Review
Biochemical Research Methods
Lanaia Itala Louzeiro Maciel, Ricardo Alves Bernardo, Rafael Oliveira Martins, Almir Custodio Batista Jr, Joao Victor Ataide Oliveira, Andrea Rodrigues Chaves, Boniek Gontijo Vaz
Summary: The imaging of biological tissues using mass spectrometry imaging (MSI) techniques allows for the visualization of the distribution of various metabolites, drugs, lipids, and glycans in complex samples. MSI methods like DESI-MSI and MALDI-MSI provide high sensitivity and the ability to evaluate/visualize multiple analytes in a single sample, overcoming limitations of classical microscopy techniques. This review discusses the application of DESI-MSI and MALDI-MSI in evaluating exogenous and endogenous molecules in biological samples, providing technical insights and recent research findings.
ANALYTICAL AND BIOANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ouyang Dan, Chuanzhe Wang, Chao Zhong, Juan Lin, Gang Xu, Guane Wang, Zian Lin
Summary: In this study, novel LDI-MS substrates were designed to enhance the sensitivity of mass signals and achieve high accuracy diagnosis of different saccharides and central precocious puberty (CPP).
Article
Materials Science, Multidisciplinary
Jean-Arthur Amalian, Tathagata Mondal, Evgeniia Konishcheva, Gianni Cavallo, Benoit Eric Petit, Jean-Francois Lutz, Laurence Charles
Summary: Sequence-defined synthetic polymers are being used as a medium to store information at the molecular level, with low storage capacity of readable chains being a current limitation. Ordering short oligomers on surfaces to compose long messages is an attractive alternative, and desorption electrospray ionization (DESI) is shown to be suitable for bidimensional data storage.
ADVANCED MATERIALS TECHNOLOGIES
(2021)
Article
Biochemistry & Molecular Biology
Sangwon Cha, Gyouwoong Jun, Yougyeong Park, Sung Jun An, Donghoon Lee
Summary: Nanospray desorption electrospray ionization (nano-DESI) was used to analyze the metabolite fingerprints on Hypericum leaves. The intensity changes of key metabolites over time were observed through full mass scan experiments and monitored using selected ion monitoring and pseudo-selected reaction monitoring experiments. The correlation between the time-dependent changes in the metabolite fingerprints and depth-wise metabolite distribution was examined by removing the surface layers of the leaves multiple times.
Article
Chemistry, Analytical
Fengjian Chu, Gaosheng Zhao, Wangyu Li, Wei Wei, Weiwei Chen, Zihan Ma, Zhan Gao, Nazifi Sani Shuaibu, Jikui Luo, Bingwen Yu, Hongru Feng, Yuanjiang Pan, Xiaozhi Wang
Summary: A microwave plasma torch-based ion/molecular reactor (MPTIR) has been developed for creating and monitoring rapid oxidation reactions without the addition of external oxidants or catalysts. The oxidation products from the MPTIR match those of the long-term environmental oxidative process, and two unreported environmental compounds were identified in actual water samples using this device.
ANALYTICAL CHEMISTRY
(2022)
Review
Pharmacology & Pharmacy
Manman Qin, Yuqing Qian, Lu Huang, Chao Zhong, Mingdong Li, Jun Yu, Huanwen Chen
Summary: Extraction electrospray ionization mass spectrometry (EESI-MS) enables effective ionization of trace molecules in complex samples without sample pretreatment, providing high sensitivity, selectivity, and response speed. It also allows for advanced functionalization of high-energy molecular species. This article systematically reviews the effects of operating conditions on the analytical performance of EESI-MS for various pharmaceutical compounds and introduces its potential application in molecular functionalization for drug discovery.
FRONTIERS IN PHARMACOLOGY
(2023)
Article
Biochemistry & Molecular Biology
Margaux Fresnais, Siwen Liang, Deniz Seven, Nevena Prodanovic, Julia Sundheimer, Walter E. Haefeli, Juergen Burhenne, Remi Longuespee
Summary: The development and validation of desorption/ionization mass spectrometric assays for drug quantification in tissue sections is crucial for their widespread application in (clinical) pharmacology. Advances in desorption electrospray ionization have demonstrated its usefulness for developing targeted quantification methods that meet validation requirements. Factors such as desorption spot morphology, analytical time, and sample surface need to be considered for successful method development. This study highlights the importance of considering desorption kinetics during DESI analyses, which can help reduce analytical time, verify solvent-based drug extraction methods, and predict feasibility of imaging assays. These findings provide valuable guidance for future development of validated DESI-profiling and imaging methods.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Review
Chemistry, Analytical
Katerina V. Djambazova, Jacqueline M. Van Ardenne, Jeffrey M. Spraggins
Summary: Imaging mass spectrometry allows for the untargeted mapping of biomolecules directly from tissue sections, with widespread clinical applicability in disease diagnosis and classification. This review summarizes the two most widely employed IMS technologies and their advancements in biomedical applications.
TRAC-TRENDS IN ANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Medicinal
Margaux Fresnais, Siwen Liang, Marius Breitkopf, Joshua Raoul Lindner, Emmanuelle Claude, Steven Pringle, Pavel A. Levkin, Konstantin Demir, Julia Benzel, Julia Sundheimer, Britta Statz, Kristian W. Pajtler, Stefan M. Pfister, Walter E. Haefeli, Juergen Burhenne, Remi Longuespee
Summary: Desorption/ionization-mass spectrometric methods are advantageous for the analysis of solid biological matrices. The development of drug quantification assays using DESI has been challenging, but new prototype source setups show promise for targeted quantitative analyses.
Article
Chemistry, Multidisciplinary
Xiaowei Song, Qingce Zang, Chao Li, Tianhao Zhou, Richard N. N. Zare
Summary: We developed an immunoassay-based desorption electrospray ionization mass spectrometry imaging (immuno-DESI-MSI) technique for visualizing functional macromolecules. Boronic acid mass tags (BMTs) were synthesized to label antibodies as MSI probes, which can be released from the antibody by cleaving the boronic ester bond under acidic conditions. The BMTs can work in both optical and MS imaging modes and can be readily identified due to the introduction of the boron element.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemical Research Methods
Alena N. Joignant, Hongxia Bai, Jacob P. Guymon, Kenneth P. Garrard, Mark Pankow, David C. Muddiman
Summary: This article presents the development and characterization of the NextGen infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) instrument, including the development of a new analysis geometry. The study demonstrates comparable results between vertically oriented transmission mode (tm)-IR-MALDESI and reflection mode (rm)-IR-MALDESI on mouse tissue. It also examines the use of glycerol as an alternative matrix, which shows little improvement in ion abundances for tm-IR-MALDESI.
RAPID COMMUNICATIONS IN MASS SPECTROMETRY
(2022)
Article
Chemistry, Analytical
Joseph H. H. Holbrook, Emily R. R. Sekera, Arbil Lopez, Brian D. D. Fries, Fernando Tobias, Kubra Akkaya, Maria M. M. Mihaylova, Amanda B. B. Hummon
Summary: Lipids are essential macromolecules that play crucial roles in numerous biological events. Matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) is a powerful tool for understanding the spatial localization of lipids in biological systems. In this study, the use of ammonium fluoride (NH4F) as a comatrix additive was found to enhance lipid detection in biological samples, with a signal increase of up to 200%. The addition of NH4F was observed to enhance the lipid signal of [M-H](-) ions, attributed to a proton transfer reaction in various lipid classes. Overall, the study shows that the NH4F comatrix additive significantly improves sensitivity for lipid detection in a MALDI system and can be applied to various applications.
ANALYTICAL CHEMISTRY
(2023)
Article
Biochemical Research Methods
Meiling Huo, Zhonghua Wang, Wenqing Fu, Lu Tian, Wanfang Li, Zhi Zhou, Yanhua Chen, Jinfeng Wei, Zeper Abliz
Summary: Spatially resolved metabolomic method utilizing AFADESI-MSI was used to study region-specific metabolic disturbances in the brains of diabetic rats. 19 discriminating metabolites related to various metabolic pathways were identified and located in the brains of the diabetic rats for the first time, providing valuable insights into the molecular pathological signature of diabetic encephalopathy.
JOURNAL OF PROTEOME RESEARCH
(2021)
Article
Biochemical Research Methods
Gwangbin Lee, Sangwon Cha
Summary: Nano-DESI MS has been explored in the forensic chemical analysis of ink directly from handwriting on paper, showing the potential for changing mass spectral profiles over time to reflect the differential distribution of analytes in a vertical direction. The study confirmed the capability of the depth-dependent analysis of nano-DESI MS.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2021)
Article
Chemistry, Analytical
Xufang Hu, Zongping Wang, Haolin Chen, An Zhao, Nianrong Sun, Chunhui Deng
Summary: An advanced metabolic analysis tool based on highly porous metal oxides derived from metal-organic frameworks (MOFs) is developed in this study. The tool successfully differentiates and stages renal cell carcinoma (RCC), as well as identifies the size of tumors. This achievement shows promising prospects for designer matrix-based analytical tools in disease diagnosis.
ANALYTICAL CHEMISTRY
(2022)
Review
Spectroscopy
Michael Caleb Bagley, Kenneth P. Garrard, David C. Muddiman
Summary: In the past 15 years, ambient ionization techniques, particularly matrix-assisted laser desorption electrospray ionization, have made significant advancements in mass spectrometry imaging. These techniques have been developed and improved with different laser systems and mass spectrometers, leading to transformative developments in the imaging platform.
MASS SPECTROMETRY REVIEWS
(2023)
Article
Biochemical Research Methods
Hongxia Bai, Jeffrey G. Manni Sr, David C. Muddiman
Summary: Infrared laser used in mass spectrometry imaging often leads to nonuniform ablation due to its Gaussian profile, which decreases image quality. To address this issue, researchers integrated a diffractive optical element into the optical path to generate homogeneous intensity distribution, ensuring complete sample removal with laser pulses.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2023)
Article
Biochemical Research Methods
Seth M. Eisenberg, Kevan T. Knizner, David C. Muddiman
Summary: Mass spectrometry imaging (MSI) is an analytical technique that detects and visualizes thousands of m/z values in two- and three-dimensional space. Discriminating sample-related analytes from ambient ions conventionally requires manual investigation of each ion heatmap, which is time-consuming and subjective. In this study, an ion classification tool (ICT) was developed using object-based image analysis in MATLAB, which accurately classified ions as on-tissue or background based on binary conversion and the number of detected objects.
ANALYTICAL AND BIOANALYTICAL CHEMISTRY
(2023)
Correction
Biochemical Research Methods
David C. Muddiman
JOURNAL OF MASS SPECTROMETRY
(2023)
Correction
Biochemical Research Methods
David C. Muddiman
JOURNAL OF MASS SPECTROMETRY
(2023)
Article
Biochemical Research Methods
Alena N. N. Joignant, Ying Xi, David C. C. Muddiman
Summary: Biospecimens with flat surfaces are needed for laser-based mass spectrometry imaging. However, imperfections in the sampling stages and non-flat samples require a deeper understanding of the laser beam's depth of focus. This tutorial explores the parameters and equations that describe the depth of focus of a Gaussian laser beam and presents methods to address surface roughness exceeding the laser's depth of focus.
JOURNAL OF MASS SPECTROMETRY
(2023)
Article
Biochemical Research Methods
Russell R. Kibbe, David C. Muddiman
Summary: Profile data collection in mass spectrometry imaging (MSI) studies often results in large files and long processing times. This study compares profile and centroid data collection methods in high-resolution accurate mass MSI. The results show that centroid data collection improves mass measurement accuracy and lipid annotation sensitivity compared to profile data collection.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2023)
Article
Biochemical Research Methods
Mary F. Wang, Alexandria L. Sohn, Juhi Samal, Kevin Erning, Tatiana Segura, David C. Muddiman
Summary: Two preparatory methods for mass spectrometry imaging (MSI), fresh-frozen and sucrose-embedded, paraformaldehyde (PFA) fixed, were evaluated in terms of ion abundance, putative lipid identifications, and preservation of analyte spatial distributions. Sucrose-embedded, PFA-fixed tissues without an ice matrix showed significantly higher numbers of putatively identified lipid species in positive and negative ion modes compared to the traditional gold-standard fresh-frozen tissue preparation with an exogenous ice matrix. Sucrose-embedded tissues also demonstrated improved spatial distribution of ions. These findings support sucrose-embedding without ice matrix as an alternative preparatory technique for IR-MALDESI-MSI.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2023)
Article
Biochemical Research Methods
Tana V. Palomino, David C. Muddiman
Summary: This study presents a new rule that can predict the number of sialic acids on a glycan. By utilizing infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) in negative-ion mode mass spectrometry, the number of sialic acids on the glycan can be predicted based on the experimental isotopic distribution of a detected glycan. This new rule improves the capability of IR-MALDESI to analyze sialylated N-linked glycans within biological tissues, providing confident glycan annotations and compositions.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2023)
Article
Biochemical Research Methods
Ying Xi, Kevan T. T. Knizner, Kenneth P. P. Garrard, David C. C. Muddiman
Summary: This study presents a mass spectrometry imaging (MSI) method that automatically corrects discernible height differences across surfaces during imaging experiments. A chromatic confocal sensor is incorporated into the infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) system to measure the sample surface height at each analytical scan location, allowing for adjustment of the z-axis position of the sample during MSI data acquisition. The method is evaluated using a tilted mouse liver section and an unsectioned Prilosec tablet, showing consistent ablated spot sizes and shapes and revealing the measured ion spatial distribution.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2023)
Article
Biochemical Research Methods
Mary F. Wang, Morgan M. Ritter, Seth W. Kullman, David C. Muddiman
Summary: In this study, the feasibility of sucrose-embedding with paraformaldehyde fixation as an alternative matrix for IR-MALDESI analysis in whole-body zebrafish samples was investigated. The results demonstrated that sucrose-embedding method obtained more lipid annotation information compared to the conventional fresh-frozen sample preparation. This is important for studying and analyzing disease states in whole-body zebrafish.
ANALYTICAL AND BIOANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Analytical
Juhi Samal, Tana V. Palomino, Judy Chen, David C. Muddiman, Tatiana Segura
Summary: N-linked glycosylation is a complex protein modification that plays a role in cellular signaling and metabolism. Aberrant protein glycosylation is a characteristic feature of many diseases. Spatial profiling of N-glycans through imaging on tissue sections can be used for disease diagnosis. Infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) is a sensitive technique that can be used for mass spectrometry imaging.
ANALYTICAL CHEMISTRY
(2023)
Article
Biochemical Research Methods
Seth M. Eisenberg, Kevan T. Knizner, David C. Muddiman
Summary: Mass spectrometry imaging (MSI) is a technique for measuring and visualizing the spatial distribution of ions in a sample. METASPACE is commonly used for annotation in high-resolution, accurate mass imaging data, but its reported confidence scores often do not accurately reflect the confidence level. The metabolite annotation confidence score (MACS) is an alternative system based on fundamental metrics to generate values that reflect the confidence of an annotation in HRAM-MSI data.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2023)
Article
Biochemical Research Methods
Alena N. Joignant, Morgan M. Ritter, Kevan T. Knizner, Kenneth P. Garrard, Seth W. Kullman, David C. Muddiman
Summary: This study proposes a novel method of mass spectrometry imaging (MSI) to reduce the acquisition time of MSI data using nested regions of interest (nROIs). By utilizing nROIs, a smaller region of interest can be imaged at higher spatial resolution nested within a larger region of interest at lower spatial resolution, conserving maximal spatial and chemical information while decreasing acquisition time. The nROI method was characterized on mouse liver and applied to top-hat MSI of zebrafish, resulting in significant improvements in acquisition time and spatial detail. The nROI method can be applied to any method where acquiring larger high-resolution ROIs poses a practical challenge.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2023)
Article
Biochemical Research Methods
Alena N. Joignant, Kevan T. Knizner, Ying Xi, David C. Muddiman
Summary: This study establishes an optimal sample thickness for IR-MALDESI-MSI at around 7 micrometers, as analyzing thicker tissue sections (>10 μm) results in lower ion abundance, decreased signal over long analysis times, and more frequent instrument cleaning.
RAPID COMMUNICATIONS IN MASS SPECTROMETRY
(2023)