Analytical Methods最新文献

{"title":"Qualitative and quantitative analysis of metronidazole formulations using a low-cost near infrared transmission spectrophotometer and chemometric tools†","authors":"Moussa Yabré, Abdoul Karim Sakira, Moumouni Bandé, Kouka Luc Delma, Isaïe Nyamba, Loconon Y. Achille Yemoa, Souleymane Fofana and Touridomon Issa Somé","doi":"10.1039/D4AY02251C","DOIUrl":"10.1039/D4AY02251C","url":null,"abstract":"<p >For effective drug quality control and detection of falsified and substandard medicines in developing countries, there is an urgent need to develop reliable, rapid, and inexpensive analytical methods. In this work, a methodology combining a low-cost near infrared transmission spectrophotometer with chemometrics and sample analysis in solution has been applied to develop qualitative and quantitative methods to analyze metronidazole in various formulations. To achieve this, calibration and validation solution samples of metronidazole at different concentrations were prepared. The qualitative method consisted of building a model based on a data driven soft independent modeling of class analogy using metronidazole samples at the concentration of 100 mg L<small>⁻¹</small> as the target class. The built model allowed a satisfactory identification of metronidazole at the target concentration and a clear discrimination of the excipient mixture and metronidazole samples at other concentration levels and related active pharmaceutical ingredients used to mimic falsified and substandard drugs. The quantitative method was based on a partial least squares regression model allowing the quantification of metronidazole in the concentration range of 50–125 mg L<small>⁻¹</small>. The regression model was fully validated according to the accuracy profile methodology. Both qualitative and quantitative methods were successfully employed to analyze various metronidazole tablet samples collected in Burkina Faso. The obtained outcomes underline the feasibility of using these economically accessible portable spectrophotometers as a first line screening tool for drug quality control and detection of falsified and substandard drugs in developing countries.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 10","pages":" 2312-2320"},"PeriodicalIF":2.7,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143456314","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Radical-triggered ring-opening of aminocyclopropane for detection of hydroxyl radicals in living cells†","authors":"Shiqi Jin, Wang Qian, Ruiyang Suo, Yi Li, Huan Ling, Shuqi Li, Kai Deng, Yongchang Wei, Bo Wu and Huaixia Chen","doi":"10.1039/D4AY02150A","DOIUrl":"10.1039/D4AY02150A","url":null,"abstract":"<p >Hydroxyl radicals (˙OH), highly reactive oxygen species involved in oxidative stress and cancer therapy, are challenging to detect intracellularly due to their short lifetime, low concentration, and high reactivity. To address this, a novel ˙OH-specific fluorescent probe, <strong>CC-7</strong>, was developed by integrating an aminocyclopropane group into a coumarin derivative. This design was inspired by the radical-mediated ring-opening of aminocyclopropanes in synthetic chemistry. The ring-opening reaction triggered by ˙OH in <strong>CC-7</strong> produces a significant “Fluorescence-ON” response with a 10-fold increase in intensity, demonstrating high selectivity for ˙OH over other reactive oxygen species. <strong>CC-7</strong> effectively visualized intracellular ˙OH, distinguished between normal (HEK-293T) and cancer cells (4T1), and monitored ˙OH generated by chemotherapeutic agents like doxorubicin and cisplatin. This study highlights <strong>CC-7</strong> as a powerful tool for selectively detecting ˙OH in living cells, with potential applications in investigating oxidative stress-related diseases and monitoring cancer therapy.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 8","pages":" 1892-1899"},"PeriodicalIF":2.7,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143381173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fluorogenic selective detection of Zn2+ using a pyrazole-ortho-vanillin conjugate: insights from DFT, molecular docking, bioimaging and anticancer applications†","authors":"Malavika S. Kumar, Sourav Pakrashy, Sounik Manna, Sujata Maiti Choudhury, Bhriguram Das, Abhishek Ghosh, Asiful H. Seikh, Malay Dolai and Avijit Kumar Das","doi":"10.1039/D4AY02218A","DOIUrl":"10.1039/D4AY02218A","url":null,"abstract":"<p >A fluorescent sensor, (<em>E</em>)-<em>N</em>′-(2-hydroxy-3-methoxybenzylidene)-3,5-dimethyl-1<em>H</em>-pyrazole-1-carbohydrazide (<strong>HMPC</strong>), was designed and synthesized for the selective fluorescence recognition of Zn<small>²⁺</small> in semi-aqueous media. Notably, <strong>HMPC</strong> exhibited a red-shifted, two-fold fluorescence “turn-on” enhancement in response to Zn<small>²⁺</small> at 490 nm, with a detection limit of 1.68 μM, which is significantly lower than the WHO guideline (76.0 μM). The binding constant of <strong>HMPC</strong> with Zn<small>²⁺</small> was calculated to be 5 × 10<small>⁴</small> M<small>⁻¹</small>. The fluorescence enhancement of <strong>HMPC</strong> in the presence of Zn<small>²⁺</small> is attributed to the suppression of the PET process and the enhancement of ICT, leading to fluorescence <em>via</em> the CHEF mechanism. The sensing mechanism was demonstrated through UV-vis, fluorescence spectroscopy, Job plots, ESI-MS, and DFT calculations. For biological applications, cytotoxicity and cell imaging studies were performed using MCF-7 cells. Molecular docking studies revealed a high binding energy of <strong>HMPC</strong> (Δ<em>G</em> = −7.1 kcal mol<small>⁻¹</small>) with the 4,5-diaryl isoxazole HSP90 chaperone protein, suggesting its potential as an anticancer agent. Additionally, its binding energy of −6.5 kcal mol<small>⁻¹</small> with the HDAC8 protein indicates greater efficacy than suberoylanilide hydroxamic acid (SAHA) in inhibiting HDAC, as it binds more strongly to the HDAC8 protein than SAHA (−7.4 kcal mol<small>⁻¹</small>). Furthermore, due to its favorable ADME profile, <strong>HMPC</strong> may be suitable for oral administration, enhancing its potential as an anticancer drug.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 9","pages":" 2125-2133"},"PeriodicalIF":2.7,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ay/d4ay02218a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143412429","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Excitation–emission matrix spectroscopy coupled with chemometrics for monitoring ozonation of olive oil and olive pomace oil†","authors":"Paula Domínguez-Lacueva, Ewa Sikorska and María J. Cantalejo-Díez","doi":"10.1039/D4AY02267J","DOIUrl":"10.1039/D4AY02267J","url":null,"abstract":"<p >The effects of ozonation on the Total Polyphenol Content (TPC) of olive oils remain largely unexplored, despite the significant role that polyphenols play in enhancing the health benefits and quality of these oils. Understanding how ozone treatment impacts phenolic compounds is vital, especially considering the documented negative effects of thermal and photochemical oxidation on TPC. The aim of this study was to explore the use of fluorescence spectroscopy combined with chemometrics to develop multivariate models for monitoring the effects of ozonation on TPC and key physicochemical parameters such as the peroxide index (PI), acidity index (AI), iodine value (IV) and viscosity (<em>V</em>) in both, virgin and pomace olive oils. Parallel factor analysis and principal component analysis of fluorescence excitation–emission matrices (EEMs) of ozonated olive oils revealed that as the ozonation process progressed, TPC and fluorescence emission decreased. And, at the same time, ozonation increased the values of oxidation indicators such as PI, AI, viscosity and intensity of the Rayleigh scattering signal. PLS models based on analysis of unfolded EEMs exhibited good predictive performance for PI (<em>R</em><small>²</small> = 0.822; RPD &gt; 2.5), and moderate for TPC and V (<em>R</em><small>²</small> = 0.792 and 0.753; RPD &gt; 2). In summary, we demonstrated the feasibility of EEM spectroscopy for monitoring the ozonation process. The use of this method can ease the characterization of ozonated olive oils and, additionally, make the analysis more sustainable.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 8","pages":" 1860-1869"},"PeriodicalIF":2.7,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ay/d4ay02267j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143363284","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A photo-elutable 8–17 DNAzyme labeling and PCR-free colorimetric quantification strategy for 5-hydroxymethylcytosine in mammalian genomic DNA†","authors":"Mingfeng Lai, Shitao Lu, Bao Huang, Yanfeng Nie, Xu Wang, Jiaying Xiong and Zhenning Yu","doi":"10.1039/D5AY00111K","DOIUrl":"10.1039/D5AY00111K","url":null,"abstract":"<p >We developed a PCR-free, cost-effective colorimetric assay using gold nanoparticles (AuNPs) to quantify 5-hydroxymethylcytosine (5hmC) without expensive MS instruments or antibodies. This method employs a photo-elutable 8–17 DNAzyme label specific to 5hmC sites, achieving accuracy comparable to ELISA when measuring 5hmC levels in various ICR mouse tissues.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 8","pages":" 1749-1753"},"PeriodicalIF":2.7,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143381148","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Analysis of phosphorylation site occupancy of peptides based on a chemical derivatization method†","authors":"Xingdan Wang, Zhenghu Min, Xiaoqiu Yang, Qiwei Zhang and Qi Zheng","doi":"10.1039/D4AY02208D","DOIUrl":"10.1039/D4AY02208D","url":null,"abstract":"<p >Phosphorylation represents one of the most pervasive and meaningful post-translational modifications of proteins. The analysis of phosphorylation site occupancy is of great importance for elucidating protein function and disease mechanisms. Nevertheless, the direct mass spectrometric analysis of modification occupancy remains a significant challenge. In this study, a two-step derivatization method was employed in conjunction with liquid chromatography-tandem mass spectrometry for the examination of the phosphorylation site occupancy of peptides. The derivatization resulted in the specific labeling of phosphorylation sites and served to reduce the discrepancy in charge properties between phosphorylated and non-phosphorylated peptides, which is advantageous for their simultaneous detection. The occupancies of multiple sites from bovine casein and goldfish tissues were successfully estimated, confirming the usefulness and reproducibility of the method in the analysis of complex biological samples. Furthermore, the application of this method allowed for the observation of peptides with low occupancy, as well as peptides with markedly different occupancy levels between fish tissues. These results suggest that this methodology may be employed as a specialized analytical technique for site occupancy studies, thereby facilitating the investigation of the regulatory mechanisms that govern protein phosphorylation in biological processes.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 8","pages":" 1923-1929"},"PeriodicalIF":2.7,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143381151","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Elastic scattering spectrum fused with Raman spectrum for rapid classification of colorectal cancer tissues†","authors":"Yanfeng Li, Shenjie Ji, Luyao Ma, Yuchi Shen, Guanghua Yuan, Jingyi Bian, Bin Liu, Fan Meng, Nongyue He and Chao Wang","doi":"10.1039/D4AY02221A","DOIUrl":"10.1039/D4AY02221A","url":null,"abstract":"<p >Currently, HE staining and microscopic imaging are the main approaches for the diagnosis of cancerous tissues, which are inefficient, and the results are heavily dependent on doctors' experience. Therefore, establishing a rapid and accurate method for identifying cancerous tissues is of great value for the preoperative and intraoperative assessments. Raman spectroscopy is a non-destructive, label-free and highly specific method, and it has been widely reported in cancer tissue research. However, the low accuracy of Raman spectral results due to the complex compositions of the tissues limits the clinical applications of Raman spectroscopy. In this study, two-dimensional features of the biochemical composition and morphological structure were combined to classify colorectal cancer tissue by innovatively fusing the elastic scattering spectrum and Raman spectrum. In this study, the elastic scattering spectrum and Raman spectrum of 20 clinical colorectal tissues were acquired using a Raman spectrometer and a homemade elastic scattering light device. After multi-modal spectrum data processing and fusion, a composite AI model called spec-transformer was trained and tested. The results showed that the new model classified colorectal tissues with an accuracy of ≥97%. Moreover, Grad-CAM technology was applied to analyse the compositional variation between normal and colorectal cancer tissues, and it demonstrated a high expression of tryptophan and unsaturated fatty acids in cancer tissues with a reduction in tyrosine and beta-carotene expression. Our approach has potential for colorectal cancer diagnosis and could be extended for diagnosis and research on other cancers.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 9","pages":" 2029-2037"},"PeriodicalIF":2.7,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439408","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An Ag-nanoplate decorated cavity-nanorod array SERS substrate for trace detection of PCB-77†","authors":"Jinran Chen, Xiurui Ke, Zhou Zhou, Wenqi Ye, Hong Liu, Wei Zhang and Xiaohong Liu","doi":"10.1039/D5AY00025D","DOIUrl":"10.1039/D5AY00025D","url":null,"abstract":"<p >We report the fabrication of a substrate with cavity-nanorods and decorated with Ag-nanoplates (C-NR@Ag). The cavities on the substrate are formed by metal assistant chemical etching, and the Ag-nanoplates in the cavities by galvanic cell deposition enhance the SERS performance effectively. Analytes in solution are adsorbed on Ag-nanoplates and located in hot spots, which enhance the SERS performance effectively. The enhancement factor of the Ag-nanoplates decorated on nanorod cavities is calculated to be 3.6 × 10<small>⁶</small>, which is about 3 fold higher than that on the nanorods. The C-NR@Ag substrate is able to detect polychlorinated biphenyls (PCBs) with the lower limit of detection at 1.0 × 10<small>⁻¹²</small> M. Additionally, due to the semi-volatile nature of PCB-77, the lower limit of detection of the C-NR@Ag substrate for PCB-77 was 1.0 × 10<small>⁻¹¹</small> M by the non-contact collection method. These results present a novel approach towards enhancing SERS performance and facilitating the rapid detection of PCB-77.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 9","pages":" 2161-2170"},"PeriodicalIF":2.7,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143432049","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Low-cost and portable 3D-printed sensor for the determination of secnidazole in pharmaceutical and seized drug samples†","authors":"Isabella C. O. F. Silva, Raquel G. Rocha, Thiago C. Oliveira, Mariana C. Marra, Luciano C. Arantes, Wallans T. P. dos Santos, Rodrigo A. A. Muñoz and Eduardo M. Richter","doi":"10.1039/D4AY02096K","DOIUrl":"10.1039/D4AY02096K","url":null,"abstract":"<p >Additive manufacturing (3D printing), particularly fused deposition modeling (FDM), has rapidly advanced, offering customized designs, reduced waste, lower costs, and fast prototyping for electroanalytical applications. Herein, the electrochemical secnidazole (SCZ) behavior was studied using additive manufactured electrodes (AMEs) based on commercial carbon black and polylactic acid (PLA) conductive filament. Before use, AMEs were submitted to electrochemical/chemical activation (+1.4 V and −1.0 V, both for 200 s) in basic medium (0.5 mol L<small>⁻¹</small> NaOH). Under optimized square wave voltammetry (SWV) conditions and using 0.12 mol L<small>⁻¹</small> Britton Robinson buffer (pH = 2.0) as supporting electrolyte, SCZ exhibited excellent linearity within the concentration range of 2.5 to 250.0 μmol L<small>⁻¹</small> (<em>R</em><small>²</small> = 0.998). The proposed method was successfully applied to detect and quantify SCZ in pharmaceutical and seized samples. The obtained results were statistically similar (95% confidence level) to the values obtained by HPLC. These findings demonstrate that the 3D-printed electrodes developed in this study provide a cost-effective, facile, and highly sensitive platform for on-site SCZ analysis, presenting significant potential for future forensic applications.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 9","pages":" 2038-2045"},"PeriodicalIF":2.7,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143389526","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Preconcentration-enhanced electrochemical detection of paraoxon in food and environmental samples using reduced graphene oxide-modified disposable sensors†","authors":"Rafael L. Zamboni, Cristiane Kalinke, Luís M. C. Ferreira, Maurício A. P. Papi, Elisa S. Orth, Craig E. Banks, Luiz H. Marcolino-Júnior and Márcio F. Bergamini","doi":"10.1039/D4AY02240H","DOIUrl":"10.1039/D4AY02240H","url":null,"abstract":"<p >Organophosphates, such as paraoxon, are widely used as insecticides in agriculture, making their detection in environmental and food samples crucial due to their high toxicity. This study presents the development of an electrochemical sensor for the detection of paraoxon, using a screen-printed carbon electrode (SPCE) modified with electrochemically reduced graphene oxide (rGO). The modification enhanced the sensor's electrical conductivity and electrochemical performance. A novel preconcentration approach, involving potential pulses at −1.0 and 0.0 V, was employed to improve the adsorption of paraoxon on the electrode surface. Detection was performed by square wave voltammetry, and under optimized conditions, the rGO-SPCE sensor exhibited a linear range from 1.0 to 30 μmol L<small>⁻¹</small>, with detection and quantification limits of 0.26 and 0.86 μmol L<small>⁻¹</small>, respectively. The sensor demonstrated excellent repeatability (RSD = 4.22%), reproducibility (RSD = 7.14%), and selectivity (RSD &lt; 9.22%). The method was successfully applied to tap water, grape and apple juices, and canned corn water samples, achieving recoveries of approximately 98% at the lowest concentration (1.0 μmol L<small>⁻¹</small>) with minimal matrix effects. This approach offers a simple, low-cost, and rapid method for paraoxon detection in water and food samples.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" 9","pages":" 2214-2223"},"PeriodicalIF":2.7,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439409","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}