研究首次利用直接拉曼检测技术,成功获取了维兰特罗、非诺特罗、班布特罗三种目标分析物的指纹光谱,并建立了相应的指纹光谱分析方法。为了进一步提高其性能,本研究通过氧化还原方法合成了金纳米颗粒,并与共价有机骨架(COF)结合,构建了一种新型的高灵敏度β2−激动剂检测平台。Au - COF复合材料具有较高的吸附性能,可显著增强靶物的SERS信号,从而实现较低的检出限,班布特罗为9.25 × 10−6 g·mL−1,维兰特罗为9.76 × 10−6 g·mL−1,非诺特罗为7.54 × 10−6 g·mL−1,这使得它有望提高β2−激动剂检测的总体灵敏度。本研究开发了一种新的分析方法,利用Au - COF复合材料进行高灵敏度的SERS检测。它开创了该策略在痕量β2激动剂的定性和定量分析中的应用。该研究不仅大大扩展了Au - COF复合材料的范围,而且为通过临床药物监测和检测运动中禁用物质来确保医疗安全提供了一种技术上有前景的方法,具有很大的实用价值。
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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 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-06 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。
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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 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub 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":"https://doi.org/10.1016/j.aca.2026.345204","url":null,"abstract":"<h3>Background</h3>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.<h3>Results</h3>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.<h3>Significance</h3>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.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"293 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2026-02-06","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
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 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub 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 operation 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), are 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 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。
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引用次数: 0
A multi-functional effervescent tablet for one-pot effervescent/derivatization/extraction: An integrated strategy for sulfonamide residue analysis 一种一锅泡腾/衍生/提取多功能泡腾片:磺胺残留综合分析策略
IF 6 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-03 DOI: 10.1016/j.aca.2026.345186
Di Chen , Yixin Ma , Xirui Pei , Wenxuan Li , Chenqi Niu , Haobo Zheng

Background

Sulfonamides are extensively used antimicrobials, but residues in food raise health risks such as allergies, antimicrobial resistance, and carcinogenicity. Strict residue limits require sensitive and efficient monitoring methods. While LC-FLD is selective and practical, conventional workflows rely on multi-step extraction and derivatization, which are time-consuming. A streamlined strategy integrating extraction and derivatization into a single operation is needed for practical residue analysis in complex food matrices.

Results

A novel multi-functional effervescent tablet was developed to unify effervescence, derivatization, and extraction in one step. The tablet incorporates effervescent precursors (Na2CO3/NaH2PO4), fluorescamine (a derivatization reagent), Fe3O4 nanoparticles, and hydroxylated multi-walled carbon nanotubes (an adsorbent). Upon immersion, CO2 bubbles promote rapid dispersion of reagents and in-situ assembly of a magnetic composite adsorbent, enabling simultaneous derivatization and efficient extraction of sulfonamides. The core tablet-mediated procedure requires only 4 min, with desorption achieved in 0.5 min using acetone. Validation demonstrated excellent linearity (R2 > 0.998), low detection limits (0.130–0.285 ng/g), and recoveries of 82.6–107.0% with RSDs <10%. Application to spiked honey confirmed accuracy, with relative errors ranging from −8.9% to +9.2%. Comparative studies showed performance equivalent to conventional multi-step protocols, while reducing handling steps and solvent use during the extraction phase.

Significance

This integrated effervescence/derivatization/extraction strategy streamlines sulfonamide residue analysis into a rapid, cost-effective, and easily automatable workflow. While sample pretreatment is still required for complex matrices, the tablet-based step significantly reduces manual handling and solvent consumption during the extraction and derivatization process. Its compatibility with LC-FLD provides a practical and cost-effective alternative to LC-MS, supporting reliable food safety surveillance within regulatory standards.
磺胺是广泛使用的抗菌剂,但食品中的残留会增加健康风险,如过敏、抗菌素耐药性和致癌性。严格的残留限量要求采用灵敏、高效的监测方法。虽然LC-FLD具有选择性和实用性,但传统的工作流程依赖于多步提取和衍生,这非常耗时。在复杂食品基质中进行实际的残留分析需要一种将提取和衍生化整合到单一操作中的流线型策略。结果研制出一种新型多功能泡腾片,使泡腾片的起泡、衍生、提取一步走。该片剂含有泡腾前体(Na2CO3/NaH2PO4)、荧光胺(衍生化试剂)、Fe3O4纳米颗粒和羟基化多壁碳纳米管(吸附剂)。浸泡后,CO2气泡促进试剂的快速分散和磁性复合吸附剂的原位组装,从而实现磺胺类化合物的同时衍生化和高效提取。核心片介导的过程只需要4分钟,使用丙酮在0.5分钟内完成解吸。验证结果表明:线性良好(R2 > 0.998),检出限低(0.130 ~ 0.285 ng/g),加样回收率为82.6 ~ 107.0%,rsd <10%。应用于加标蜂蜜证实了准确性,相对误差范围为-8.9%至+9.2%。对比研究表明,其性能与传统的多步骤方案相当,同时减少了提取阶段的处理步骤和溶剂使用。这种集成的起泡/衍生化/提取策略将磺胺残留分析简化为快速,经济高效且易于自动化的工作流程。虽然复杂的基质仍然需要样品前处理,但基于片剂的步骤显著减少了提取和衍生过程中的人工处理和溶剂消耗。它与LC-FLD的兼容性为LC-MS提供了一种实用且具有成本效益的替代方案,支持在监管标准内可靠的食品安全监测。
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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 Pub 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。
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引用次数: 0
Aptamer Modified NPA Hollow Nanozymes with Intrinsic Peroxidase-Like Activity for Colorimetric Sensing of H1N1 具有内在过氧化物酶样活性的核酸适体修饰的NPA中空纳米酶用于H1N1的比色检测
IF 6.2 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-02 DOI: 10.1016/j.aca.2026.345189
Jianjun Wang, Shuyuan Zhang, Qingqing Wang, Haijiang Gong, Boyu Chen, Qi Liu, Lili Feng, Shili Gai, Piaoping Yang
A colorimetric sensor based on aptamer-functionalized nanozyme probes was successfully developed for the sensitive and specific detection of influenza A (H1N1) virus. In this study, trimetallic nickel-palladium-gold hollow nanozymes (NPA) with excellent peroxidase (POD)-like activity were used as catalytic probes. Compared to the horseradish peroxidase (HRP), the NPA nanozyme exhibits superior peroxidase-like activity, demonstrating a lower Michaelis constant (Km) and a higher maximum reaction rate (Vmax) for the substrates TMB and H2O2, indicating enhanced substrate affinity. Via the gold-sulfur bond interaction, thiol-modified aptamers that could specifically recognize H1N1 hemagglutinin (HA) were immobilized on the nanozyme surface, enabling accurate HA recognition under two detection methods: (1) For the colorimetric biosensor, the binding of HA to the aptamer formed an interfacial steric hindrance layer on the nanozyme surface, which inhibited the catalytic reaction, leading to a significant decrease in absorbance; (2) In the modified ELISA, the "antibody-HA-aptamer" sandwich structure enriched nanozymes at the detection interface, and a color signal enhancement correlated with HA concentration was observed after adding the chromogenic substrate. Experimental results showed that the dual-mode method achieved linear detection ranges of 2–250 ng·mL-1 and 2–62.5 ng·mL-1 for HA protein, with limits of detection (LODs) as low as 1.5 ng·mL-1 and 1.2 ng·mL-1, respectively. This method also exhibited good specificity against other influenza virus subtypes (e.g., H5N1) and was successfully applied to the detection of inactivated H1N1 virus in serum samples. Furthermore, by integrating a smartphone-based colorimetric analysis system, demonstrating its potential for rapid and on-site detection of the H1N1 virus. This work provides a new insight for the development of target-specific nanozyme sensors.
成功研制了一种基于适体功能化纳米酶探针的比色传感器,用于甲型H1N1流感病毒的灵敏和特异性检测。本研究以具有优异过氧化物酶(POD)样活性的三金属镍钯金空心纳米酶(NPA)作为催化探针。与辣根过氧化物酶(HRP)相比,NPA纳米酶表现出更强的过氧化物酶样活性,对底物TMB和H2O2具有更低的米切里斯常数(Km)和更高的最大反应速率(Vmax),表明其对底物的亲和力增强。通过金-硫键相互作用,将巯基修饰的能特异性识别H1N1血凝素(HA)的适体固定在纳米酶表面,通过两种检测方法实现对HA的准确识别:(1)比色生物传感器,HA与适体的结合在纳米酶表面形成界面位阻层,抑制了催化反应,导致吸光度显著降低;(2)在改进后的ELISA中,“抗体-HA-适体”三明治结构在检测界面富集了纳米酶,添加显色底物后观察到与HA浓度相关的颜色信号增强。实验结果表明,双模法对HA蛋白的线性检测范围为2 ~ 250 ng·mL-1和2 ~ 62.5 ng·mL-1,检出限(lod)分别低至1.5 ng·mL-1和1.2 ng·mL-1。该方法对其他流感病毒亚型(如H5N1)也表现出良好的特异性,并成功应用于血清样品中灭活H1N1病毒的检测。此外,通过集成基于智能手机的比色分析系统,展示了其快速和现场检测H1N1病毒的潜力。这项工作为靶向纳米酶传感器的发展提供了新的见解。
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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 Pub 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。
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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 2区 化学 Q1 CHEMISTRY, ANALYTICAL Pub 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
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引用次数: 0
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Analytica Chimica Acta
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