Xiaoqi Shi , Wen Zhu , Qing Zeng , Yao Luo , Zhong Chen , Yanqin Lin
{"title":"Selective-excitation-based method for measurement of NMR relaxation time","authors":"Xiaoqi Shi , Wen Zhu , Qing Zeng , Yao Luo , Zhong Chen , Yanqin Lin","doi":"10.1016/j.aca.2024.343465","DOIUrl":"10.1016/j.aca.2024.343465","url":null,"abstract":"<div><h3>Background</h3><div>Relaxation time provides invaluable insights into the molecular structure, interactions, and dynamics in nuclear magnetic resonance spectroscopy. However, conventional relaxation-time measurement techniques produce inaccurate relaxation times when the spectral peaks overlap because of the narrow chemical-shift range and <em>J</em>-coupled splitting. While the combination of pure-shift methods can solve this issue, they are not widely used due to their inherent drawbacks such as low sensitivity and long acquisition time. There is a great need for a feasible and sensitive method to measure the relaxation time for overlapping peaks. (87).</div></div><div><h3>Results</h3><div>This study proposes a new method that combines selective excitation with a conventional relaxation-time measurement method, named GEM-IR/CPMG, to accurately measure the longitudinal and transverse relaxation times in the samples with overlapping peaks. The method has a similar acquisition time as the conventional method with small sensitivity loss. The feasibility and effectiveness of the method were demonstrated through experiments using three types of samples: 1-bromobutane, a mixture of butanol and butyric acid, and 17β-estradiol. The results show that the relaxation times measured by this method are in general agreement with the results of the conventional method. In addition, to demonstrate the advantages of the method for low-concentration samples, a sample of estradiol at 8 mM was measured with the results obtained matching the high concentration. (125).</div></div><div><h3>Significance</h3><div>The GEM-IR/CPMG method eliminates interference from overlapping peaks in proton relaxation-time measurement and preserves the crucial coupling information of the sample, thus allowing accurate measurement of the relaxation time. Moreover, it selectively excites the spin of interest in a single scan, demonstrating a minor loss of spectral sensitivity and facilitating the measurement of low-concentration samples, making it widely applicable to chemical analyses. (62).</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1335 ","pages":"Article 343465"},"PeriodicalIF":5.7,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684921","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}
{"title":"Construction of Zinc-based metal-organic frameworks for visual ratiometric fluorescence detection of tetracycline","authors":"Yating Zhong, Haocheng Gao, Jingqi Yang, Xinru Wang, Ying Yu, Yujuan Cao, Manli Guo, Bixia Lin","doi":"10.1016/j.aca.2024.343461","DOIUrl":"10.1016/j.aca.2024.343461","url":null,"abstract":"<div><h3>Background</h3><div>Tetracycline (TC) is frequently utilized as additives in animal feed. The misuse can lead to the residue in food and threaten human health.</div></div><div><h3>Results</h3><div>A ratiometric fluorescence method for tetracycline detection is developed based on Zinc-based metal-organic framework (Zn-MOF) materials. A series of Zn-MOFs are synthesized with phthalic acid derivatives as ligand, and their luminescence properties and interaction with tetracycline are investigated. Thereinto, Zn-BDC-OH MOF synthesized with 2-hydroxyterephthalic acid (BDC-OH) as ligand exhibits sensitive fluorescence response to tetracycline. The blue fluorescence of Zn-BDC-OH at 434 nm is quenched by tetracycline due to inner filter effect (IFE), and the green fluorescence of TC at 531 nm is enhanced because of coordination with Zn<sup>2+</sup>. The fluorescence intensity ratio I<sub>531</sub>/I<sub>434</sub> shows a linear relationship with TC concentration in the range of 0.10–40.0 μM with a limit of detection at 79 nM. The fluorescence colors of Zn-BDC-OH MOF change from blue to cyan to green accompanying with increasing TC concentration, which enables the visual and semi-quantitative detection of tetracycline by naked eyes. Moreover, combined with a smartphone, the RGB value of the fluorescence color can be further identified. The ratio (G/B) of green channel to blue channel shows a linear relationship with the TC concentration in the range of 0.25–25.0 μM with a limit of detection at 0.2 μM. Afterwards, Zn-BDC-OH MOF is successfully applied to detect tetracycline in honey, and the results are consistent with those obtained from chromatography.</div></div><div><h3>Significance</h3><div>The established method exhibits great potential for field visualization and rapid detection of tetracycline.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1335 ","pages":"Article 343461"},"PeriodicalIF":5.7,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142690748","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}
Yuzhou Song , Zongyu Hou , Xiang Yu , Weili Yao , Zhe Wang
{"title":"Exploring the impact mechanism of ambient gas properties on laser-induced breakdown spectroscopy to guide the raw signal improvement","authors":"Yuzhou Song , Zongyu Hou , Xiang Yu , Weili Yao , Zhe Wang","doi":"10.1016/j.aca.2024.343464","DOIUrl":"10.1016/j.aca.2024.343464","url":null,"abstract":"<div><h3>Background</h3><div>Laser-induced breakdown spectroscopy (LIBS) has long been regarded as the future superstar for chemical analysis. However, hindered by the fact that the signal source of LIBS is a spatially and temporally unstable plasma that interacts dramatically with ambient gases, LIBS has always suffered from poor signal quality, especially low signal repeatability. Although ambient gases act as one of the most direct and critical factors affecting LIBS signals, a clear understanding on how ambient gas properties impact LIBS signals is still lacking to act as guideline for the signal quality improvement.</div></div><div><h3>Results</h3><div>In this work, the impact mechanism of three main ambient gas properties, including specific heat ratio (<span><math><mrow><mi>γ</mi></mrow></math></span>), molar mass (<span><math><mrow><mi>M</mi></mrow></math></span>), and ionization energy (<span><math><mrow><mi>E</mi></mrow></math></span>) was investigated by ignoring secondary properties, accurately proportioning gas mixtures, and experimental comparative study by applying various plasma diagnosis methods. The results indicate that these three properties impact signal repeatability by impacting the intensity of the back-pressing process within the plasma, where the sound speed determined by <span><math><mrow><mi>γ</mi></mrow></math></span> and <span><math><mrow><mi>M</mi></mrow></math></span> plays an important role. The properties impact the signal intensity by impacting three energy transfer processes in the plasma, including the laser energy absorption, the energy allocation between gas and sample species, and the heat dissipation. Based on the impact mechanism, guidelines of regulating the ambient gas properties to improvement LIBS signal were further provided.</div></div><div><h3>Significance</h3><div>For the first time, the impact mechanism of main ambient gas properties on LIBS signals was clearly and intuitively revealed. The impact mechanism not only provided a deeper understanding of the plasma evolution process but also provided practical guidelines for improving LIBS signal quality, facilitating accurate quantification of the LIBS technique.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1335 ","pages":"Article 343464"},"PeriodicalIF":5.7,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684920","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}
L. Gutierrez-Romero , B. Gallego , E. Blanco , U. Karst , R. Rodríguez , M. Montes-Bayon
{"title":"Single cell combined with laser ablation ICP-MS to study cisplatinum (IV) loaded nanoparticles penetration pathways in osteosarcoma spheroids","authors":"L. Gutierrez-Romero , B. Gallego , E. Blanco , U. Karst , R. Rodríguez , M. Montes-Bayon","doi":"10.1016/j.aca.2024.343462","DOIUrl":"10.1016/j.aca.2024.343462","url":null,"abstract":"<div><h3>Background</h3><div>3D cellular structures have been considered the following step in the evaluation of drugs penetration after 2D cultures since they are more physiologically representative in cancer cell biology. Here the penetration capabilities of Pt (IV)-loaded ultrasmall iron oxide nanoparticles in 143B osteosarcoma multicellular spheroids of different sizes is conducted by a multidimensional quantitative approach. Single cell (SC) and imaging techniques (laser ablation, LA) coupled to inductively coupled plasma-mass spectrometry (ICP-MS) are used to visualize their penetration pathways and distribution in comparison to those of cisplatin.</div></div><div><h3>Results</h3><div>The analysis of Pt in disaggregated individual cells from spheroids shows levels of incorporation dependent on the spheroid surface to volume ratio and considerably higher than those observed for cisplatin. These results in combination with the total Pt determination in the complete spheroids reveal a preferential transcellular incorporation pathway of the Pt(IV)-loaded NPs. Elemental imaging by LA-ICP-MS shows the co—localization of Pt/Fe in hot spots at distances up to 100 μm from the spheroid surface reaching concentrations of Pt up to 200 μg g<sup>−1</sup> when exposed to Pt(IV)-loaded NPs. A more homogeneous distribution all along the spheroid is observed in the cisplatin-treated models.</div></div><div><h3>Significance</h3><div>The multidimensional ICP-MS based analytical methodology developed through this work offers a generalizable approach to quantitatively study the tissue penetration of nano-transported drugs to be applied in the design of nanoparticles with high accumulation at a target site.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1336 ","pages":"Article 343462"},"PeriodicalIF":5.7,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142690750","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Capillary electrophoresis separations with Betaine:Urea, a deep eutectic solvent as the separation medium","authors":"Haoxiang Meng, Sihui Ding, Song Xue, Siyao Liu, Qing Wu, Qi Zhang","doi":"10.1016/j.aca.2024.343467","DOIUrl":"https://doi.org/10.1016/j.aca.2024.343467","url":null,"abstract":"<h3>Background</h3>Capillary electrophoresis (CE) is a highly versatile separation technique widely used in analytical chemistry. Traditionally, CE can be categorized as either aqueous or non-aqueous systems based on the buffer solvents employed. For decades, non-aqueous CE has been predominantly associated with the use of organic solvents, a perception deeply ingrained in the scientific community. However, growing concerns about the health and environmental impacts of these solvents, driven by the principles of green chemistry, have prompted a reevaluation of their use. In response to these concerns, our group recently introduced a deep eutectic solvent (DES), specifically Proline:Urea, as an innovative and eco-friendly separation medium for CE. This approach not only enhances the sustainability of CE separations but also offers a new perspective for the development of innovative CE separation media.<h3>Results</h3>Building on our previous work, here we report the use of the second DES, Betaine:Urea (BU), as a new separation medium that offers further improved performance for CE applications. The DES was systematically characterized, with key physical properties relevant to CE separations, such as thermal properties, viscosity, dielectric constant, Joule heating effect, and UV transmittance, being thoroughly examined. Using a complex sample of 10 structurally similar naphthalene derivatives, we demonstrated the efficiency of BU in capillary zone electrophoresis (CZE) for separating analytes with varying charges (including cations, neutrals, and anions) and sizes. Additionally, we established the first micellar electrokinetic chromatography (MEKC) system in this DES using sodium dodecyl sulfate (SDS) as the surfactant. This system successfully resolved 6 structurally similar neutrals that could not be separated by conventional aqueous SDS-MEKC, highlighting the versatility of this DES-type separation medium. Furthermore, BU showed several advantages over the previously reported DES, Proline:Urea, particularly in terms of stability, viscosity, and Joule heating effects.<h3>Significance</h3>This study holds the potential to challenge the traditional notion that “CE separation media are merely categorized into aqueous and organic solvents”. Given that DESs are “designer” solvents with highly tunable properties and environmentally friendly characteristics, the introduction of BU as a viable alternative to traditional solvents not only expands the media available for CE separations, but also offers a more efficient and potentially more sustainable option for specific analyses.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"135 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684974","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}
{"title":"Dual-CRISPR/Cas12a-assisted RT-RAA visualization system for rapid on-site detection of nervous necrosis virus (NNV)","authors":"Jie Gao , Siyou Huang , Jing Jiang, Qijin Miao, Rui Zheng, Yiling Kang, Wanting Tang, Hongliang Zuo, Jianguo He, Junfeng Xie","doi":"10.1016/j.aca.2024.343469","DOIUrl":"10.1016/j.aca.2024.343469","url":null,"abstract":"<div><h3>Background</h3><div>Nervous necrosis virus (NNV) poses a severe threat to the aquaculture industry, particularly infecting fish fry with devastating mortality rates and inflicting heavy economic losses. Traditional detection methods, such as cell culture and conventional RT-PCR, are not only time-consuming and require specialized laboratory facilities but also hard to eliminate contamination. Rapid and accurate on-site detection methods in aquaculture settings are crucial for effective control of NNV outbreaks in fish farms.</div></div><div><h3>Results</h3><div>This study developed a one-tube visualization system for rapid and precise identification of NNV in a pond-side setting. This system utilizes the dual-clustered regularly interspaced short palindromic repeats (CRISPR)/Cas12a-assisted reverse transcription-recombinase aided amplification (RT-RAA) detection method, employing fluorescence intensity to indicate positive results for easy interpretation by field operators. The key to this system involved the meticulous selection of RT-RAA primer sets and CRISPR RNA (crRNA) primer sets targeting two genes of NNV, the capsid protein (CP) and RNA-dependent RNA polymerase (RdRp), distributing on two particles of genomic sequences. The assay demonstrated a speed and efficiency process within 30 min and a detection limit of 0.5 copies/μL, achieving 100 % accuracy when compared to qRT-PCR. The practical utility and effectiveness were validated by using 32 field samples. The results underscored the simplicity, rapidity, and reliability of the system, confirming its potential as a robust tool for NNV diagnosis in fish farms.</div></div><div><h3>Significance</h3><div>This study introduces the first application of a dual-CRISPR/Cas12a-assisted RT-RAA visualization system for diagnosing NNV infections. The novel approach substantially enhances on-site diagnostic capabilities, offering a rapid, reliable, and cost-effective solution for fish farm operators. This innovation not only streamlines the detection process but also ensures timely intervention, thereby mitigating the impact of NNV on aquaculture.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1335 ","pages":"Article 343469"},"PeriodicalIF":5.7,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684970","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}
Yimin Tang , Shuang He , Xiuwen Wang , Bing Zhao , Xin Jiang , Libin Yang
{"title":"(001) facet-supported TiO2 facet heterojunction with abundant active sites and high-efficiency carrier separation for ultrasensitive SERS detection of antibiotic residues in foods","authors":"Yimin Tang , Shuang He , Xiuwen Wang , Bing Zhao , Xin Jiang , Libin Yang","doi":"10.1016/j.aca.2024.343470","DOIUrl":"10.1016/j.aca.2024.343470","url":null,"abstract":"<div><h3>Background</h3><div>Antibiotic residues in animal-derived foods are seriously threatening human health and have attracted growing public attention. It is very important and valuable to carry out a rapid ultrasensitive detection of antibiotic residues, especially accurate identification based on molecular fingerprints.</div></div><div><h3>Results</h3><div>Here, a (001) facet-supported TiO<sub>2</sub> facet heterojunction with abundant active sites (SF–TiO<sub>2</sub>) was developed as a surface-enhanced Raman scattering (SERS) substrate for ultrasensitive detection of antibiotic residues in milk and honey foods. Exposure of more (001) facets in SF-TiO<sub>2</sub> can not only provide abundant surface-active sites for efficient chemical recognition of target molecules, but also form effective facet heterojunctions to achieve high-efficient carrier separation for charge transfer between substrate and molecule, which are together responsible for ultrasensitive SERS detection of target molecules with an enhancement factor of 1.3 × 10<sup>7</sup>. The detection limit of enrofloxacin, enoxacin, ciprofloxacin and chloramphenicol residues in milk or honey reaches to 10<sup>−10</sup>-10<sup>−9</sup> M, far lower than the EU standard. And, a simultaneous identification of multi-component residues in foods can be realized. The developed substrate exhibits excellent stability, anti-interference ability, and recyclability in the actual detection.</div></div><div><h3>Significance</h3><div>This work not only provides a novel SERS method for ultrasensitive detection of antibiotic residues in animal-derived foods, but also provides new ideas and concepts for the development of new-type semiconductor SERS substrates and their practical application.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1335 ","pages":"Article 343470"},"PeriodicalIF":5.7,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684971","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}
{"title":"Polypeptide functionalized gold nanoprobes for SERS-fluorescence detection and imaging of caspase-9 during apoptosis","authors":"Xiaoyuan Ma , Yue Pan , Xichi Lin , Zhouping Wang","doi":"10.1016/j.aca.2024.343458","DOIUrl":"10.1016/j.aca.2024.343458","url":null,"abstract":"<div><h3>Background</h3><div>Deoxynivalenol is one of the common fungal toxins in processed grain foods. It has the characteristic of high temperature resistance. Dietary intake of DON contaminated food can cause adverse symptoms. Its cytotoxicity is mainly associated with the expression of apoptosis and interfering with protein synthesis. Among which, caspase family proteases play a crucial role in different types of apoptosis signaling pathways. Thus, it is important to develop a platform for real-time and in situ monitoring of caspase in living cells.</div></div><div><h3>Results</h3><div>In this paper, a polypeptide functionalized gold nanoprobe was designed for real-time and in situ detection of caspase-9 in living cells during DON induced apoptosis. Highly anisotropic gold nanostars (AuNSs) with good LSPR effect were synthesized. It could either serve as the surface enhanced Raman scattering (SERS) substrate or quench fluorescence through fluorescence resonance energy transfer (FRET). Polypeptide containing the LEHD (Leu-Glu-His-Asp) sequence was connected to AuNSs through Au–S bonds. During DON induced cell apoptosis, caspase-9 was activated, which could specifically cleave the recognition site LEHD, causing the polypeptide chain modified with Rhodamine B (Rb) signal group to fall off and move away from AuNSs, ultimately reducing the SERS signal and enhancing the fluorescence signal in the system. The experimental results showed that the nanoprobe had high sensitivity, with a linear range of 5 ng/mL to 400 ng/mL and a minimum detection limit of 0.38 ng/mL.</div></div><div><h3>Significance</h3><div>This method achieved dual signal quantification and visualization imaging of fluorescence and SERS for caspase-9 in living cells. The application of nanomaterials has been broadened and the assay was well versatile in different human cell lines. It provided a new platform in studying the relationship between food safety and cellular homeostasis mechanisms.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1335 ","pages":"Article 343458"},"PeriodicalIF":5.7,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678801","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}
Andong Xue , Linlin Kong , Jialin Li , Yuxin Jiao , Zhishang Hu , Bin Fu , Guibin Wang , Wanjun Zhang , Jianheng Li , Weijie Qin
{"title":"Comprehensive host cell proteins profiling in biopharmaceuticals by a sensitivity enhanced mass spectrometry strategy using TMT-labeling and signal boosting","authors":"Andong Xue , Linlin Kong , Jialin Li , Yuxin Jiao , Zhishang Hu , Bin Fu , Guibin Wang , Wanjun Zhang , Jianheng Li , Weijie Qin","doi":"10.1016/j.aca.2024.343445","DOIUrl":"10.1016/j.aca.2024.343445","url":null,"abstract":"<div><h3>Background</h3><div>Host Cell Proteins (HCPs) are impurities expressed in host cells during the biopharmaceutical production process, whichmay compromise product quality and potentially leading to immunogenic reactions or other adverse effects. Mass spectrometry (MS)-based strategy is more and more considered as a promising method for HCPs analysis, since it is capable of simultaneously quantifying thousands of proteins in a single test. However, considering the large excess biopharmaceutical product protein present in the system and the extremely low abundance of HCPs, sensitive MS methods are urgently needed in HCPs analysis.</div></div><div><h3>Results</h3><div>In this work, we introduced a novel approach that leveraged host cell lysate as a boosting channel to enhance the MS signal of the residue HCPs in biopharmaceutical products using isobaric TMT labeling, thereby elevating the low-abundant HCPs to detectable and quantifiable levels of current MS without using enrichment or depletion method to avoid disturbance of the original concentration of the HCPs. Our method surpassed previous benchmarks by identifying a significantly higher number (23844 unique peptides for 3475 proteins) compared to existing records (4541 unique peptides for 848 proteins) for HCPs analysis in RM8671 NIST monoclonal antibody (mAb), demonstrating unparalleled sensitivity and robustness. Furthermore, our workflow successfully identified 44 of 48 UPS1 proteins across a concentration range of 0.32–4.15 ppm in monoclonal antibodies (mAbs), proving its effectiveness for in-depth HCPs analysis in biopharmaceuticals.</div></div><div><h3>Significance</h3><div>Present even at sub-ppm levels, HCPs may compromise the stability and safety of product proteins and alter pharmacokinetics or neutralization of therapeutic effects. Our MS signal enhancing method presented an advancement in HCP analysis, combining improved sensitivity and increased scale of HCPs with a streamlined and robust workflow. This method allowed HCPs quantification at <1 ppm level without disturbance of the original HCPs concentration, which is still rare in the field.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1335 ","pages":"Article 343445"},"PeriodicalIF":5.7,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678803","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}
Nuria Guijarro-Ramírez , Iraide Sáez-Zamacona , Daniel Torregrosa , Guillermo Grindlay , Luis Gras , Carmen Pire , Juan Mora , Rosa María Martínez-Espinosa
{"title":"Characterization of biogenic selenium nanoparticles in hypersaline media by single particle inductively coupled plasma mass spectrometry: Haloferax mediterranei case","authors":"Nuria Guijarro-Ramírez , Iraide Sáez-Zamacona , Daniel Torregrosa , Guillermo Grindlay , Luis Gras , Carmen Pire , Juan Mora , Rosa María Martínez-Espinosa","doi":"10.1016/j.aca.2024.343453","DOIUrl":"10.1016/j.aca.2024.343453","url":null,"abstract":"<div><h3>Background</h3><div>Single particle inductively coupled plasma mass spectrometry (spICP-MS) is extensively employed for the characterization of biogenic selenium nanoparticles (SeNPs) produced by mesophilic microorganisms. Nevertheless, because halophilic microorganisms are also well-known to produce SeNPs, further research efforts are required to investigate spICP-MS applicability for characterizing such nanomaterials in hypersaline media. The goal of this work is to develop a methodology for characterizing SeNPs in hypersaline media by spICP-MS. To this end, plasma operating conditions, non-spectral interferences and calibration strategies were investigated. The proposed method was employed to investigate the capabilities of the halophilic archaea <em>Haloferax mediterranei</em> to produce SeNPs.</div></div><div><h3>Results</h3><div>By the appropriate selection of experimental conditions, SeNPs can be accurately analyzed in hypersaline media by spICP-MS. Unlike previous works in the literature, no differences in ionic signal were observed between SeNPs and dissolved Se and, hence, there is no need to apply any empirical corrector factor for obtaining accurate particle size distributions. Non-spectral interferences are mitigated by diluting the sample at least 1:10<sup>3</sup> which allows the use of water standards. Size (30 nm) and particle (7 × 10<sup>5</sup> particles mL<sup>−1</sup>) detection limits were low enough to characterize biogenic SeNPs produced by halophilic microorganisms. The use of the optimized methodology reveals that <em>Haloferax mediterranei</em> can produce SeNPs when it is exposed to selenite up to 1 mM, but no formation is produced for selenate exposure. Depending on incubation parameters (selenite concentration and time), the particle median diameter ranged from 80 to 100 nm, whereas particle concentration varied from 0.8 to 1.9 × 10<sup>13</sup> particles mL<sup>−1</sup>.</div></div><div><h3>Significance</h3><div>This represents the first methodology for characterizing biogenic SeNPs in hypersaline media by spICP-MS with accuracy and precision using non-matrix matched standards. It opens the opportunity to investigate the capabilities of halophilic microorganisms (e.g., <em>H. mediterranei</em>) to produce Se-based nanomaterials.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1335 ","pages":"Article 343453"},"PeriodicalIF":5.7,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678841","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}