Analytical and Bioanalytical Chemistry最新文献

{"title":"The sensitive detection of low molecular mass peptide drugs in dried blood spots by solid-phase extraction and LC-HRMS.","authors":"Wei Chang, Siyu Yan, Xiya Yan, Zhanliang Wang, Boya Gu, Yunxi Liu, Yufeng Zhang, Sheng Yang","doi":"10.1007/s00216-024-05480-w","DOIUrl":"https://doi.org/10.1007/s00216-024-05480-w","url":null,"abstract":"<p><p>Dried blood spot (DBS) technique has become a new popular topic in anti-doping field in recent years due to its advantages of sample stability and easy operation. It can be employed as a supplementary method to routine urine analysis. However, the small volume of DBS samples (usually 10-20 μL) significantly reduces the application value of this technique. Therefore, the development of sensitive detection methods for the analysis of prohibited substances in DBS is particularly important. In this study, based on the characteristics of low molecular mass peptide (LMMP) drugs, systematic optimization strategies were utilized for the first time to establish a sensitive detection method for LMMPs in DBS. Without using DMSO to enhance mass spectrometry ionization efficiency of peptides, the limits of detection (LOD) ranged between 0.05 and 3.74 ng/mL, significantly better than the previously reported method (0.5-20 ng/mL). This method was validated according to the guidelines of the World Anti-Doping Agency (WADA), and corresponding post-administration study was conducted, demonstrating that the method could be applied to routine analysis of LMMP drugs in DBS. Moreover, since DMSO is not involved, this method also has the potential to simultaneously detect both LMMP and small molecular drugs.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142046136","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":"An advancement of the gravimetric isotope mixture method rendering the knowledge of the spike purity superfluous.","authors":"Lukas Flierl, Olaf Rienitz, Jochen Vogl, Axel Pramann","doi":"10.1007/s00216-024-05465-9","DOIUrl":"https://doi.org/10.1007/s00216-024-05465-9","url":null,"abstract":"<p><p>The gravimetric isotope mixture method is the primary method to determine absolute isotope ratios. This method, however, depends on the existence of suitable spike materials and knowledge of their purities. Determining the purity of the spikes can be tedious and labour-intensive. In this publication, an advancement of the gravimetric isotope mixture method, rendering the determination of the purity of the spike materials unnecessary, is presented. The advancement combines mass spectrometry and ion chromatography leading to an approach being independent of the purity of the spike materials. In the manuscript the mathematical background and the basic idea of the novel approach are described using a two-isotope system like copper or lithium.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142034828","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":"Basic accuracy of a 1D NOESY with presaturation method using standard solutions of amino and maleic acids.","authors":"Naoki Saito","doi":"10.1007/s00216-024-05491-7","DOIUrl":"https://doi.org/10.1007/s00216-024-05491-7","url":null,"abstract":"<p><p>1D NOESY with presaturation (NOESY-presat) is the most popular water suppression method. When D₂O solutions of L-phenylalanine or L-valine were measured using NOESY, the absolute concentration biases increased with longer mixing and evolution times, reaching a maximum of 54% with respect to the preparation values. At mixing and evolution times of 0 ms and 0 µs, respectively, the absolute concentration biases were reduced to less than 3%. The remaining biases were caused by the off-resonance effect, which was prevented by setting the frequency offset to an intermediate value between the analyte and internal standard 3-(trimethylsilyl)-1-propanesulfonic acid-d₆ (DSS-d₆) signals. Nevertheless, NOESY-presat gave maximum absolute biases of 26% and 11% for glycine and maleic acid concentrations, respectively, in three H₂O/D₂O (90/10 vol%) solutions. The proposed NOESY-dual-presat method reduced the absolute biases to below 4%. However, water suppression was insufficient but was improved by setting the frequency offset to the same as the presaturation offset with the H₂O signal, although the absolute biases rose to 5 to 13%. Quantitative analyses using NOESY-presat and NOESY-dual-presat require careful consideration of the off-resonance effect.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142034829","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":"Exploring the manganese-dependent interaction between a transcription factor and its corresponding DNA: insights from gas-phase electrophoresis on a nES GEMMA instrument.","authors":"Ivana Leščić Ašler, Katarina Radman, Zoe Jelić Matošević, Branimir Bertoša, Victor U Weiss, Martina Marchetti-Deschmann","doi":"10.1007/s00216-024-05473-9","DOIUrl":"https://doi.org/10.1007/s00216-024-05473-9","url":null,"abstract":"<p><p>Manganese ion homeostasis is vital for bacteria and is achieved via manganese-dependent transcription factors. Manganese mediation of transcription factor attachment to the corresponding oligonucleotide sequences can be investigated, e.g. via electrophoretic mobility shift assays (EMSA). Formation of specific biocomplexes leads to differences in the migration pattern upon gel electrophoresis. Focusing on electrophoresis in the gas-phase, applying a nano electrospray gas-phase electrophoretic mobility molecular analyzer (nES GEMMA) also known as nES differential mobility analyzer (nES DMA), and on transcription factors (MntR proteins) from Bacillus subtilis and Mycobacterium tuberculosis, we took interest in the gas-phase electrophoresis of the corresponding biospecific complexes. We compared nES GEMMA, separating analytes in the nanometer regime (a few to several hundred nm in diameter) in the gas-phase in their native state according to particle size, to EMSA data. Indeed we were able to demonstrate manganese-mediated attachment of MntR to target genomic sequences with both analytical techniques. Despite some inherent pitfalls of the nES GEMMA method like analyte/instrument surface interactions, we were able to detect the target complexes. Moreover, we were able to calculate the molecular weight (MW) of the obtained species by application of a correlation function based on nES GEMMA obtained data. As gas-phase electrophoresis also offers the possibility of offline hyphenation to orthogonal analysis techniques, we are confident that nES GEMMA measurements are not just complementary to EMSA, but will offer the possibility of further in-depth characterization of biocomplexes in the future.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142016000","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":"Real-time monitoring of voltage-responsive biomolecular binding onto electro-switchable surfaces.","authors":"Nathan E Pringle, Paula M Mendes, Walter F Paxton","doi":"10.1007/s00216-024-05493-5","DOIUrl":"https://doi.org/10.1007/s00216-024-05493-5","url":null,"abstract":"<p><p>Voltage-responsive biosensors capable of monitoring real-time adsorption behavior of biological analytes onto electroactive surfaces offer attractive strategies for disease detection, separations, and other adsorption-dependent analytical techniques. Adsorption of biological analytes onto electrically switchable surfaces can be modelled using neutravidin and biotin. Here, we report self-assembled monolayers formed from voltage-switchable biotinylated molecules on gold surfaces with tunable sensitivity to neutravidin in response to applied voltages. By using electrochemical quartz crystal microbalance (EQCM), we demonstrated real-time switchable behavior of these bio-surfaces and investigate the range of sensitivity by varying the potential of the same surfaces from -400 mV to open circuit potential (+155 mV) to +300 mV. We compared the tunability of the mixed surfaces to bare Au surfaces, voltage inert surfaces, and switchable biotinylated surfaces. Our results indicate that quartz crystal microbalance allows real-time changes in analyte binding behavior, which enabled observing the evolution of neutravidin sensitivity as the applied voltage was shifted. EQCM could in principle be used in kinetic studies or to optimize voltage-switchable surfaces in adsorption-based diagnostics.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142016002","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":"An acidless microwave-assisted wet digestion of biological samples as a greener alternative: applications from COVID-19 monitoring to plant nanobiotechnology.","authors":"Ana Beatriz Santos da Silva, Ketolly Natanne da Silva Leal, Marco Aurélio Zezzi Arruda","doi":"10.1007/s00216-024-05472-w","DOIUrl":"https://doi.org/10.1007/s00216-024-05472-w","url":null,"abstract":"<p><p>Sample preparation in an analytical sequence increases the number of errors, is highly time-consuming, and involves the manipulation of hazardous reagents. Therefore, when an improvement in an analytical method is required, the sample preparation step needs to be optimised or redesigned. Moreover, this step can involve significant toxic reagents and a high volume of waste. In that regard, this study proposes a new procedure based on microwave-assisted wet digestion combining two green strategies: a miniaturised system (with a few microlitres of volume) and the only use of hydrogen peroxide. Three biological samples (human serum, urine, and plant in vitro material) were chosen due to their high potential for disease monitoring, toxicological studies, and biotechnology applications. Several trace elements (Ca, Cd, Co, Cu, Fe, Mg, Mn, Mo, Ni, Se, and Zn) were determined by inductively coupled plasma optical emission spectroscopy and inductively coupled plasma mass spectrometry. For human serum and urine, a certified reference material was used to check for accuracy; the recovery ranged from 72% (Cd, ICP-MS) to 105% (Mg, ICP OES) for serum, while for urine, they varied from 82% (Ni, ICP-MS) to 122% (Zn, ICP-MS). For the soybean callus sample (in vitro plant material), a comparison between the proposed method and the acid digestion method was conducted to evaluate the accuracy, and the results agreed. The detection limits were 0.001-60 µg L^-1 (lowest for Cd), thus demonstrating a suitable sensitivity. Moreover, the decomposition efficiency was demonstrated by determining the residual carbon, and a low amount was found in the final product digested (below 0.8% w v^-1). A green metric approach was calculated for the proposed method, and according to AGREEprep software, it was found to be around 0.4. Finally, the method was applied to urine samples collected in patients with COVID-19 and soybean callus cultivated with silver nanoparticles. This sample preparation method is a new acidless and miniaturised alternative for elemental analysis involving biological samples.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142008008","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":"High-coverage characterization and discovery of molecular markers for quality control of natural fragrant plant extracts using UPLC-HRMS-based untargeted metabolomics.","authors":"Jinfeng Huo, Wei Zhe, Yipeng Zhang, Qianxu Yang, Zhongda Zeng","doi":"10.1007/s00216-024-05478-4","DOIUrl":"https://doi.org/10.1007/s00216-024-05478-4","url":null,"abstract":"<p><p>The chemical components of natural fragrant plant extracts are of high complexity, and the strategies for quality control (QC) and further discovery of fragrance mechanisms still need to be further investigated. This study integrated the strategies and methods of untargeted metabolomics and chemometrics and statistical modeling to attain the goal. The techniques of reversed-phase and HILIC analysis of ultra-performance liquid chromatography-high-resolution mass spectrometry (UPLC-HRMS) were simultaneously used to collect data in both positive and negative ion modes. The pattern analysis of fingerprints and discovery of characteristic molecular markers for QC analysis were comprehensively employed to reach in-depth analysis of the quality variation and discovery of differential molecules among natural fragrant plant extracts. The former uses fingerprint technique to analyze their overall similarities and differences, and the latter comprehensively discovers molecular substances characterizing the chemical characteristics of fragrant extracts with the help of metabolomics and univariate and multivariate methods. The findings are expected to be used as the molecular markers in product manufacturing, sales, and consumption to achieve accurate quality control and recognition of targeted molecules for potential quality monitoring using spectroscopy techniques. In this work, 27 natural fragrant extracts were applied as examples, and their chemical components were comprehensively analyzed with discovery of markers for quality control. After data integration, 1178 molecules were annotated, and 267 differential metabolite molecules with the values of variable importance in the projection (VIP) larger than 1.0 were found. The results show that the method proposed in this work is of great significance for high-coverage analysis, QC marker discovery, and aroma mechanism elucidation, which has potential applications in the areas of food, cosmetics, pharmaceuticals, tobacco, and others.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142016001","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":"Applications of MALDI mass spectrometry in forensic science.","authors":"Camila M de Almeida, Nayara A Dos Santos, Valdemar Lacerda, Xin Ma, Facundo M Fernández, Wanderson Romão","doi":"10.1007/s00216-024-05470-y","DOIUrl":"https://doi.org/10.1007/s00216-024-05470-y","url":null,"abstract":"<p><p>Forensic chemistry literature has grown exponentially, with many analytical techniques being used to provide valuable information to help solve criminal cases. Among them, matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS), particularly MALDI MS imaging (MALDI MSI), has shown much potential in forensic applications. Due to its high specificity, MALDI MSI can analyze a wide variety of compounds in complex samples without extensive sample preparation, providing chemical profiles and spatial distributions of given analyte(s). This review introduces MALDI MS(I) to forensic scientists with a focus on its basic principles and the applications of MALDI MS(I) to the analysis of fingerprints, drugs of abuse, and their metabolites in hair, medicine samples, animal tissues, and inks in documents.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142003291","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":"Analysis of human biological samples using porous graphitic carbon columns and liquid chromatography-mass spectrometry: a review.","authors":"Taís Betoni Rodrigues, Ricardo Leal Cunha, Paulo Emílio Pereira Barci, Álvaro José Santos-Neto, Fernando Mauro Lanças","doi":"10.1007/s00216-024-05458-8","DOIUrl":"https://doi.org/10.1007/s00216-024-05458-8","url":null,"abstract":"<p><p>Liquid chromatography-mass spectrometry (LC-MS) has emerged as a powerful analytical technique for analyzing complex biological samples. Among various chromatographic stationary phases, porous graphitic carbon (PGC) columns have attracted significant attention due to their unique properties-such as the ability to separate both polar and non-polar compounds and their stability through all pH ranges and to high temperatures-besides the compatibility with LC-MS. This review discusses the applicability of PGC for SPE and separation in LC-MS-based analyses of human biological samples, highlighting the diverse applications of PGC-LC-MS in analyzing endogenous metabolites, pharmaceuticals, and biomarkers, such as glycans, proteins, oligosaccharides, sugar phosphates, and nucleotides. Additionally, the fundamental principles underlying PGC column chemistry and its advantages, challenges, and advances in method development are explored. This comprehensive review aims to provide researchers and practitioners with a valuable resource for understanding the capabilities and limitations of PGC columns in LC-MS-based analysis of human biological samples, thereby facilitating advancements in analytical methodologies and biomedical research.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141999186","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":"Carbon-13-isotopomics and metabolomics of fatty acids from triacylglycerols: overcoming the limitations of GC-C-IRMS for short- and medium-acyl chains.","authors":"Tania Mhanna, Mathilde Grand, Anne-Marie Schiphorst, Romain Le Balch, Toufic Rizk, Joseph Bejjani, Gérald S Remaud, Illa Tea","doi":"10.1007/s00216-024-05479-3","DOIUrl":"https://doi.org/10.1007/s00216-024-05479-3","url":null,"abstract":"<p><p>Carbon-13 isotopomics of triacylglycerol (TAG) fatty acids or free fatty acids in biological matrices holds considerable potential in food authentication, forensic investigations, metabolic studies, and medical research. However, challenges arise in the isotopic analysis of short- and medium-chain (C4 to C10) fatty acid methyl esters (SMCFAMEs) through gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). The high volatility of these esters results in losses during their preparation, leading to isotopic fractionation. Moreover, the methoxy group added to acyl chains requires the correction of δ¹³C values, thereby increasing the uncertainty of the final results. Analyzing free fatty acids (FFAs) addresses both issues encountered with SMCFAMEs. To achieve this objective, we have developed a new protocol enabling the isotopomics of individual fatty acids (FAs) by GC-C-IRMS. The same experiment also provides the FA profile, i.e., the relative percentage of each FA in the TAG hydrolysate or its concentration in the studied matrix. The method exhibited high precision, as evidenced by the repeatability and within-lab reproducibility of results when tested on TAGs from both animal and vegetal origins. Compared to the analysis of FAMEs by GC-C-IRMS, the current procedure also brings several improvements in alignment with the principles of green analytical chemistry and green sample preparation. Thus, we present a two-in-one method for ¹³C-isotopomic and metabolomic biomarker quantitation within quasi-universal TAG compounds, encompassing the short- and medium-acyl chains.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142003292","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}